X-ray photoelectron spectroscopy analysis for the chemical impact of solvent addition rate on electromagnetic shielding effectiveness of HCl-doped polyaniline nanopowders

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

Tantawy, Hesham Ramzy; Aston, D. Eric, E-mail: aston@uidaho.edu; Kengne, Blaise-Alexis F.

2015-11-07

An in-depth analysis of the chemical functionality in HCl-doped polyaniline (PANI) nanopowders is discussed through interpretations of x-ray photoelectron spectra. The distinctions between three PANI sample types, produced under varied synthesis conditions, are compared on the basis correlations between newly collected electron spectra for chemical analysis (or also x-ray photoelectron spectroscopy) and electromagnetic (EM) shielding effectiveness (SE) within two frequency bands (100–1500 MHz and ∼2–14 GHz). The findings are discussed with reference to previous data analysis of electrical conductivities and Raman and UV-vis spectra analyzed from replicates of the same PANI nanopowders, where only the 8–12 GHz range for SE was tested.more » They further corroborate previous results for limited-solvent conditions that enhance EM shielding. The three nanopowder types show distinctive differences in polaron, bipolaron, and polar lattice contributions. The collective findings describe the chemical connections between controlling and, most importantly, limiting the available solvent for polymerization with simultaneously doping and how it is that the newly developed solvent-limited approach for HCl-PANI nanopowders provides better shielding than traditionally solvent-rich methods by having more extended and perhaps even faster polaron delocalization than other PANI-based products. The maximum oxidation (50%) and doping (49%) levels obtained in the solvent-free nanopowders also produced the highest SE values of 37.3 ± 3.7 dB (MHz band) and 68.6 ± 4.6 dB (GHz band)« less

Synthetic studies of the zoanthamine alkaloids: the total syntheses of norzoanthamine and zoanthamine.

PubMed

Yoshimura, Fumihiko; Sasaki, Minoru; Hattori, Izumi; Komatsu, Kei; Sakai, Mio; Tanino, Keiji; Miyashita, Masaaki

2009-07-06

The zoanthamine alkaloids, a type of heptacyclic marine alkaloid isolated from colonial zoanthids of the genus Zoanthus sp., have distinctive biological and pharmacological properties in addition to their unique chemical structures with stereochemical complexity. Namely, norzoanthamine (1) can suppress the loss of bone weight and strength in ovariectomized mice and has been expected as a promising candidate for a new type of antiosteoporotic drug, while zoanthamine (2) has exhibited potent inhibitory activity toward phorbol myristate-induced inflammation in addition to powerful analgesic effects. Recently, norzoanthamine derivatives were demonstrated to inhibit strongly the growth of P-388 murine leukemia cell lines, in addition to their potent antiplatelet activities on human platelet aggregation. Their distinctive biological properties, combined with novel chemical structures, make this family of alkaloids extremely attractive targets for chemical synthesis. However, the chemical synthesis of the zoanthamine alkaloids has been impeded owing to their densely functionalized complex stereostructures. In this paper, we report the first and highly efficient total syntheses of norzoanthamine (1) and zoanthamine (2) in full detail, which involve stereoselective synthesis of the requisite triene (18) for an intramolecular Diels-Alder reaction via the sequential three-component coupling reactions, the key intramolecular Diels-Alder reaction, and subsequent crucial bis-aminoacetalization as the key steps. Ultimately, we achieved the total synthesis of norzoanthamine (1) in 41 steps with an overall yield of 3.5 % (an average of 92 % yield each step) and that of zoanthamine (2) in 43 steps with an overall yield of 2.2 % (an average of 91 % yield each step) starting from (R)-5-methylcyclohexenone (3), respectively.

Drug Insight: mechanisms of action and therapeutic applications for agonists of peroxisome proliferator-activated receptors.

PubMed

Gervois, Philippe; Fruchart, Jean-Charles; Staels, Bart

2007-02-01

Intensive preclinical investigations have delineated a role for peroxisome proliferator-activated receptors (PPARs) in energy metabolism and inflammation. PPARs are activated by natural lipophilic ligands such as fatty acids and their derivatives. Normalization of lipid and glucose metabolism is achieved via pharmacological modulation of PPAR activity. PPARs may also alter atherosclerosis progression through direct effects on the vascular wall. PPARs regulate genes involved in the recruitment of leukocytes to endothelial cells, in vascular inflammation, in macrophage lipid homeostasis, and in thrombosis. PPARs therefore modulate metabolic and inflammatory perturbations that predispose to cardiovascular diseases and type 2 diabetes. The hypolipidemic fibrates and the antidiabetic thiazolidinediones are drugs that act via PPARalpha and PPARgamma, respectively, and are used in clinical practice. PPARbeta/delta ligands are currently in clinical evaluation. The pleiotropic actions of PPARs and the fact that chemically diverse PPAR agonists may induce distinct pharmacological responses have led to the emergence of new concepts for drug design. A more precise understanding of the molecular pathways implicated in the response to chemically distinct PPAR agonists should provide new opportunities for targeted therapeutic applications in the management of the metabolic syndrome, type 2 diabetes, and cardiovascular diseases.

Elucidating determinants of aerosol composition through particle-type-based receptor modeling

NASA Astrophysics Data System (ADS)

McGuire, M. L.; Jeong, C.-H.; Slowik, J. G.; Chang, R. Y.-W.; Corbin, J. C.; Lu, G.; Mihele, C.; Rehbein, P. J. G.; Sills, D. M. L.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

2011-03-01

An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed at a semi-rural site in Southern Ontario to characterize the size and chemical composition of individual particles. Particle-type-based receptor modelling of these data was used to investigate the determinants of aerosol chemical composition in this region. Individual particles were classified into particle-types and positive matrix factorization (PMF) was applied to their temporal trends to separate and cross-apportion particle-types to factors. The extent of chemical processing for each factor was assessed by evaluating the internal and external mixing state of the characteristic particle-types. The nine factors identified helped to elucidate the coupled interactions of these determinants. Nitrate-laden dust was found to be the dominant type of locally emitted particles measured by ATOFMS. Several factors associated with aerosol transported to the site from intermediate local-to-regional distances were identified: the Organic factor was associated with a combustion source to the north-west; the ECOC Day factor was characterized by nearby local-to-regional carbonaceous emissions transported from the south-west during the daytime; and the Fireworks factor consisted of pyrotechnic particles from the Detroit region following holiday fireworks displays. Regional aerosol from farther emissions sources were reflected through three factors: two biomass burning factors and a highly chemically processed long range transport factor. The biomass burning factors were separated by PMF due to differences in chemical processing which were caused in part by the passage of two thunderstorm gust fronts with different air mass histories. The remaining two factors, ECOC Night and Nitrate Background, represented the night-time partitioning of nitrate to pre-existing particles of different origins. The distinct meteorological conditions observed during this month-long study in the summer of 2007 provided a unique range of temporal variability, enabling the elucidation of the determinants of aerosol chemical composition, including source emissions, chemical processing, and transport, at the Canada-US border. This paper presents the first study to characterize the coupled influences of these determinants on temporal variability in aerosol chemical composition using single particle-type-based receptor modelling.

Elucidating determinants of aerosol composition through particle-type-based receptor modeling

NASA Astrophysics Data System (ADS)

McGuire, M. L.; Jeong, C.-H.; Slowik, J. G.; Chang, R. Y.-W.; Corbin, J. C.; Lu, G.; Mihele, C.; Rehbein, P. J. G.; Sills, D. M. L.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

2011-08-01

An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed at a semi-rural site in southern Ontario to characterize the size and chemical composition of individual particles. Particle-type-based receptor modelling of these data was used to investigate the determinants of aerosol chemical composition in this region. Individual particles were classified into particle-types and positive matrix factorization (PMF) was applied to their temporal trends to separate and cross-apportion particle-types to factors. The extent of chemical processing for each factor was assessed by evaluating the internal and external mixing state of the characteristic particle-types. The nine factors identified helped to elucidate the coupled interactions of these determinants. Nitrate-laden dust was found to be the dominant type of locally emitted particles measured by ATOFMS. Several factors associated with aerosol transported to the site from intermediate local-to-regional distances were identified: the Organic factor was associated with a combustion source to the north-west; the ECOC Day factor was characterized by nearby local-to-regional carbonaceous emissions transported from the south-west during the daytime; and the Fireworks factor consisted of pyrotechnic particles from the Detroit region following holiday fireworks displays. Regional aerosol from farther emissions sources was reflected through three factors: two Biomass Burning factors and a highly chemically processed Long Range Transport factor. The Biomass Burning factors were separated by PMF due to differences in chemical processing which were in part elucidated by the passage of two thunderstorm gust fronts with different air mass histories. The remaining two factors, ECOC Night and Nitrate Background, represented the night-time partitioning of nitrate to pre-existing particles of different origins. The distinct meteorological conditions observed during this month-long study in the summer of 2007 provided a unique range of temporal variability, enabling the elucidation of the determinants of aerosol chemical composition, including source emissions, chemical processing, and transport, at the Canada-US border. This paper presents the first study to elucidate the coupled influences of these determinants on temporal variability in aerosol chemical composition using single particle-type-based receptor modelling.

Impurity profiling of a chemical weapon precursor for possible forensic signatures by comprehensive two-dimensional gas chromatography/mass spectrometry and chemometrics.

PubMed

Hoggard, Jamin C; Wahl, Jon H; Synovec, Robert E; Mong, Gary M; Fraga, Carlos G

2010-01-15

In this report we present the feasibility of using analytical and chemometric methodologies to reveal and exploit the chemical impurity profiles from commercial dimethyl methylphosphonate (DMMP) samples to illustrate the type of forensic information that may be obtained from chemical-attack evidence. Using DMMP as a model compound of a toxicant that may be used in a chemical attack, we used comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOF-MS) to detect and identify trace organic impurities in six samples of commercially acquired DMMP. The GC x GC/TOF-MS data was analyzed to produce impurity profiles for all six DMMP samples using 29 analyte impurities. The use of PARAFAC for the mathematical resolution of overlapped GC x GC peaks ensured clean spectra for the identification of many of the detected analytes by spectral library matching. The use of statistical pairwise comparison revealed that there were trace impurities that were quantitatively similar and different among five of the six DMMP samples. Two of the DMMP samples were revealed to have identical impurity profiles by this approach. The use of nonnegative matrix factorization indicated that there were five distinct DMMP sample types as illustrated by the clustering of the multiple DMMP analyses into five distinct clusters in the scores plots. The two indistinguishable DMMP samples were confirmed by their chemical supplier to be from the same bulk source. Sample information from the other chemical suppliers supported the idea that the other four DMMP samples were likely from different bulk sources. These results demonstrate that the matching of synthesized products from the same source is possible using impurity profiling. In addition, the identified impurities common to all six DMMP samples provide strong evidence that basic route information can be obtained from impurity profiles. Finally, impurities that may be unique to the sole bulk manufacturer of DMMP were found in some of the DMMP samples.

Chemical composition of crystalline rock fragments from Luna 16 and Luna 20 fines

NASA Technical Reports Server (NTRS)

Cimbalnikova, A.; Palivcova, M.; Frana, J.; Mastalka, A.

1977-01-01

The chemical composition (bulk, rare earth, and trace elements) of the Luna 16 mare regolith and luna 20 highland regolith is discussed. The rock samples considered are 14 basaltic rock fragments (Luna 16) and 13 rock fragments of the ANT suite (Luna 20). On the basis of bulk composition, two types of basaltic rocks have been differentiated and defined in the Luna 16 regolith: mare basalts (fundamental crystalline rocks of Mare Fecunditatis) and high-alumina basalts. The bulk analyses of rock fragments of the ANT suite also enabled distinction of two rock types: anorthositic norites and troctolites and/or spinal-troctolites (the most abundant crystalline rocks of the highland region, the landing site of luna 20), and anorthosites. The chemical compositions of Luna 16 and Luna 20 regolith samples are compared. Differences in the chemistry of the Luna 16 mare regolith and that of mare basalts are discussed. The chemical affinity between the Luna 20 highland regolith and (a) anorthositic norites and (b) troctolites and/or spinel-troctolites has been ascertained.

Compositional changes of soil organic matter with cropping time were more profound in subsoils and distinct between Phaeozem and Chernozem in Northeast China

USDA-ARS?s Scientific Manuscript database

Soil organic matter (SOM) contributes to soil processes and is found both in shallow and deep soil layers. Its activity can be affected by its chemical composition, yet knowledge is incomplete of how land use alters the structural composition of SOM throughout the profiles of different soil types. T...

Size dependence of chondrule textural types

NASA Technical Reports Server (NTRS)

Goswami, J. N.

1984-01-01

Chrondrule textural types were studied for size sorted chondrules from the ordinary chondrites Dhajala, Eston and Chainpur and the CM chondrite Murchison. Aliquot samples from size sorted Dhajala chondrules were studied for their oxygen isotopic composition and chondrules from Weston were studied for their precompaction irradiation records by nuclear track technique. Correlations between chondrule textural types and oxygen isotope or track data were identified. A distinct dependence of chondrule textural type on chondrule size was evident in the data for both Dhajala and Weston chondrules. No significant deviation was noticed in the abundance pattern of nonporphyritic chondrules within individual size fractions in the 200 to 800 micron size interval. Overabundance is found of nonporphyritic chondrules in the 100 to 200 micron size fraction of Murchison chondrules, the trend is not as distinct for Chainpur chondrules. Two hundred microns is suggested as the cutoff size below which radiative cooling is extremely efficient during the chondrule forming process. It is suggested that this offers a possibility for use of physical and chemical characteristics of small chondrules to constrain the temperature history during the chondrule formation process.

Chemical zoning and homogenization of Pasamonte-type pyroxene and their bearing on thermal metamorphism of a howardite parent body

NASA Technical Reports Server (NTRS)

Miyamoto, M.; Duke, M. B.; Mckay, D. S.

1985-01-01

The Mg-Fe zoning of pyroxenes in Pasamonte and Juvinas eucrites is examined in order to gain a better understanding of the metamorphism in the surface layer of a eucrite/howardite parent body. Three distinct types of Ca-Mg-Fe zoning of Pasamonte pyroxenes are identified. The wide compositional range of the zoned pyroxenes suggests that Pasamonte is less metamorphosed than previously believed. It is also found that a Pasamonte-type pyroxene may yield a Juvinas-type pyroxene by thermal metamorphism. Calculations imply that the homogenization of Juvinas pyroxenes may have occurred during later reheating events rather than during initial cooling.

CEST: from basic principles to applications, challenges and opportunities

PubMed Central

Vinogradov, Elena; Sherry, A Dean; Lenkinski, Robert E

2012-01-01

Chemical Exchange Saturation Transfer (CEST) offers a new type of contrast for MRI that is molecule specific. In this approach, a slowly exchanging NMR active nucleus, typically a proton, possessing a chemical shift distinct from water is selectively saturated and the saturated spin is transferred to the bulk water via chemical exchange. Many molecules can act as CEST agents, both naturally occurring endogenous molecules and new types of exogenous agents. A large variety of molecules have been demonstrated as potential agents, including small diamagnetic molecules, complexes of paramagnetic ions, endogenous macromolecules, dendrimers and liposomes. In this review we described the basic principles of the CEST experiment, with emphasis on the similarity to earlier saturation transfer experiments described in the literature. Interest in quantitative CEST has also resulted in the development of new exchange-sensitive detection schemes. Some emerging clinical applications of CEST are described and the challenges and opportunities associated with translation of these methods to the clinical environment are discussed. PMID:23273841

Classification of an unidentified meteorite through TXRF technique and the chemical comparison with a known meteorite

NASA Astrophysics Data System (ADS)

Zaki, Wafaa

2013-12-01

Meteorites, space rocks, are characterized by several distinctive properties that distinguish them from terrestrial (Earth) rocks. Meteorites may have all or most of such properties. Sometimes, meteorite characterization requires detailed chemical analyses. Two types of meteorites were studied and chemically analyzed. One, had already been located and listed internationally (AL-Taamem Meteorite77). The other one is not listed yet as it fell in 1993 at the northern Kurdistan region of Iraq. The chemical analysis of grinded meteorite was conducted using TXRF technique. The analysis involved the utilization of one type of carrier and one type of disks (quartz). High purity silicon was used for fixing the meteorite powder onto the quartz glass disks for vacuum uses. Each sample test was carried out twice using the Bruker S2 Picofox TXRF instrument (for 600s). The spectra were investigated and several indicative characteristics were concluded. The samples were identified as meteorite, particularly for the appearance of the typical nickel peak near the iron peak in the spectra. This is in accordance with the method of classification of meteorites and by comparison between the listed and unlisted samples. All these analyses were conducted in the laboratories of Chemistry for Technologies in Brescia University, Italy).

[A new taxonomic system of the genus Murraya (Rutaceae) based on integration of morphology-based taxonomy and chemotaxonomy; and a philological survey on M. exotica in view of the relationship between Okinawa and China].

PubMed

Kinoshita, Takeshi

2014-01-01

This review concerns the taxonomic status of the genus Murraya in tribe Clausenae, subfamily Aurantioideae, family Rutaceae, and presents a new system integrating both morphology-based taxonomy and chemotaxonomy. This genus has been morphologically divided into the sects Murraya and Bergera. This dichotomy is justified by the noticeable difference of secondary metabolites with 3-prenylindoles in Murraya and carbazoles in Bergera. As for other metabolites of genus Murraya, coumarins are found in both sects, but differ clearly in types; 8-prenylcoumarins occur throughout the sect Murraya whereas geranylated furocoumarins are known from some species of the sect Bergera. As far as chemical properties are concerned, sect Bergera is much closer to genus Clausena than sect Murraya, suggesting the dichotomy of genus Murraya to be generic rather than sectional. 8-Prenylcoumarins characterizing sect Murraya play a decisive role in the distinction of M. exotica from M. paniculata that occurs most widely in subtropical and tropical Asia and is well known for morphologic as well as chemical diversity. Though the morphological difference between the two species is slight only in leaves and leaflets, the distinction is well substantiated by the following chemical feature: 7-OMe-8-prenylcoumarins occur in M. exotica whereas 5,7-di-OMe-8-prenylcoumarins in M. paniculata. Sect Murraya has a very close relation to genus Merrillia that is chemically characterized by similar types of 8-prenylcoumarins, and is also related to a certain extent to genus Micromelum. M. exotica is philologically surveyed in view of the delicate relationships between Okinawa, the only habitat of this plant in Japan, and China in order to clarify its historical background.

Isolation and separation of physicochemically distinct fimbrial types expressed on a single culture of Escherichia coli O7:K1:H6.

PubMed Central

Karch, H; Leying, H; Büscher, K H; Kroll, H P; Opferkuch, W

1985-01-01

The fimbrial (pili) profile of a single strain of Escherichia coli O7:K1:H6 (WF96) was evaluated. Fimbriae were isolated by sucrose density gradient ultracentrifugation, purified from flagellae by the use of 0.4% sodium dodecyl sulfate (SDS), and separated into distinct fimbrial types. Analysis of the purified WF96 fimbriae by SDS-polyacrylamide gel electrophoresis revealed two polypeptide bands with molecular weights of 16,000 and 21,000. Treatment of the fimbrial mixture with saturated guanidine hydrochloride resulted in the appearance of a third band with a molecular weight of 19,500. The relative susceptibilities of the WF96 fimbrial types to disrupting chemicals (octyl-glucoside, urea, SDS, and guanidine hydrochloride) were assessed by exposure of the fimbrial mixture to each agent, separation of the depolymerized fimbriae from intact fimbriae by gel filtration on Sepharose CL-4B, and identification of the disaggregated fimbrial types by SDS-polyacrylamide gel electrophoresis of column fractions. The physicochemical heterogeneity of the three fimbrial types coexpressed on WF96 was exploited to develop a method for separation of individual fimbriae. Images PMID:2857155

A comparative study of Northern Ireland's estuaries based on the results of beam trawl fish surveys

NASA Astrophysics Data System (ADS)

Harrison, Trevor D.; Armour, Neil D.; McNeill, Michael T.; Moorehead, Peter W.

2017-11-01

The fish communities of Northern Ireland's estuaries were described and compared using data collected with a modified beam trawl over a six year period from 2009 to 2014. Multivariate analyses identified four estuary groups based on variations in their physico-chemical attributes. These groups broadly corresponded with the distribution and variation of estuary geomorphic types identified around the Irish coast. The dominant fish species captured were also among the main species reported in other North East Atlantic estuaries. A significant link between the estuary types and their fish communities was found; each estuary group contained a somewhat distinctive fish community. The fish communities also showed a significant relationship with the physico-chemical characteristics of the estuaries. Differences in fish species composition are attributed to habitat and environmental preferences of key estuary-associated species.

Geochemical patterns of arsenic-enriched ground water in fractured, crystalline bedrock, Northport, Maine, USA

USGS Publications Warehouse

Lipfert, G.; Reeve, A.S.; Sidle, W.C.; Marvinney, R.

2006-01-01

High mean As concentrations of up to 26.6 ??mol/L (1990 ??g/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 ??mol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO 3 type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO3 type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO3 and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO4 concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions. Crown Copyright ?? 2006 Published by Elsevier Ltd. All rights reserved.

Multiscale Simulations of Reactive Transport

NASA Astrophysics Data System (ADS)

Tartakovsky, D. M.; Bakarji, J.

2014-12-01

Discrete, particle-based simulations offer distinct advantages when modeling solute transport and chemical reactions. For example, Brownian motion is often used to model diffusion in complex pore networks, and Gillespie-type algorithms allow one to handle multicomponent chemical reactions with uncertain reaction pathways. Yet such models can be computationally more intensive than their continuum-scale counterparts, e.g., advection-dispersion-reaction equations. Combining the discrete and continuum models has a potential to resolve the quantity of interest with a required degree of physicochemical granularity at acceptable computational cost. We present computational examples of such "hybrid models" and discuss the challenges associated with coupling these two levels of description.

Photocatalysis versus photosynthesis: A sensitivity analysis of devices for solar energy conversion and chemical transformations

DOE PAGES

Osterloh, Frank E.

2017-01-18

Here, the chemical literature often does not differentiate between photocatalytic (PC) and photosynthetic (PS) processes (including artificial photosynthesis) even though these reactions differ in their thermodynamics. Photocatalytic processes are thermodynamically downhill (ΔG < 0) and are merely accelerated by the catalyst, whereas photosynthetic processes are thermodynamically unfavorable (ΔG > 0) and require photochemical energy input to occur. Here we apply this differentiation to analyze the basic functions of PC and PS devices and to formulate design criteria for improved performance. As will be shown, the corresponding devices exhibit distinctly different sensitivities to their functional parameters. For example, under conditions ofmore » optimal light absorption, carrier lifetimes, and electrochemical rates, the performance of PCs is limited only by their surface area, while type 1 PS devices are limited by their carrier mobility and mass transport, and type 2 PS devices are limited by electrochemical charge-transfer selectivity. Strategies for the optimization of type 1 and 2 photosynthetic devices and photocatalysts are also discussed.« less

Photocatalysis versus photosynthesis: A sensitivity analysis of devices for solar energy conversion and chemical transformations

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

Osterloh, Frank E.

Here, the chemical literature often does not differentiate between photocatalytic (PC) and photosynthetic (PS) processes (including artificial photosynthesis) even though these reactions differ in their thermodynamics. Photocatalytic processes are thermodynamically downhill (ΔG < 0) and are merely accelerated by the catalyst, whereas photosynthetic processes are thermodynamically unfavorable (ΔG > 0) and require photochemical energy input to occur. Here we apply this differentiation to analyze the basic functions of PC and PS devices and to formulate design criteria for improved performance. As will be shown, the corresponding devices exhibit distinctly different sensitivities to their functional parameters. For example, under conditions ofmore » optimal light absorption, carrier lifetimes, and electrochemical rates, the performance of PCs is limited only by their surface area, while type 1 PS devices are limited by their carrier mobility and mass transport, and type 2 PS devices are limited by electrochemical charge-transfer selectivity. Strategies for the optimization of type 1 and 2 photosynthetic devices and photocatalysts are also discussed.« less

Probing the type of anomalous diffusion with single-particle tracking.

PubMed

Ernst, Dominique; Köhler, Jürgen; Weiss, Matthias

2014-05-07

Many reactions in complex fluids, e.g. signaling cascades in the cytoplasm of living cells, are governed by a diffusion-driven encounter of reactants. Yet, diffusion in complex fluids often exhibits an anomalous characteristic ('subdiffusion'). Since different types of subdiffusion have distinct effects on timing and equilibria of chemical reactions, a thorough determination of the reactants' type of random walk is key to a quantitative understanding of reactions in complex fluids. Here we introduce a straightforward and simple approach for determining the type of subdiffusion from single-particle tracking data. Unlike previous approaches, our method also is sensitive to transient subdiffusion phenomena, e.g. obstructed diffusion below the percolation threshold. We validate our strategy with data from experiment and simulation.

Distinction of Fly Artifacts from Human Blood using Immunodetection.

PubMed

Rivers, David B; Acca, Gillian; Fink, Marc; Brogan, Rebecca; Chen, Dorothy; Schoeffield, Andrew

2018-02-21

Insect stains produced by necrophagous flies are indistinguishable morphologically from human bloodstains. At present, no diagnostic tests exist to overcome this deficiency. As the first step toward developing a chemical test to recognize fly artifacts, polyclonal antisera were generated in rats against three distinct antigenic sequences of fly cathepsin D-like proteinase, an enzyme that is structurally distinct in cyclorrhaphous Diptera from other animals. The resulting rat antisera bound to artifacts produced by Protophormia terraenovae and synthetic peptides used to generate the polyclonal antisera, but not with any type of mammalian blood tested in immunoassays. Among the three antisera, anti-md3 serum displayed the highest reactivity for fly stains, demonstrated cross-reactivity for all synthetic peptides representing antigenic sequences of the mature fly enzyme, and bound artifacts originating from the fly digestive tract. Further work is needed to determine whether the antisera are suitable for non-laboratory conditions. © 2018 American Academy of Forensic Sciences.

Regional studies of dolomites and their included fluids: recognizing multiple chemically distinct fluids during the complex diagenetic history of Lower Carboniferous (Mississippian) rocks of the Irish Zn-Pb ore field

NASA Astrophysics Data System (ADS)

Johnson, Aaron W.; Shelton, Kevin L.; Gregg, Jay M.; Somerville, Ian D.; Wright, Wayne R.; Nagy, Zsolt R.

2009-05-01

This study provides a regional framework within which studies of ore-related dolomite and dolomite cements may be placed. Fluid inclusion data indicate the presence of three distinct fluids following early dolomitization: 1) a ubiquitous low-temperature, higher salinity fluid found in saddle dolomite; 2) a low-temperature, lower salinity fluid limited to sub-Waulsortian and Waulsortian carbonates; and 3) a higher temperature, lower salinity fluid found in Waulsortian and supra-Waulsortian rocks. Similar fluids have been reported in ore-associated minerals and postmineralization dolomite (Type 1) and in ore-stage carbonates and sphalerite (Types 2 and 3). The halogen geochemistry of included fluids indicates genesis from evaporated seawater. Type 1 fluids are enriched in chloride relative to bromide, reflecting a component of salinity derived via dissolution of halite or from dehydration of seawater. These data suggest that dolomitization and mineralization of Mississippian rocks in the Midlands requires both regionally extensive and localized fluid flow.

EAG Eminent Speaker: Two types of Archean continental crust: plume and plate tectonics on early Earth

NASA Astrophysics Data System (ADS)

Van Kranendonk, M. J.

2012-04-01

Over 4.5 billion years, Earth has evolved from a molten ball to a cooler planet with large continental plates, but how and when continents grew and plate tectonics started remain poorly understood. In this paper, I review the evidence that 3.5-3.2 Ga continental nuclei of the Pilbara (Australia) and Kaapvaal (southern Africa) cratons formed as thick volcanic plateaux over hot, upwelling mantle and survived due to contemporaneous development of highly depleted, buoyant, unsubductable mantle roots. This type of crust is distinct from, but complimentary to, high-grade gneiss terranes, as exemplified by the North Atlantic Craton of West Greenland, which formed through subduction-accretion tectonics on what is envisaged as a vigorously convecting early Earth with small plates. Thus, it is proposed that two types of crust formed on early Earth, in much the same way as in modern Earth, but with distinct differences resulting from a hotter Archean mantle. Volcanic plateaux provided a variety of stable habitats for early life, including chemical nutrient rich, shallow-water hydrothermal systems and shallow marine carbonate platforms.

Differentiating Left- and Right-Handed Carbon Nanotubes by DNA.

PubMed

Ao, Geyou; Streit, Jason K; Fagan, Jeffrey A; Zheng, Ming

2016-12-28

New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness and a multitude of helicities that give rise to three distinct types of electronic structures: metals, quasi-metals, and semiconductors. Here we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure that binds to a nanotube of defined handedness and helicity and resembles a well-folded biomacromolecule with innate stereoselectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes.

Differentiating Left- and Right-handed Carbon Nanotubes by DNA

NASA Astrophysics Data System (ADS)

Zheng, Ming

New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness, and a multitude of helicity that gives rise to three distinct types of electronic structures - metals, quasi-metals, and semiconductors. Here, we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure bound to a nanotube of defined handedness and helicity, resembling a well-folded biomacromolecule with innate stereo-selectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, respectively, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA, and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes. .

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath

NASA Astrophysics Data System (ADS)

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-05-01

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely “suspense” or “comedy” caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising.

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath.

PubMed

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-05-10

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely "suspense" or "comedy" caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising.

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath

PubMed Central

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-01-01

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely “suspense” or “comedy” caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising. PMID:27160439

Formulating orange oil-in-water beverage emulsions for effective delivery of bioactives: Improvements in chemical stability, antioxidant activity and gastrointestinal fate of lycopene using carrier oils.

PubMed

Meroni, Erika; Raikos, Vassilios

2018-04-01

The influence of carrier oil type on the chemical stability, antioxidant properties and bioaccessibility of lycopene in orange oil-in-water beverage emulsions was investigated. The emulsions were formulated with orange oil (A), which was partially (50%) replaced with tributyrin (B) or corn oil (C) because of their distinctively different fatty acid composition. The addition of corn oil enhanced the physical stability of the beverage during chilled storage by inhibiting Ostwald ripening. The formation of oxidation products was insignificant after storage for 28 days at 4 °C, regardless the type of added oil. Lycopene was more susceptible to chemical degradation in the presence of unsaturated, long chain triglycerides and the retention followed the order: A (87.94%), B (64.41%) and C (57.39%). Interestingly, bioaccessibility of lycopene was significantly lower for emulsions formulated with 50% corn oil as opposed to 100% orange oil as indicated by the simulated in vitro gastric digestion model. Copyright © 2018 Elsevier Ltd. All rights reserved.

Whewell on classification and consilience.

PubMed

Quinn, Aleta

2017-08-01

In this paper I sketch William Whewell's attempts to impose order on classificatory mineralogy, which was in Whewell's day (1794-1866) a confused science of uncertain prospects. Whewell argued that progress was impeded by the crude reductionist assumption that all macroproperties of crystals could be straightforwardly explained by reference to the crystals' chemical constituents. By comparison with biological classification, Whewell proposed methodological reforms that he claimed would lead to a natural classification of minerals, which in turn would support advances in causal understanding of the properties of minerals. Whewell's comparison to successful biological classification is particularly striking given that classificatory biologists did not share an understanding of the causal structure underlying the natural classification of life (the common descent with modification of all organisms). Whewell's key proposed methodological reform is consideration of multiple, distinct principles of classification. The most powerful evidence in support of a natural classificatory claim is the consilience of claims arrived at through distinct lines of reasoning, rooted in distinct conceptual approaches to the target objects. Mineralogists must consider not only elemental composition and chemical affinities, but also symmetry and polarity. Geometrical properties are central to what makes an individual mineral the type of mineral that it is. In Whewell's view, function and organization jointly define life, and so are the keys to understanding what makes an organism the type of organism that it is. I explain the relationship between Whewell's teleological account of life and his natural theology. I conclude with brief comments about the importance of Whewell's classificatory theory for the further development of his philosophy of science and in particular his account of consilience. Copyright © 2017 Elsevier Ltd. All rights reserved.

Growth behavior of carbon nanotubes on multilayered metal catalyst film in chemical vapor deposition

NASA Astrophysics Data System (ADS)

Cui, H.; Eres, G.; Howe, J. Y.; Puretkzy, A.; Varela, M.; Geohegan, D. B.; Lowndes, D. H.

2003-06-01

The temperature and time dependences of carbon nanotube (CNT) growth by chemical vapor deposition are studied using a multilayered Al/Fe/Mo catalyst on silicon substrates. Within the 600-1100 °C temperature range of these studies, narrower temperature ranges were determined for the growth of distinct types of aligned multi-walled CNTs and single-walled CNTs by using high-resolution transmission electron microscopy and Raman spectroscopy. At 900 °C, in contrast to earlier work, double-walled CNTs are found more abundant than single-walled CNTs. Defects also are found to accumulate faster than the ordered graphitic structure if the growth of CNTs is extended to long durations.

“Playing around” with Field-Effect Sensors on the Basis of EIS Structures, LAPS and ISFETs

PubMed Central

Schöning, Michael J.

2005-01-01

Microfabricated semiconductor devices are becoming increasingly relevant, also for the detection of biological and chemical quantities. Especially, the “marriage” of biomolecules and silicon technology often yields successful new sensor concepts. The fabrication techniques of such silicon-based chemical sensors and biosensors, respectively, will have a distinct impact in different fields of application such as medicine, food technology, environment, chemistry and biotechnology as well as information processing. Moreover, scientists and engineers are interested in the analytical benefits of miniaturised and microfabricated sensor devices. This paper gives a survey on different types of semiconductor-based field-effect structures that have been recently developed in our laboratory.

Hydrothermal alteration of felsic volcanic rocks at the Helen Siderite Deposit, Wawa, Ontario

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

Morton, R.L.; Nebel, M.L.

1984-09-01

Felsic lavas and pyroclastic rocks, underlying the Archean Helen iron-formation, have been variably altered by hydrothermal solutions which, when discharged onto the sea floor, formed the Helen siderite deposit. Within the footwall volcanic sequence five chemically and mineralogically distinct alteration types have been defined: least altered, sericite, chlorite chloritoid, and ankerite. Based on mineralogy and chemistry of the altered rocks and on the geometry of the alteration zones, an alteration model is proposed.

PRISM 3: expanded prediction of natural product chemical structures from microbial genomes

PubMed Central

Skinnider, Michael A.; Merwin, Nishanth J.; Johnston, Chad W.

2017-01-01

Abstract Microbial natural products represent a rich resource of pharmaceutically and industrially important compounds. Genome sequencing has revealed that the majority of natural products remain undiscovered, and computational methods to connect biosynthetic gene clusters to their corresponding natural products therefore have the potential to revitalize natural product discovery. Previously, we described PRediction Informatics for Secondary Metabolomes (PRISM), a combinatorial approach to chemical structure prediction for genetically encoded nonribosomal peptides and type I and II polyketides. Here, we present a ground-up rewrite of the PRISM structure prediction algorithm to derive prediction of natural products arising from non-modular biosynthetic paradigms. Within this new version, PRISM 3, natural product scaffolds are modeled as chemical graphs, permitting structure prediction for aminocoumarins, antimetabolites, bisindoles and phosphonate natural products, and building upon the addition of ribosomally synthesized and post-translationally modified peptides. Further, with the addition of cluster detection for 11 new cluster types, PRISM 3 expands to detect 22 distinct natural product cluster types. Other major modifications to PRISM include improved sequence input and ORF detection, user-friendliness and output. Distribution of PRISM 3 over a 300-core server grid improves the speed and capacity of the web application. PRISM 3 is available at http://magarveylab.ca/prism/. PMID:28460067

Litsea cubeba leaf essential oil from Vietnam: chemical diversity and its impacts on antibacterial activity.

PubMed

Nguyen, H V; Meile, J-C; Lebrun, M; Caruso, D; Chu-Ky, S; Sarter, S

2018-03-01

The threat of bacterial resistance to antibiotics has created an urgent need to develop new antimicrobials. The aim of this study was to characterize the chemical diversity of Litsea cubeba leaf essential oil (EO) and its impacts on the antibacterial activity against pathogenic bacteria. Essential oils collected from seven provinces in North Vietnam (n = 25) were characterized by their high content in either 1,8-cineole or linalool. Linalool-type EOs were more effective against the eight bacterial strains tested than 1,8-cineole-type. Oil samples, LC19 (50% 1,8-cineole) and BV27 (94% linalool), were selected to investigate their antibacterial mechanisms against Escherichia coli. A strong bactericidal effect was observed after 4 and 2 h of exposure respectively. Microscopic analysis of treated E. coli cultures clearly showed that EOs caused changes in cell morphology, loss of integrity and permeability of the cell membrane, as well as DNA loss. However, the effects of both EOs were distinct. LC19 mostly affected cell membrane, led to a significant cell filamentation rate and altered cell width, whereas BV27 damaged cell membrane integrity leading to cell permeabilization and altered nucleoid morphology with the appearance of spot and visibly altered compaction. This study aimed to characterize the chemical diversity of Litsea cubeba leaf essential oil (EO) and its impacts on its antibacterial activity. Two major chemotypes (1,8-cineole or linalool rich) were identified in North Vietnam and both were bactericidal against several pathogenic bacteria. A distinct inhibitory effect of EO samples on Escherichia coli was observed. 1,8-cineole-rich sample (LC19) affected cell membrane, led to cell filamentation and perturbation of cell width, while the linalool-rich one (BV27) induced damages in the cell membrane and changes in the nucleoid morphology. The study demonstrates the importance of considering chemotype variations in terms of chemical composition as well as the mode of action. © 2017 The Society for Applied Microbiology.

Antennal olfactory sensilla responses to insect chemical repellents in the common bed bug, Cimex lectularius.

PubMed

Liu, Feng; Haynes, Kenneth F; Appel, Arthur G; Liu, Nannan

2014-06-01

Populations of the common bed bug Cimex lectularius (Hemiptera; Cimicidae), a temporary ectoparasite on both humans and animals, have surged in many developed countries. Similar to other haematophagous arthropods, C. lectularius relies on its olfactory system to detect semiochemicals in the environment, including both attractants and repellents. To elucidate the olfactory responses of the common bed bug to commonly used insect chemical repellents, particularly haematophagous repellents, we investigated the neuronal responses of individual olfactory sensilla in C. lectularius' antennae to 52 insect chemical repellents, both synthetic and botanic. Different types of sensilla displayed highly distinctive response profiles. While C sensilla did not respond to any of the insect chemical repellents, Dγ sensilla proved to be the most sensitive in response to terpene-derived insect chemical repellents. Different chemical repellents elicited neuronal responses with differing temporal characteristics, and the responses of the olfactory sensilla to the insect chemical repellents were dose-dependent, with an olfactory response to the terpene-derived chemical repellent, but not to the non-terpene-derived chemical repellents. Overall, this study furnishes a comprehensive map of the olfactory response of bed bugs to commonly used insect chemical repellents, providing useful information for those developing new agents (attractants or repellents) for bed bug control.

Thermal and chemical evolution in the early solar system as recorded by FUN CAIs: Part I - Petrology, mineral chemistry, and isotopic composition of Allende FUN CAI CMS-1

NASA Astrophysics Data System (ADS)

Williams, C. D.; Ushikubo, T.; Bullock, E. S.; Janney, P. E.; Hines, R. R.; Kita, N. T.; Hervig, R. L.; MacPherson, G. J.; Mendybaev, R. A.; Richter, F. M.; Wadhwa, M.

2017-03-01

Detailed petrologic, geochemical and isotopic analyses of a new FUN CAI from the Allende CV3 meteorite (designated CMS-1) indicate that it formed by extensive melting and evaporation of primitive precursor material(s). The precursor material(s) condensed in a 16O-rich region (δ17O and δ18O ∼ -49‰) of the inner solar nebula dominated by gas of solar composition at total pressures of ∼10-3-10-6 bar. Subsequent melting of the precursor material(s) was accompanied by evaporative loss of magnesium, silicon and oxygen resulting in large mass-dependent isotope fractionations in these elements (δ25Mg = 30.71-39.26‰, δ29Si = 14.98-16.65‰, and δ18O = -41.57 to -15.50‰). This evaporative loss resulted in a bulk composition similar to that of compact Type A and Type B CAIs, but very distinct from the composition of the original precursor condensate(s). Kinetic fractionation factors and the measured mass-dependent fractionation of silicon and magnesium in CMS-1 suggest that ∼80% of the silicon and ∼85% of the magnesium were lost from its precursor material(s) through evaporative processes. These results suggest that the precursor material(s) of normal and FUN CAIs condensed in similar environments, but subsequently evolved under vastly different conditions such as total gas pressure. The chemical and isotopic differences between normal and FUN CAIs could be explained by sorting of early solar system materials into distinct physical and chemical regimes, in conjunction with discrete heating events, within the protoplanetary disk.

Influence of substrate rocks on Fe Mn crust composition

NASA Astrophysics Data System (ADS)

Hein, James R.; Morgan, Charles L.

1999-05-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Influence of substrate rocks on Fe-Mn crust composition

USGS Publications Warehouse

Hein, J.R.; Morgan, C.L.

1999-01-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Soil properties discriminating Araucaria forests with different disturbance levels.

PubMed

Bertini, Simone Cristina Braga; Azevedo, Lucas Carvalho Basilio; Stromberger, Mary E; Cardoso, Elke Jurandy Bran Nogueira

2015-04-01

Soil biological, chemical, and physical properties can be important for monitoring soil quality under one of the most spectacular vegetation formation on Atlantic Forest Biome, the Araucaria Forest. Our aim was to identify a set of soil variables capable of discriminating between disturbed, reforested, and native Araucaria forest soils such that these variables could be used to monitor forest recovery and maintenance. Soil samples were collected at dry and rainy season under the three forest types in two state parks at São Paulo State, Brazil. Soil biological, chemical, and physical properties were evaluated to verify their potential to differentiate the forest types, and discriminant analysis was performed to identify the variables that most contribute to the differentiation. Most of physical and chemical variables were sensitive to forest disturbance level, but few biological variables were significantly different when comparing native, reforested, and disturbed forests. Despite more than 20 years following reforestation, the reforested soils were chemically and biologically distinct from native and disturbed forest soils, mainly because of the greater acidity and Al3+ content of reforested soil. Disturbed soils, in contrast, were coarser in texture and contained greater concentrations of extractable P. Although biological properties are generally highly sensitive to disturbance and amelioration efforts, the most important soil variables to discriminate forest types in both seasons included Al3+, Mg2+, P, and sand, and only one microbial attribute: the NO2- oxidizers. Therefore, these five variables were the best candidates, of the variables we employed, for monitoring Araucaria forest disturbance and recovery.

Drug Hypersensitivity: How Drugs Stimulate T Cells via Pharmacological Interaction with Immune Receptors.

PubMed

Pichler, Werner J; Adam, Jacqueline; Watkins, Stephen; Wuillemin, Natascha; Yun, James; Yerly, Daniel

2015-01-01

Small chemicals like drugs tend to bind to proteins via noncovalent bonds, e.g. hydrogen bonds, salt bridges or electrostatic interactions. Some chemicals interact with other molecules than the actual target ligand, representing so-called 'off-target' activities of drugs. Such interactions are a main cause of adverse side effects to drugs and are normally classified as predictable type A reactions. Detailed analysis of drug-induced immune reactions revealed that off-target activities also affect immune receptors, such as highly polymorphic human leukocyte antigens (HLA) or T cell receptors (TCR). Such drug interactions with immune receptors may lead to T cell stimulation, resulting in clinical symptoms of delayed-type hypersensitivity. They are assigned the 'pharmacological interaction with immune receptors' (p-i) concept. Analysis of p-i has revealed that drugs bind preferentially or exclusively to distinct HLA molecules (p-i HLA) or to distinct TCR (p-i TCR). P-i reactions differ from 'conventional' off-target drug reactions as the outcome is not due to the effect on the drug-modified cells themselves, but is the consequence of reactive T cells. Hence, the complex and diverse clinical manifestations of delayed-type hypersensitivity are caused by the functional heterogeneity of T cells. In the abacavir model of p-i HLA, the drug binding to HLA may result in alteration of the presenting peptides. More importantly, the drug binding to HLA generates a drug-modified HLA, which stimulates T cells directly, like an allo-HLA. In the sulfamethoxazole model of p-i TCR, responsive T cells likely require costimulation for full T cell activation. These findings may explain the similarity of delayed-type hypersensitivity reactions to graft-versus-host disease, and how systemic viral infections increase the risk of delayed-type hypersensitivity reactions. © 2015 The Author(s) Published by S. Karger AG, Basel.

[Chemical peels and management of skin aging].

PubMed

Pelletier-Louis, M-L

2017-10-01

Chemical peels are an alternative and/or a complementary treatment to the surgical procedures for skin aging. The purpose of this article is to specify the procedures and the indications of the three principal types of chemical peels: alpha-hydroxy acids, trichloracetic acid, phenol-croton oil peel. The clinical examination will determine the depth of the lesions to treat and will take into consideration counter-indications and specific limits to each patient. Chemical peel is a four step procedure: pre-peel preparation, peeling itself, recovery phase and maintenance phase. The preparation is a very important phase which requires a thorough knowledge of cosmetics. This preparation can extend to any medical or surgical treatment for aging skin. Various techniques of peelings: superficial, medium, deep, combined and mosaïc peel will be detailed. These procedures require a rigorous training and a distinct learning curve. The follow up will be specified as well as the management of the possible complications. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Persistent hydrogen bonding in polymorphic crystal structures.

PubMed

Galek, Peter T A; Fábián, László; Allen, Frank H

2009-02-01

The significance of hydrogen bonding and its variability in polymorphic crystal structures is explored using new automated structural analysis methods. The concept of a chemically equivalent hydrogen bond is defined, which may be identified in pairs of structures, revealing those types of bonds that may persist, or not, in moving from one polymorphic form to another. Their frequency and nature are investigated in 882 polymorphic structures from the Cambridge Structural Database. A new method to compare conformations of equivalent molecules is introduced and applied to derive distinct subsets of conformational and packing polymorphs. The roles of chemical functionality and hydrogen-bond geometry in persistent interactions are systematically explored. Detailed structural comparisons reveal a large majority of persistent hydrogen bonds that are energetically crucial to structural stability.

Nanotubule and Tour Molecule Based Molecular Electronics: Suggestion for a Hybrid Approach

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Saini, Subhash (Technical Monitor)

1998-01-01

Recent experimental and theoretical attempts and results indicate two distinct broad pathways towards future molecular electronic devices and architectures. The first is the approach via Tour type ladder molecules and their junctions which can be fabricated with solution phase chemical approaches. Second are fullerenes or nanotubules and their junctions which may have better conductance, switching and amplifying characteristics but can not be made through well controlled and defined chemical means. A hybrid approach combining the two pathways to take advantage of the characteristics of both is suggested. Dimension and scale of such devices would be somewhere in between isolated molecule and nanotubule based devices but it maybe possible to use self-assembly towards larger functional and logicalunits.

Transport-induced shifts in condensate dew-point and composition in multicomponent systems with chemical reaction

NASA Technical Reports Server (NTRS)

Rosner, D. E.; Nagarajan, R.

1985-01-01

Partial heterogeneous condensation phenomena in multicomponent reacting systems are analyzed taking into consideration the chemical element transport phenomena. It is demonstrated that the dew-point surface temperature in chemically reactive systems is not a purely thermodynamic quantity, but is influenced by the multicomponent diffusion and Soret-mass diffusion phenomena. Several distinct dew-points are shown to exist in such systems and, as a result of transport constraints, the 'sharp' locus between two chemically distinct condensates is systematically moved to a difference mainstream composition.

Two Distinct RNase Activities of CRISPR-C2c2 Enable Guide RNA Processing and RNA Detection

PubMed Central

East-Seletsky, Alexandra; O’Connell, Mitchell R.; Knight, Spencer C.; Burstein, David; Cate, Jamie H. D.; Tjian, Robert; Doudna, Jennifer A.

2017-01-01

Bacterial adaptive immune systems employ CRISPRs (clustered regularly interspaced short palindromic repeats) and CRISPR-associated (Cas) proteins for RNA-guided nucleic acid cleavage1,2. Although generally targeted to DNA substrates3–5, the Type III and Type VI CRISPR systems direct interference complexes against single-stranded RNA (ssRNA) substrates6–9. In Type VI systems, the single-subunit C2c2 protein functions as an RNA-guided RNA endonuclease9,10. How this enzyme acquires mature CRISPR RNAs (crRNAs) essential for immune surveillance and its mechanism of crRNA-mediated RNA cleavage remain unclear. Here we show that C2c2 possesses a unique ribonuclease activity responsible for CRISPR RNA maturation that is distinct from its RNA-activated ssRNA-degradation activity. These dual ribonuclease functions are chemically and mechanistically different from each other and from the crRNA-processing behavior of the evolutionarily unrelated CRISPR enzyme Cpf111. We show that the two ribonuclease activities of C2c2 enable multiplexed processing and loading of guide RNAs that in turn allow for sensitive cellular transcript detection. PMID:27669025

Neural network recognition of chemical class information in mobility spectra obtained at high temperatures

NASA Technical Reports Server (NTRS)

Bell, S.; Nazarov, E.; Wang, Y. F.; Rodriguez, J. E.; Eiceman, G. A.

2000-01-01

A minimal neural network was applied to a large library of high-temperature mobility spectra drawn from 16 chemical classes including 154 substances with 2000 spectra at various concentrations. A genetic algorithm was used to create a representative subset of points from the mobility spectrum as input to a cascade-type back-propagation network. This network demonstrated that significant information specific to chemical class was located in the spectral region near the reactant ions. This network failed to generalize the solution to unfamiliar compounds necessitating the use of complete spectra in network processing. An extended back-propagation network classified unfamiliar chemicals by functional group with a mean for average values of 0.83 without sulfides and 0.79 with sulfides. Further experiments confirmed that chemical class information was resident in the spectral region near the reactant ions. Deconvolution of spectra demonstrated the presence of ions, merged with the reactant ion peaks that originated from introduced samples. The ability of the neural network to generalize the solution to unfamiliar compounds suggests that these ions are distinct and class specific.

Physico-chemical and metabolomic characterization of KAMUT® Khorasan and durum wheat fermented dough.

PubMed

Balestra, Federica; Laghi, Luca; Taneyo Saa, Danielle; Gianotti, Andrea; Rocculi, Pietro; Pinnavaia, GianGaetano

2015-11-15

Investigations were made in order to evaluate the influence of the flour type, chemical acidification and fermentation on characteristics of doughs obtained with durum wheat and KAMUT® Khorasan flour. Doughs were observed immediately after mixing, 90 and 360 min of leavening at 30 °C. Fundamental rheology, yeasts heat production by isothermal microcalorimetry and the interaction between water and biopolymers by means of time domain nuclear magnetic resonance were evaluated. In addition aromatic metabolite development was followed by means of the combined application of gas-chromatography and electronic nose. KAMUT® Khorasan flour was found to be more suitable than durum wheat for the fermentation processes tested, especially at acidic conditions, as shown by the increase of the volume and the metabolic heat production by yeast. In acidified dough the pattern of volatile metabolites allowed a clear distinction between the types of dough. Moreover the water/starch proton pool was characterized by higher T2 values in the KAMUT® Khorasan samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Phenolic chemistry of the seagrass Zostera noltei Hornem. Part 1: First evidence of three infraspecific flavonoid chemotypes in three distinctive geographical regions.

PubMed

Grignon-Dubois, Micheline; Rezzonico, Bernadette

2018-02-01

The flavonoid content of Zostera noltei leaves was investigated over a broad spatial scale using chromatographic and spectroscopic techniques (HPLC-DAD, LC/MS and NMR). Samples were collected at fifteen localities covering Mediterranean Sea and NE Atlantic coast, and representative of three types of coastal ecosystems: mesotidal bays, coastal lagoons, and open-sea. Three geographically distinct flavonoid chemotypes were identified on the basis of their respective major compound. One is characterized by apigenin 7-sulfate (Eastern part of Gulf of Cadiz), one by diosmetin 7-sulfate (French Atlantic coast and Mediterranean Sea), and the third contained similar quantities of the above two compounds (Mauritania and South Portugal). Our results show that metabolomic profiling using a combination of analytical techniques is a tool of choice to characterize chemical phenotype accurately. This work emphasizes for the first time the spatial variability in the flavonoid chemistry of Z. noltei throughout Atlantic and Mediterranean range, and constitutes the first report of chemical races in the Zosteraceae family. This infraspecific chemical differentiation should be considered when dealing with the role of Z. noltei in coastal ecosystems or in the selection of the best population donor for Z. noltei beds restoration. Combined with molecular identification, phenolic fingerprinting might be helpful to elucidate the evolutionary history of Z. noltei. Copyright © 2017 Elsevier Ltd. All rights reserved.

Asymmetric Membranes from Two Chemically Distinct Triblock Terpolymers Blended during Standard Membrane Fabrication.

PubMed

Li, Yuk Mun; Srinivasan, Divya; Vaidya, Parth; Gu, Yibei; Wiesner, Ulrich

2016-10-01

Deviating from the traditional formation of block copolymer derived isoporous membranes from one block copolymer chemistry, here asymmetric membranes with isoporous surface structure are derived from two chemically distinct block copolymers blended during standard membrane fabrication. As a first proof of principle, the fabrication of asymmetric membranes is reported, which are blended from two chemically distinct triblock terpolymers, poly(isoprene-b-styrene-b-(4-vinyl)pyridine) (ISV) and poly(isoprene-b-styrene-b-(dimethylamino)ethyl methacrylate) (ISA), differing in the pH-responsive hydrophilic segment. Using block copolymer self-assembly and nonsolvent induced phase separation process, pure and blended membranes are prepared by varying weight ratios of ISV to ISA. Pure and blended membranes exhibit a thin, selective layer of pores above a macroporous substructure. Observed permeabilities at varying pH values of blended membranes depend on relative triblock terpolymer composition. These results open a new direction for membrane fabrication through the use of mixtures of chemically distinct block copolymers enabling the tailoring of membrane surface chemistries and functionalities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Movements of Diadromous Fish in Large Unregulated Tropical Rivers Inferred from Geochemical Tracers

PubMed Central

Walther, Benjamin D.; Dempster, Tim; Letnic, Mike; McCulloch, Malcolm T.

2011-01-01

Patterns of migration and habitat use in diadromous fishes can be highly variable among individuals. Most investigations into diadromous movement patterns have been restricted to populations in regulated rivers, and little information exists for those in unregulated catchments. We quantified movements of migratory barramundi Lates calcarifer (Bloch) in two large unregulated rivers in northern Australia using both elemental (Sr/Ba) and isotope (87Sr/86Sr) ratios in aragonitic ear stones, or otoliths. Chemical life history profiles indicated significant individual variation in habitat use, particularly among chemically distinct freshwater habitats within a catchment. A global zoning algorithm was used to quantify distinct changes in chemical signatures across profiles. This algorithm identified between 2 and 6 distinct chemical habitats in individual profiles, indicating variable movement among habitats. Profiles of 87Sr/86Sr ratios were notably distinct among individuals, with highly radiogenic values recorded in some otoliths. This variation suggested that fish made full use of habitats across the entire catchment basin. Our results show that unrestricted movement among freshwater habitats is an important component of diadromous life histories for populations in unregulated systems. PMID:21494693

Qualitative photoluminescence study of defect activation in telecommunication fibers and Bragg gratings in hydrogen-loaded fibers

NASA Astrophysics Data System (ADS)

Bastola, B.; Fischer, B.; Roths, J.; Ruediger, A.

2018-07-01

Despite the relevance of glass fibers and integrated optical circuits for an increasing number of cutting-edge applications ranging from telecommunication to sensing and quantum photonics, the knowledge about their structural and chemical properties is still in its infancy. Optical spectroscopy techniques are challenged due to the intrinsically low cross-sections for inelastic processes. Our approach is to detect these properties along the core, extending the interaction to the fiber length. We report on in-situ temperature-dependent photoluminescence (PL) measurements in transmission geometry of a) pristine optical glass fibers (standard commercial telecom grade and different types of photosensitive fibers) and b) type I fiber Bragg grating (FBG) in hydrogen-loaded fibers of the same type. A laser with 473 nm wavelength and TEM 00 mode is coupled to an optical spectrometer through different fibers. The fibers are thermally cycled between room temperature and 950° Celsius. As a first observation, we detect a clearly visible red emission from the uncoated fibers at the location of the fiber Bragg grating. Fitting the luminescence spectra with a single Gaussian and monitoring the intensity as a function of temperature reveals an irreversible, thermally activated degradation of the luminescence associated to the fiber Bragg gratings. A closer inspection of pristine glass fibers without FBG revealed a faint, yet thermally stable luminescence with similar spectral characteristics. Analyzing qualitative data for two consecutive heating cycles confirmed two distinct activation energies. This may be due to several reasons such as different defects at the basis of this emission or different structural or chemical environments for the same defect. Further experiment will be carried out in the future to investigate the main reason of two distinct activation energies.

The Structural Enzymology of Iterative Aromatic Polyketide Synthases: A Critical Comparison with Fatty Acid Synthases.

PubMed

Tsai, Shiou-Chuan Sheryl

2018-06-20

Polyketides are a large family of structurally complex natural products including compounds with important bioactivities. Polyketides are biosynthesized by polyketide synthases (PKSs), multienzyme complexes derived evolutionarily from fatty acid synthases (FASs). The focus of this review is to critically compare the properties of FASs with iterative aromatic PKSs, including type II PKSs and fungal type I nonreducing PKSs whose chemical logic is distinct from that of modular PKSs. This review focuses on structural and enzymological studies that reveal both similarities and striking differences between FASs and aromatic PKSs. The potential application of FAS and aromatic PKS structures for bioengineering future drugs and biofuels is highlighted.

Surface Tension: Mechanics, Thermodynamics, and Relaxation Times

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2018-06-01

A microscopic analysis is presented of the existing definitions of equilibrium surface tension, which can be divided into two types: mechanical and thermodynamic. Each type of definition can be studied from the presentation below according to thermodynamic hypotheses or molecular calculations. An analysis of the planar interface is given and its generalization for curved (spherical) interfaces is considered. The distinction between approaches describing the surface tension of metastable and equilibrium droplets is discussed. Based on nonequilibrium thermodynamics, it is shown that the introduction of metastable droplets is due to a violation of the relationship between the times of impulse and chemical potential relaxation in condensed phases. Problems of calculating the surface tension in nonequilibrium situations are created.

PRISM 3: expanded prediction of natural product chemical structures from microbial genomes.

PubMed

Skinnider, Michael A; Merwin, Nishanth J; Johnston, Chad W; Magarvey, Nathan A

2017-07-03

Microbial natural products represent a rich resource of pharmaceutically and industrially important compounds. Genome sequencing has revealed that the majority of natural products remain undiscovered, and computational methods to connect biosynthetic gene clusters to their corresponding natural products therefore have the potential to revitalize natural product discovery. Previously, we described PRediction Informatics for Secondary Metabolomes (PRISM), a combinatorial approach to chemical structure prediction for genetically encoded nonribosomal peptides and type I and II polyketides. Here, we present a ground-up rewrite of the PRISM structure prediction algorithm to derive prediction of natural products arising from non-modular biosynthetic paradigms. Within this new version, PRISM 3, natural product scaffolds are modeled as chemical graphs, permitting structure prediction for aminocoumarins, antimetabolites, bisindoles and phosphonate natural products, and building upon the addition of ribosomally synthesized and post-translationally modified peptides. Further, with the addition of cluster detection for 11 new cluster types, PRISM 3 expands to detect 22 distinct natural product cluster types. Other major modifications to PRISM include improved sequence input and ORF detection, user-friendliness and output. Distribution of PRISM 3 over a 300-core server grid improves the speed and capacity of the web application. PRISM 3 is available at http://magarveylab.ca/prism/. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

An activity canyon characterization of the pharmacological topography.

PubMed

Kulkarni, Varsha S; Wild, David J

2016-01-01

Highly chemically similar drugs usually possess similar biological activities, but sometimes, small changes in chemistry can result in a large difference in biological effects. Chemically similar drug pairs that show extreme deviations in activity represent distinctive drug interactions having important implications. These associations between chemical and biological similarity are studied as discontinuities in activity landscapes. Particularly, activity cliffs are quantified by the drop in similar activity of chemically similar drugs. In this paper, we construct a landscape using a large drug-target network and consider the rises in similarity and variation in activity along the chemical space. Detailed analysis of structure and activity gives a rigorous quantification of distinctive pairs and the probability of their occurrence. We analyze pairwise similarity (s) and variation (d) in activity of drugs on proteins. Interactions between drugs are quantified by considering pairwise s and d weights jointly with corresponding chemical similarity (c) weights. Similarity and variation in activity are measured as the number of common and uncommon targets of two drugs respectively. Distinctive interactions occur between drugs having high c and above (below) average d (s). Computation of predicted probability of distinctiveness employs joint probability of c, s and of c, d assuming independence of structure and activity. Predictions conform with the observations at different levels of distinctiveness. Results are validated on the data used and another drug ensemble. In the landscape, while s and d decrease as c increases, d maintains value more than s. c ∈ [0.3, 0.64] is the transitional region where rises in d are significantly greater than drops in s. It is fascinating that distinctive interactions filtered with high d and low s are different in nature. It is crucial that high c interactions are more probable of having above average d than s. Identification of distinctive interactions is better with high d than low s. These interactions belong to diverse classes. d is greatest between drugs and analogs prepared for treatment of same class of ailments but with different therapeutic specifications. In contrast, analogs having low s would treat ailments from distinct classes. Intermittent spikes in d along the axis of c represent canyons in the activity landscape. This new representation accounts for distinctiveness through relative rises in s and d. It provides a mathematical basis for predicting the probability of occurrence of distinctiveness. It identifies the drug pairs at varying levels of distinctiveness and non-distinctiveness. The predicted probability formula is validated even if data approximately satisfy the conditions of its construction. Also, the postulated independence of structure and activity is of little significance to the overall assessment. The difference in distinctive interactions obtained by s and d highlights the importance of studying both of them, and reveals how the choice of measurement can affect the interpretation. The methods in this paper can be used to interpret whether or not drug interactions are distinctive and the probability of their occurrence. Practitioners and researchers can rely on this identification for quantitative modeling and assessment.

STRUCTURE OF THE VIBRIO CHOLERAE TYPE IVB PILUS AND STABILITY COMPARISON WITH THE NEISSERIA GONORRHOEAE TYPE IVA PILUS

PubMed Central

Li, Juliana; Egelman, Edward H.; Craig, Lisa

2012-01-01

Type IV pili are multifunctional filaments displayed on many bacterial pathogens. Members of the Type IVa pilus subclass are found on a diverse group of human pathogens whereas Type IVb pili are almost exclusively on enteric bacteria. The Type IVa and IVb subclasses are distinguished by differences in the pilin subunits, including the fold of the globular domain. To understand the implications of the distinct pilin folds we compared the stabilities of pilin subunits and pilus filaments for the Type IVa GC pilus from Neisseria gonorrhoeae and the Type IVb toxin-coregulated pilus (TCP) from Vibrio cholerae. We show that while recombinant TCP pilin is more stable than GC pilin, the GC pili are more resistant than TCP to proteolysis, heat and chemical denaturation, remaining intact in 8 M urea. To understand these differences we determined the TCP structure by electron microscopy and 3D image reconstruction. TCP have a similar architecture to GC pili, with subunits arranged in a right-handed one-start helix and related by an 8.4 Å axial rise and a 96.8° azimuthal rotation. However, the TCP subunits are not as tightly packed as GC pilins and the distinct Type IVb pilin fold exposes a segment of the α-helical core of TCP. Hydrophobic interactions dominate for both pilus subtypes, but base-stacking by aromatic residues conserved among the Type IVa pilins may contribute to GC pilus stability. The extraordinary stability of GC pili may represent an adaptation of the Type IVa pili to harsh environments and the need to retract against external forces. PMID:22361030

Structure-Activity Relationships of the Human Immunodeficiency Virus Type 1 Maturation Inhibitor PF-46396.

PubMed

Murgatroyd, Christopher; Pirrie, Lisa; Tran, Fanny; Smith, Terry K; Westwood, Nicholas J; Adamson, Catherine S

2016-09-15

HIV-1 maturation inhibitors are a novel class of antiretroviral compounds that consist of two structurally distinct chemical classes: betulinic acid derivatives and the pyridone-based compound PF-46396. It is currently believed that both classes act by similar modes of action to generate aberrant noninfectious particles via inhibition of CA-SP1 cleavage during Gag proteolytic processing. In this study, we utilized a series of novel analogues with decreasing similarity to PF-46396 to determine the chemical groups within PF-46396 that contribute to antiviral activity, Gag binding, and the relationship between these essential properties. A spectrum of antiviral activity (active, intermediate, and inactive) was observed across the analogue series with respect to CA-SP1 cleavage and HIV-1 (NL4-3) replication kinetics in Jurkat T cells. We demonstrate that selected inactive analogues are incorporated into wild-type (WT) immature particles and that one inactive analogue is capable of interfering with PF-46396 inhibition of CA-SP1 cleavage. Mutations that confer PF-46396 resistance can impose a defective phenotype on HIV-1 that can be rescued in a compound-dependent manner. Some inactive analogues retained the capacity to rescue PF-46396-dependent mutants (SP1-A3V, SP1-A3T, and CA-P157S), implying that they can also interact with mutant Gag. The structure-activity relationships observed in this study demonstrate that (i) the tert-butyl group is essential for antiviral activity but is not an absolute requirement for Gag binding, (ii) the trifluoromethyl group is optimal but not essential for antiviral activity, and (iii) the 2-aminoindan group is important for antiviral activity and Gag binding but is not essential, as its replacement is tolerated. Combinations of antiretroviral drugs successfully treat HIV/AIDS patients; however, drug resistance problems make the development of new mechanistic drug classes an ongoing priority. HIV-1 maturation inhibitors are novel as they target the Gag protein, specifically by inhibiting CA-SP1 proteolytic cleavage. The lack of high-resolution structural information of the CA-SP1 target in Gag has hindered our understanding of the inhibitor-binding pocket and maturation inhibitor mode of action. Therefore, we utilized analogues of the maturation inhibitor PF-46396 as chemical tools to determine the chemical components of PF-46396 that contribute to antiviral activity and Gag binding and the relationship between these essential properties. This is the first study to report structure-activity relationships of the maturation inhibitor PF-46396. PF-46396 is chemically distinct from betulinic acid-derived maturation inhibitors; therefore, our data provide a foundation of knowledge that will aid our understanding of how structurally distinct maturation inhibitors act by similar modes of action. Copyright © 2016 Murgatroyd et al.

Two distinct RNase activities of CRISPR-C2c2 enable guide-RNA processing and RNA detection.

PubMed

East-Seletsky, Alexandra; O'Connell, Mitchell R; Knight, Spencer C; Burstein, David; Cate, Jamie H D; Tjian, Robert; Doudna, Jennifer A

2016-10-13

Bacterial adaptive immune systems use CRISPRs (clustered regularly interspaced short palindromic repeats) and CRISPR-associated (Cas) proteins for RNA-guided nucleic acid cleavage. Although most prokaryotic adaptive immune systems generally target DNA substrates, type III and VI CRISPR systems direct interference complexes against single-stranded RNA substrates. In type VI systems, the single-subunit C2c2 protein functions as an RNA-guided RNA endonuclease (RNase). How this enzyme acquires mature CRISPR RNAs (crRNAs) that are essential for immune surveillance and how it carries out crRNA-mediated RNA cleavage remain unclear. Here we show that bacterial C2c2 possesses a unique RNase activity responsible for CRISPR RNA maturation that is distinct from its RNA-activated single-stranded RNA degradation activity. These dual RNase functions are chemically and mechanistically different from each other and from the crRNA-processing behaviour of the evolutionarily unrelated CRISPR enzyme Cpf1 (ref. 11). The two RNase activities of C2c2 enable multiplexed processing and loading of guide RNAs that in turn allow sensitive detection of cellular transcripts.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Speciated Chemical Composition of Biomass Burning Aerosol from Various Fuels during FIREX

NASA Astrophysics Data System (ADS)

Jen, C.; Hatch, L. E.; Kreisberg, N. M.; Selimovic, V.; Yokelson, R. J.; Barsanti, K.; Goldstein, A. H.

2017-12-01

Biomass burning is the largest global source of atmospheric primary carbonaceous aerosols and the second largest global source of non-methane organic compounds, including volatile and semi-volatile organic compounds that are now understood to be major contributors to secondary particle formation in the atmosphere. As wildfires in forested regions such as the western United States become larger and more frequent, understanding the chemical composition of biomass burning organic aerosol is needed to better predict their increasing impact on human health, air quality, and climate. This study presents emission profiles of chemically speciated intermediate and semi-volatile organic compounds present in biomass burning aerosol particles ≤1.0 μm. Biomass burning organic aerosol (BBOA) samples from a variety of fuel types and burning conditions were collected during the FIREX campaign at the USDA Fire Lab (Missoula, MT). Fuels were primarily selected from vegetation commonly found in the western United States, such as ponderosa pine, lodgepole pine, ceanothus, and chaparral. Collected BBOA was thermally desorbed from the filters and analyzed using online derivatization and 2-dimensional gas chromatography with an electron impact (70 eV) and vacuum ultra violet light (10.5 eV) high resolution time of flight mass spectrometer for compound identification. Emission profiles for specific compounds (e.g., levoglucosan) and families of compounds (e.g., sugars and methoxyphenols) show distinct variations between different fuel types, with major differences between fresh and partially decomposed fuels. Results also illustrate the variability in chemical species between burns conducted under similar conditions. Furthermore, chemical fingerprints, representing ratios of normalized emissions for key chemical compounds, were measured for specific fuels/conditions and could be used in future field studies to help identify contributions of various vegetation to total BBOA and in models to estimate the chemical composition of BBOA emissions.

Fundamental Concepts in the Teaching of Chemistry.

ERIC Educational Resources Information Center

Loeffler, Paul A.

1989-01-01

Presented is a simple, unified approach to chemical nomenclature which employs the distinction between the terms chemical substance and chemical species. The classification of matter and chemical nomenclature are used as examples to illustrate this scheme. (CW)

Suicidal Behavior in Chemically Dependent Adolescents.

ERIC Educational Resources Information Center

Cavaiola, Alan A.; Lavender, Neil

1999-01-01

Study explores distinctions between chemically dependent suicide attempters, chemically dependent nonsuicidal adolescents, and high school students with no history of chemical dependency (N=250). Results reveal that there were significant differences between the chemically dependent groups. It was also found that the majority of suicidal gestures…

Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) with Raman Imaging Applied to Lunar Meteorites.

PubMed

Smith, Joseph P; Smith, Frank C; Booksh, Karl S

2018-03-01

Lunar meteorites provide a more random sampling of the surface of the Moon than do the returned lunar samples, and they provide valuable information to help estimate the chemical composition of the lunar crust, the lunar mantle, and the bulk Moon. As of July 2014, ∼96 lunar meteorites had been documented and ten of these are unbrecciated mare basalts. Using Raman imaging with multivariate curve resolution-alternating least squares (MCR-ALS), we investigated portions of polished thin sections of paired, unbrecciated, mare-basalt lunar meteorites that had been collected from the LaPaz Icefield (LAP) of Antarctica-LAP 02205 and LAP 04841. Polarized light microscopy displays that both meteorites are heterogeneous and consist of polydispersed sized and shaped particles of varying chemical composition. For two distinct probed areas within each meteorite, the individual chemical species and associated chemical maps were elucidated using MCR-ALS applied to Raman hyperspectral images. For LAP 02205, spatially and spectrally resolved clinopyroxene, ilmenite, substrate-adhesive epoxy, and diamond polish were observed within the probed areas. Similarly, for LAP 04841, spatially resolved chemical images with corresponding resolved Raman spectra of clinopyroxene, troilite, a high-temperature polymorph of anorthite, substrate-adhesive epoxy, and diamond polish were generated. In both LAP 02205 and LAP 04841, substrate-adhesive epoxy and diamond polish were more readily observed within fractures/veinlet features. Spectrally diverse clinopyroxenes were resolved in LAP 04841. Factors that allow these resolved clinopyroxenes to be differentiated include crystal orientation, spatially distinct chemical zoning of pyroxene crystals, and/or chemical and molecular composition. The minerals identified using this analytical methodology-clinopyroxene, anorthite, ilmenite, and troilite-are consistent with the results of previous studies of the two meteorites using electron microprobe analysis. To our knowledge, this is the first report of MCR-ALS with Raman imaging used for the investigation of both lunar and other types of meteorites. We have demonstrated the use of multivariate analysis methods, namely MCR-ALS, with Raman imaging to investigate heterogeneous lunar meteorites. Our analytical methodology can be used to elucidate the chemical, molecular, and structural characteristics of phases in a host of complex, heterogeneous geological, geochemical, and extraterrestrial materials.

Market Basket Analysis: a new tool in ecology to describe chemical relations in the environment--a case study of the fern Athyrium distentifolium in the Tatra National Park in Poland.

PubMed

Samecka-Cymerman, Aleksandra; Stankiewicz, Andrzej; Kolon, Krzysztof; Kempers, Alexander J; Leuven, Rob S E W

2010-09-01

In this study, the novel data mining technique Market Basket Analysis (MBA) was applied for the first time in biogeochemical and ecological investigations. The method was tested on the fern Athyrium distentifolium, in which we measured concentrations of the elements Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn. Plants were sampled from sites with different types of bedrock in the Tatra National Park in Poland. MBA was used to investigate whether specimens of Athyrium distentifolium that contain elevated levels of certain elements occur more frequently on a specific type of bedrock and to identify relationships between the type of bedrock and the concentrations of the elements in this fern. The results were compared with those of the commonly used principal component and classification analysis (PCCA) technique. MBA and PCCA ordination both yielded distinct groups of ferns growing on different types of bedrock. Although the results of MBA and PCCA were similar, MBA has the advantage of being independent of the size of the data set. In addition, MBA revealed not only dominant elements but, in the case of limestone bedrock, also showed very low concentrations of Cd, Fe, Mn, and Pb in ferns growing on this type of parent material. MBA, thus, appeared to be a promising data mining method to reveal chemical relations in the environment as well as the accumulation of chemical elements in bioindicators. This technique can be used to reveal associations and correlations among items in large data sets collected on a national or even larger scale.

Discovery of 4-Methyl-N-(4-((4-methylpiperazin-1-yl)methyl)-3-(trifluoromethyl)phenyl)-3-((1-nicotinoylpiperidin-4-yl)oxy)benzamide (CHMFL-ABL/KIT-155) as a Novel Highly Potent Type II ABL/KIT Dual Kinase Inhibitor with a Distinct Hinge Binding.

PubMed

Wang, Qiang; Liu, Feiyang; Wang, Beilei; Zou, Fengming; Qi, Ziping; Chen, Cheng; Yu, Kailin; Hu, Chen; Qi, Shuang; Wang, Wenchao; Hu, Zhenquan; Liu, Juan; Wang, Wei; Wang, Li; Liang, Qianmao; Zhang, Shanchun; Ren, Tao; Liu, Qingsong; Liu, Jing

2017-01-12

The discovery of a novel potent type II ABL/c-KIT dual kinase inhibitor compound 34 (CHMFL-ABL/KIT-155), which utilized a hydrogen bond formed by NH on the kinase backbone and carbonyl oxygen of 34 as a unique hinge binding, is described. 34 potently inhibited purified ABL (IC 50 : 46 nM) and c-KIT kinase (IC 50 : 75 nM) in the biochemical assays and displayed high selectivity (S Score (1) = 0.03) at the concentration of 1 μM among 468 kinases/mutants in KINOMEscan assay. It exhibited strong antiproliferative activities against BCR-ABL/c-KIT driven CML/GISTs cancer cell lines through blockage of the BCR-ABL/c-KIT mediated signaling pathways, arresting cell cycle progression and induction of apoptosis. 34 possessed a good oral PK property and effectively suppressed the tumor progression in the K562 (CML) and GIST-T1 (GISTs) cells mediated xenograft mouse model. The distinct hinge-binding mode of 34 provided a novel pharmacophore for expanding the chemical structure diversity for the type II kinase inhibitors discovery.

Modeling the characteristic etch morphologies along specific crystallographic orientations by anisotropic chemical etching

NASA Astrophysics Data System (ADS)

Li, Kun-Dar; Miao, Jin-Ru

2018-02-01

To improve the advanced manufacturing technology for functional materials, a sophisticated control of chemical etching process is highly demanded, especially in the fields of environment and energy related applications. In this study, a phase-field-based model is utilized to investigate the etch morphologies influenced by the crystallographic characters during anisotropic chemical etching. Three types of etching modes are inspected theoretically, including the isotropic, <100> and <111> preferred oriented etchings. Owing to the specific etching behavior along the crystallographic directions, different characteristic surface structures are presented in the simulations, such as the pimple-like, pyramidal hillock and ridge-like morphologies. In addition, the processing parameters affecting the surface morphological formation and evolution are also examined systematically. According to the numerical results, the growth mechanism of surface morphology in a chemical etching is revealed distinctly. While the etching dynamics plays a dominant role on the surface formation, the characteristic surface morphologies corresponding to the preferred etching direction become more apparent. As the atomic diffusion turned into a determinative factor, a smoothened surface would appear, even under the anisotropic etching conditions. These simulation results provide fundamental information to enhance the development and application of anisotropic chemical etching techniques.

Doping of silicon by carbon during laser ablation process

NASA Astrophysics Data System (ADS)

Raciukaitis, G.; Brikas, M.; Kazlauskiene, V.; Miskinis, J.

2007-04-01

Effect of laser ablation on properties of remaining material was investigated in silicon. It was established that laser cutting of wafers in air induced doping of silicon by carbon. The effect was found to be more distinct by the use of higher laser power or UV radiation. Carbon ions created bonds with silicon in the depth of silicon. Formation of the silicon carbide type bonds was confirmed by SIMS, XPS and AES measurements. Modeling of the carbon diffusion was performed to clarify its depth profile in silicon. Photo-chemical reactions of such type changed the structure of material and could be a reason for the reduced quality of machining. A controlled atmosphere was applied to prevent carbonization of silicon during laser cutting.

Characteristics and antioxidant of Ulva intestinalis sulphated polysaccharides extracted with different solvents.

PubMed

Peasura, Napassorn; Laohakunjit, Natta; Kerdchoechuen, Orapin; Wanlapa, Sorada

2015-11-01

Ulva intestinalis, a tubular green seaweed, is a rich source of nutrient, especially sulphated polysaccharides. Sulphated polysaccharides from U. intestinalis were extracted with distilled water, 0.1N HCl, and 0.1N NaOH at 80°C for 1, 3, 6, 12, and 24h to study the effect of the extraction solvent and time on their chemical composition and antioxidant activity. Different types of solvents and extraction time had a significant influence on the chemical characteristics and antioxidant activity (p<0.05). Monosaccharide composition and FT-IR spectra analyses revealed that sulphated polysaccharides from all solvent extractions have a typical sugar backbone (glucose, rhamnose, and sulphate attached at C-2 or C-3 of rhamnose). Sulphated polysaccharides extracted with acid exhibited greater antioxidant activity than did those extracted with distilled water and alkali. The results indicated that solvent extraction could be an efficacious method for enhancing antioxidant activity by distinct molecular weight and chemical characteristic of sulphated polysaccharides. Copyright © 2015 Elsevier B.V. All rights reserved.

Chemical Analysis of a "Miller-Type" Complex Prebiotic Broth. Part II: Gas, Oil, Water and the Oil/Water-Interface

NASA Astrophysics Data System (ADS)

Scherer, Sabrina; Wollrab, Eva; Codutti, Luca; Carlomagno, Teresa; da Costa, Stefan Gomes; Volkmer, Andreas; Bronja, Amela; Schmitz, Oliver J.; Ott, Albrecht

2017-12-01

We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡ C or C≡ N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps.

Charge transfer in crystalline germanium/monolayer MoS 2 heterostructures prepared by chemical vapor deposition

DOE PAGES

Lin, Yung-Chen; Bilgin, Ismail; Ahmed, Towfiq; ...

2016-09-21

Heterostructuring provides novel opportunities for exploring emergent phenomena and applications by developing designed properties beyond those of homogeneous materials. Advances in nanoscience enable the preparation of heterostructures formed incommensurate materials. Two-dimensional (2D) materials, such as graphene and transition metal dichalcogenides, are of particular interest due to their distinct physical characteristics. There have been recent changes in new research areas related to 2D/2D heterostructures. But, other heterostructures such as 2D/three-dimensional (3D) materials have not been thoroughly studied yet although the growth of 3D materials on 2D materials creating 2D/3D heterostructures with exceptional carrier transport properties has been reported. Here also wemore » report a novel heterostructure composed of Ge and monolayer MoS 2, prepared by chemical vapor deposition. A single crystalline Ge (110) thin film was grown on monolayer MoS 2. The electrical characteristics of Ge and MoS 2 in the Ge/MoS 2 heterostructure were remarkably different from those of isolated Ge and MoS 2. The field-effect conductivity type of the monolayer MoS 2 is converted from n-type to p-type by growth of the Ge thin film on top of it. Undoped Ge on MoS 2 is highly conducting. The observations can be explained by charge transfer in the heterostructure as opposed to chemical doping via the incorporation of impurities, based on our first-principles calculations.« less

Chemical Analysis of a "Miller-Type" Complex Prebiotic Broth : Part II: Gas, Oil, Water and the Oil/Water-Interface.

PubMed

Scherer, Sabrina; Wollrab, Eva; Codutti, Luca; Carlomagno, Teresa; da Costa, Stefan Gomes; Volkmer, Andreas; Bronja, Amela; Schmitz, Oliver J; Ott, Albrecht

2017-12-01

We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡C or C≡N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps.

Neuronal somata and extrasomal compartments play distinct roles during synapse formation between Lymnaea neurons.

PubMed

Xu, Fenglian; Luk, Collin C; Wiersma-Meems, Ryanne; Baehre, Kelly; Herman, Cameron; Zaidi, Wali; Wong, Noelle; Syed, Naweed I

2014-08-20

Proper synapse formation is pivotal for all nervous system functions. However, the precise mechanisms remain elusive. Moreover, compared with the neuromuscular junction, steps regulating the synaptogenic program at central cholinergic synapses remain poorly defined. In this study, we identified different roles of neuronal compartments (somal vs extrasomal) in chemical and electrical synaptogenesis. Specifically, the electrically synapsed Lymnaea pedal dorsal A cluster neurons were used to study electrical synapses, whereas chemical synaptic partners, visceral dorsal 4 (presynaptic, cholinergic), and left pedal dorsal 1 (LPeD1; postsynaptic) were explored for chemical synapse formation. Neurons were cultured in a soma-soma or soma-axon configuration and synapses explored electrophysiologically. We provide the first direct evidence that electrical synapses develop in a soma-soma, but not soma-axon (removal of soma) configuration, indicating the requirement of gene transcription regulation in the somata of both synaptic partners. In addition, the soma-soma electrical coupling was contingent upon trophic factors present in Lymnaea brain-conditioned medium. Further, we demonstrate that chemical (cholinergic) synapses between soma-soma and soma-axon pairs were indistinguishable, with both exhibiting a high degree of contact site and target cell type specificity. We also provide direct evidence that presynaptic cell contact-mediated, clustering of postsynaptic cholinergic receptors at the synaptic site requires transmitter-receptor interaction, receptor internalization, and a protein kinase C-dependent lateral migration toward the contact site. This study provides novel insights into synaptogenesis between central neurons revealing both distinct and synergistic roles of cell-cell signaling and extrinsic trophic factors in executing the synaptogenic program. Copyright © 2014 the authors 0270-6474/14/3411304-12$15.00/0.

Size determination of Acipenser ruthenus spermatozoa in different types of electron microscopy.

PubMed

Psenicka, Martin; Tesarová, Martina; Tesitel, Jakub; Nebesárová, Jana

2010-07-01

In this study three types of scanning electron microscopes were used for the size determination of spermatozoa of sterlet Acipenser ruthenus - high vacuum scanning electron microscope (SEM, JEOL 6300), environmental scanning electron microscope (ESEM, Quanta 200 FEG), field emission scanning electron microscope (FESEM, JEOL 7401F) with cryoattachment Alto 2500 (Gatan) and transmission electron microscope (TEM, JEOL 1010). The use of particular microscopes was tied with different specimen preparation techniques. The aim of this study was to evaluate to what degree the type of used electron microscope can influence the size of different parts of spermatozoa. For high vacuum SEM the specimen was prepared using two slightly different procedures. After chemical fixation with 2.5% glutaraldehyde in 0.1M phosphate buffer and post-fixation by 1% osmium tetroxide, the specimen was dehydrated by acetone series and dried either by critical point method or by means of t-butylalcohol. For ESEM fresh, unfixed material was used, which was dropped on microscopic copper grids. In FESEM working in cryo-mode the specimen was observed in a frozen state. Ultrathin sections from chemically fixed and Epon embedded specimens were prepared for TEM observation. Distinct parts of sterlet spermatozoa were measured in each microscope and the data obtained was statistically processed. Results confirmed that the classical chemical procedure of specimen preparation for SEM including critical point drying method led to a significant contraction of all measured values, which could deviate up to 30% in comparison with values measured on the fresh chemically untreated specimen in ESEM. Surprisingly sperm dimensions determinated on ultrathin sections by TEM are comparable with values obtained in ESEM or FESEM. Copyright 2010 Elsevier Ltd. All rights reserved.

Immobilization of carbon nanotubes on functionalized graphene film grown by chemical vapor deposition and characterization of the hybrid material.

PubMed

Adhikari, Prashanta Dhoj; Jeon, Seunghan; Cha, Myoung-Jun; Jung, Dae Sung; Kim, Yooseok; Park, Chong-Yun

2014-02-01

We report the surface functionalization of graphene films grown by chemical vapor deposition and fabrication of a hybrid material combining multi-walled carbon nanotubes and graphene (CNT-G). Amine-terminated self-assembled monolayers were prepared on graphene by the UV-modification of oxidized groups introduced onto the film surface. Amine-termination led to effective interaction with functionalized CNTs to assemble a CNT-G hybrid through covalent bonding. Characterization clearly showed no defects of the graphene film after the immobilization reaction with CNT. In addition, the hybrid graphene material revealed a distinctive CNT-G structure and p-n type electrical properties. The introduction of functional groups on the graphene film surface and fabrication of CNT-G hybrids with the present technique could provide an efficient, novel route to device fabrication.

Ants regulate colony spatial organization using multiple chemical road-signs

PubMed Central

Heyman, Yael; Shental, Noam; Brandis, Alexander; Hefetz, Abraham; Feinerman, Ofer

2017-01-01

Communication provides the basis for social life. In ant colonies, the prevalence of local, often chemically mediated, interactions introduces strong links between communication networks and the spatial distribution of ants. It is, however, unknown how ants identify and maintain nest chambers with distinct functions. Here, we combine individual tracking, chemical analysis and machine learning to decipher the chemical signatures present on multiple nest surfaces. We present evidence for several distinct chemical ‘road-signs' that guide the ants' movements within the dark nest. These chemical signatures can be used to classify nest chambers with different functional roles. Using behavioural manipulations, we demonstrate that at least three of these chemical signatures are functionally meaningful and allow ants from different task groups to identify their specific nest destinations, thus facilitating colony coordination and stabilization. The use of multiple chemicals that assist spatiotemporal guidance, segregation and pattern formation is abundant in multi-cellular organisms. Here, we provide a rare example for the use of these principles in the ant colony. PMID:28569746

Ants regulate colony spatial organization using multiple chemical road-signs.

PubMed

Heyman, Yael; Shental, Noam; Brandis, Alexander; Hefetz, Abraham; Feinerman, Ofer

2017-06-01

Communication provides the basis for social life. In ant colonies, the prevalence of local, often chemically mediated, interactions introduces strong links between communication networks and the spatial distribution of ants. It is, however, unknown how ants identify and maintain nest chambers with distinct functions. Here, we combine individual tracking, chemical analysis and machine learning to decipher the chemical signatures present on multiple nest surfaces. We present evidence for several distinct chemical 'road-signs' that guide the ants' movements within the dark nest. These chemical signatures can be used to classify nest chambers with different functional roles. Using behavioural manipulations, we demonstrate that at least three of these chemical signatures are functionally meaningful and allow ants from different task groups to identify their specific nest destinations, thus facilitating colony coordination and stabilization. The use of multiple chemicals that assist spatiotemporal guidance, segregation and pattern formation is abundant in multi-cellular organisms. Here, we provide a rare example for the use of these principles in the ant colony.

High-Throughput Screening of Chemical Effects on Steroidogenesis Using H295R Human Adrenocortical Carcinoma Cells.

PubMed

Karmaus, Agnes L; Toole, Colleen M; Filer, Dayne L; Lewis, Kenneth C; Martin, Matthew T

2016-04-01

Disruption of steroidogenesis by environmental chemicals can result in altered hormone levels causing adverse reproductive and developmental effects. A high-throughput assay using H295R human adrenocortical carcinoma cells was used to evaluate the effect of 2060 chemical samples on steroidogenesis via high-performance liquid chromatography followed by tandem mass spectrometry quantification of 10 steroid hormones, including progestagens, glucocorticoids, androgens, and estrogens. The study employed a 3 stage screening strategy. The first stage established the maximum tolerated concentration (MTC; ≥ 70% viability) per sample. The second stage quantified changes in hormone levels at the MTC whereas the third stage performed concentration-response (CR) on a subset of samples. At all stages, cells were prestimulated with 10 µM forskolin for 48 h to induce steroidogenesis followed by chemical treatment for 48 h. Of the 2060 chemical samples evaluated, 524 samples were selected for 6-point CR screening, based in part on significantly altering at least 4 hormones at the MTC. CR screening identified 232 chemical samples with concentration-dependent effects on 17β-estradiol and/or testosterone, with 411 chemical samples showing an effect on at least one hormone across the steroidogenesis pathway. Clustering of the concentration-dependent chemical-mediated steroid hormone effects grouped chemical samples into 5 distinct profiles generally representing putative mechanisms of action, including CYP17A1 and HSD3B inhibition. A distinct pattern was observed between imidazole and triazole fungicides suggesting potentially distinct mechanisms of action. From a chemical testing and prioritization perspective, this assay platform provides a robust model for high-throughput screening of chemicals for effects on steroidogenesis. © The Author 2016. Published by Oxford University Press on behalf of the Society of Toxicology.

High-Throughput Screening of Chemical Effects on Steroidogenesis Using H295R Human Adrenocortical Carcinoma Cells

PubMed Central

Toole, Colleen M.; Filer, Dayne L.; Lewis, Kenneth C.; Martin, Matthew T.

2016-01-01

Disruption of steroidogenesis by environmental chemicals can result in altered hormone levels causing adverse reproductive and developmental effects. A high-throughput assay using H295R human adrenocortical carcinoma cells was used to evaluate the effect of 2060 chemical samples on steroidogenesis via high-performance liquid chromatography followed by tandem mass spectrometry quantification of 10 steroid hormones, including progestagens, glucocorticoids, androgens, and estrogens. The study employed a 3 stage screening strategy. The first stage established the maximum tolerated concentration (MTC; ≥ 70% viability) per sample. The second stage quantified changes in hormone levels at the MTC whereas the third stage performed concentration-response (CR) on a subset of samples. At all stages, cells were prestimulated with 10 µM forskolin for 48 h to induce steroidogenesis followed by chemical treatment for 48 h. Of the 2060 chemical samples evaluated, 524 samples were selected for 6-point CR screening, based in part on significantly altering at least 4 hormones at the MTC. CR screening identified 232 chemical samples with concentration-dependent effects on 17β-estradiol and/or testosterone, with 411 chemical samples showing an effect on at least one hormone across the steroidogenesis pathway. Clustering of the concentration-dependent chemical-mediated steroid hormone effects grouped chemical samples into 5 distinct profiles generally representing putative mechanisms of action, including CYP17A1 and HSD3B inhibition. A distinct pattern was observed between imidazole and triazole fungicides suggesting potentially distinct mechanisms of action. From a chemical testing and prioritization perspective, this assay platform provides a robust model for high-throughput screening of chemicals for effects on steroidogenesis. PMID:26781511

Statistics for the Relative Detectability of Chemicals in Weak Gaseous Plumes in LWIR Hyperspectral Imagery

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

Metoyer, Candace N.; Walsh, Stephen J.; Tardiff, Mark F.

2008-10-30

The detection and identification of weak gaseous plumes using thermal imaging data is complicated by many factors. These include variability due to atmosphere, ground and plume temperature, and background clutter. This paper presents an analysis of one formulation of the physics-based model that describes the at-sensor observed radiance. The motivating question for the analyses performed in this paper is as follows. Given a set of backgrounds, is there a way to predict the background over which the probability of detecting a given chemical will be the highest? Two statistics were developed to address this question. These statistics incorporate data frommore » the long-wave infrared band to predict the background over which chemical detectability will be the highest. These statistics can be computed prior to data collection. As a preliminary exploration into the predictive ability of these statistics, analyses were performed on synthetic hyperspectral images. Each image contained one chemical (either carbon tetrachloride or ammonia) spread across six distinct background types. The statistics were used to generate predictions for the background ranks. Then, the predicted ranks were compared to the empirical ranks obtained from the analyses of the synthetic images. For the simplified images under consideration, the predicted and empirical ranks showed a promising amount of agreement. One statistic accurately predicted the best and worst background for detection in all of the images. Future work may include explorations of more complicated plume ingredients, background types, and noise structures.« less

Lithology, age and structure of early proterozoic greenstone belts, West African shield

NASA Technical Reports Server (NTRS)

Attoh, K.

1986-01-01

Lithologic and chemical data have been compiled for belts in the Proterozoic terrane. Available stratigraphic information from geologic maps of these areas indicate that a typical sequence is comprised of predominately mafic lava flows (basalt-andesite) at the base, which are overlain by felsic volcanic rocks including pyroclastic rocks and lavas. Lithostratigraphic data indicate the volcanic succession is 6-8 km thick. This is followed by 3-4 km of basaltic lava flows which are locally pillowed, the top of the unit is marked by a distinctive manganese formation (MF) consisting of Mn-Fe rich cherts up to 200 m thick. The youngest volcanic unit consists of mafic tuffs and breccia with a distinctive fragmental texture. Of about 100 chemical analyses reported calc-alkaline rocks constitute 55% and tholeiites 45%. Quartz-normative basalt constitutes 99% of the rock type in the tholeiitic suite. In the calc-alkaline suite, 9% of the analyses is basalt, 45% andesite and the rest is dacite and rhyodacite. The available data lead to the conclusion that the minimum age for the volcanic activity must be between 2200 and 2100 million years. It is significant that Archean ages have not been reported from any of the volcanic belts (1-10).

Alkaline volcanic rocks from the Columbia Hills, Gusev crater, Mars

USGS Publications Warehouse

McSween, H.Y.; Ruff, S.W.; Morris, R.V.; Bell, J.F.; Herkenhoff, K.; Gellert, Ralf; Stockstill, K.R.; Tornabene, L.L.; Squyres, S. W.; Crisp, J.A.; Christensen, P.R.; McCoy, T.J.; Mittlefehldt, D. W.; Schmidt, M.

2006-01-01

Irvine, Backstay, and Wishstone are the type specimens for three classes of fine-grained or fragmental, relatively unaltered rocks with distinctive thermal emission spectra, found as float on the flanks of the Columbia Hills. Chemical analyses indicate that these rocks are mildly alkaline basalt, trachybasalt, and tephrite, respectively. Their mineralogy consists of Na- and K-rich feldspar(s), low- and high-Ca pyroxenes, ferroan olivine, Fe-Ti (and possibly Cr) oxides, phosphate, and possibly glass. The texture of Wishstone is consistent with a pyroclastic origin, whereas Irvine and Backstay are lavas or possibly dike rocks. Chemical compositions of these rocks plot on or near liquid lines of descent for most elements calculated for Adirondack class rocks (olivine-rich basalts from the Gusev plains) at various pressures from 0.1 to 1.0 GPa. We infer that Wishstone-, Backstay-, and Irvine-class magmas may have formed by fractionation of primitive, oxidized basaltic magma similar to Adirondack-class rocks. The compositions of all these rocks reveal that the Gusev magmatic province is alkaline, distinct from the subalkaline volcanic rocks thought to dominate most of the planet's surface. The fact that differentiated volcanic rocks were not encountered on the plains prior to ascending Husband Hill may suggest a local magma source for volcanism beneath Gusev crater. Copyright 2006 by the American Geophysical Union.

U-Series Disequilibria across the New Southern Ocean Mantle Province, Australian-Antarctic Ridge

NASA Astrophysics Data System (ADS)

Scott, S. R.; Sims, K. W. W.; Park, S. H.; Langmuir, C. H.; Lin, J.; Kim, S. S.; Blichert-Toft, J.; Michael, P. J.; Choi, H.; Yang, Y. S.

2017-12-01

Mid-ocean ridge basalts (MORB) provide a unique window into the temporal and spatial scales of mantle evolution. Long-lived radiogenic isotopes in MORB have demonstrated that the mantle contains many different chemical components or "flavors". U-series disequilibria in MORB have further shown that different chemical components/lithologies in the mantle contribute differently to mantle melting processes beneath mid-ocean ridges. Recent Sr, Nd, Hf, and Pb isotopic analyses from newly collected basalts along the Australian-Antarctic Ridge (AAR) have revealed that a large distinct mantle province exists between the Australian-Antarctic Discordance and the Pacific-Antarctic Ridge, extending from West Antarctica and Marie Byrd Land to New Zealand and Eastern Australia (Park et al., submitted). This southern mantle province is located between the Indian-type mantle and the Pacific-type mantle domains. U-series measurements in the Southeast Indian Ridge and East Pacific Rise provinces show distinct signatures suggestive of differences in melting processes and source lithology. To examine whether the AAR mantle province also exhibits different U-series systematics we have measured U-Th-Ra disequilibria data on 38 basalts from the AAR sampled along 500 km of ridge axis from two segments that cross the newly discovered Southern Ocean Mantle province. We compare the data to those from nearby ridge segments show that the AAR possesses unique U-series disequilibria, and are thus undergoing distinct mantle melting dynamics relative to the adjacent Pacific and Indian ridges. (230Th)/(238U) excesses in zero-age basalts (i.e., those with (226Ra)/(230Th) > 1.0) range from 1.3 to 1.7, while (226Ra)/(230Th) ranges from 1.0 to 2.3. (226Ra)/(230Th) and (230Th)/(238U) are negatively correlated, consistent with the model of mixing between deep and shallow melts. The AAR data show higher values of disequilibria compared to the Indian and Pacific Ridges, which can be explained by either lower melting rates and porosities, or a higher gt/cpx ratio in their mantle source. That both long-lived radiogenic isotopes and U-series disequilibria are distinct in these three adjacent mantle provinces suggests that lithological differences are strongly influencing the melting process beneath each of these mid-ocean ridges.

Informatic deconvolution of biased GPCR signaling mechanisms from in vivo pharmacological experimentation.

PubMed

Maudsley, Stuart; Martin, Bronwen; Janssens, Jonathan; Etienne, Harmonie; Jushaj, Areta; van Gastel, Jaana; Willemsen, Ann; Chen, Hongyu; Gesty-Palmer, Diane; Luttrell, Louis M

2016-01-01

Ligands possessing different physico-chemical structures productively interact with G protein-coupled receptors generating distinct downstream signaling events due to their abilities to activate/select idiosyncratic receptor entities ('receptorsomes') from the full spectrum of potential receptor partners. We have employed multiple novel informatic approaches to identify and characterize the in vivo transcriptomic signature of an arrestin-signaling biased ligand, [D-Trp(12),Tyr(34)]-bPTH(7-34), acting at the parathyroid hormone type 1 receptor (PTH1R), across six different murine tissues after chronic drug exposure. We are able to demonstrate that [D-Trp(12),Tyr(34)]-bPTH(7-34) elicits a distinctive arrestin-signaling focused transcriptomic response that is more coherently regulated, in an arrestin signaling-dependent manner, across more tissues than that of the pluripotent endogenous PTH1R ligand, hPTH(1-34). This arrestin-focused response signature is strongly linked with the transcriptional regulation of cell growth and development. Our informatic deconvolution of a conserved arrestin-dependent transcriptomic signature from wild type mice demonstrates a conceptual framework within which the in vivo outcomes of biased receptor signaling may be further investigated or predicted. Published by Elsevier Inc.

27 CFR 4.62 - Mandatory statements.

Code of Federal Regulations, 2010 CFR

2010-04-01

..., type, and distinctive designation. The advertisement shall contain a conspicuous statement of the class, type, or distinctive designation to which the product belongs, corresponding with the statement of class, type, or distinctive designation which is required to appear on the label of the product. (c...

CM and CO chondrites: A common parent body or asteroidal neighbors? Insights from chondrule silicates

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Davidson, Jemma

2017-10-01

By investigating the petrology and chemical composition of type II (FeO-rich) chondrules in the Mighei-like carbonaceous (CM) chondrites we constrain their thermal histories and relationship to the Ornans-like carbonaceous (CO) chondrites. We identified FeO-rich relict grains in type II chondrules by their Fe/Mn ratios; their presence indicates chondrule recycling among type II chondrules. The majority of relict grains in type II chondrules are FeO-poor olivine grains. Consistent with previous studies, chemical similarities between CM and CO chondrite chondrules indicate that they had similar formation conditions and that their parent bodies probably formed in a common region within the protoplanetary disk. However, important differences such as mean chondrule size and the lower abundance of FeO-poor relicts in CM chondrite type II chondrules than in CO chondrites suggest CM and CO chondrules did not form together and they likely originate from distinct parent asteroids. Despite being aqueously altered, many CM chondrites contain pre-accretionary anhydrous minerals (i.e., olivine) that are among the least thermally metamorphosed materials in chondrites according to the Cr2O3 content of their ferroan olivine. The presence of these minimally altered pre-accretionary chondrule silicates suggests that samples to be returned from aqueously altered asteroids by the Hayabusa2 and OSIRIS-REx asteroid sample return missions, even highly hydrated, may contain silicates that can provide information about the pre-accretionary histories and conditions of asteroids Ryugu and Bennu, respectively.

Identifying three ecological chemotypes of Xanthium strumarium glandular trichomes using a combined NMR and LC-MS method.

PubMed

Chen, Fangfang; Hao, Fuhua; Li, Changfu; Gou, Junbo; Lu, Dayan; Gong, Fujun; Tang, Huiru; Zhang, Yansheng

2013-01-01

Xanthanolides, as the sesquiterpene lactones, are reportedly the major components for the pharmacological properties of X. strumarium L. species. Phytochemical studies indicated that the glandular structures on the surface of plant tissues would form the primary sites for the accumulation of this class of the compounds. As the interface between plants and their natural enemies, glandular trichomes may vary with respect to which of their chemicals are sequestered against different herbivores in different ecologies. However, to date, no data are available on the chemical characterisation of X. strumarium glandular cells. In this study, the trichome secretions of the X. strumarium species originating from nineteen unique areas across eleven provinces in China, were analysed by HPLC, LC-ESI-MS and NMR. For the first time three distinct chemotypes of X. strumarium glandular trichomes were discovered along with the qualitative and quantitative evaluations of their presence of xanthanolides; these were designated glandular cell Types I, II, and III, respectively. The main xanthanolides in Type I cells were 8-epi-xanthatin and xanthumin while no xanthatin was detected. Xanthatin, 8-epi-xanthatin, and xanthumin dominated in Type II cells with comparable levels of each being present. For Type III cells, significantly higher concentrations of 8-epi-xanthatin or xanthinosin (relative to xanthatin) were detected with xanthinosin only being observed in this type. Further research will focus on understanding the ecological and molecular mechanism causing these chemotype differences in X. strumarium glandular structures.

Identifying Three Ecological Chemotypes of Xanthium strumarium Glandular Trichomes Using a Combined NMR and LC-MS Method

PubMed Central

Gou, Junbo; Lu, Dayan; Gong, Fujun; Tang, Huiru; Zhang, Yansheng

2013-01-01

Xanthanolides, as the sesquiterpene lactones, are reportedly the major components for the pharmacological properties of X. strumarium L. species. Phytochemical studies indicated that the glandular structures on the surface of plant tissues would form the primary sites for the accumulation of this class of the compounds. As the interface between plants and their natural enemies, glandular trichomes may vary with respect to which of their chemicals are sequestered against different herbivores in different ecologies. However, to date, no data are available on the chemical characterisation of X. strumarium glandular cells. In this study, the trichome secretions of the X. strumarium species originating from nineteen unique areas across eleven provinces in China, were analysed by HPLC, LC-ESI-MS and NMR. For the first time three distinct chemotypes of X. strumarium glandular trichomes were discovered along with the qualitative and quantitative evaluations of their presence of xanthanolides; these were designated glandular cell Types I, II, and III, respectively. The main xanthanolides in Type I cells were 8-epi-xanthatin and xanthumin while no xanthatin was detected. Xanthatin, 8-epi-xanthatin, and xanthumin dominated in Type II cells with comparable levels of each being present. For Type III cells, significantly higher concentrations of 8-epi-xanthatin or xanthinosin (relative to xanthatin) were detected with xanthinosin only being observed in this type. Further research will focus on understanding the ecological and molecular mechanism causing these chemotype differences in X. strumarium glandular structures. PMID:24098541

Nonequilibrium description of de novo biogenesis and transport through Golgi-like cisternae

NASA Astrophysics Data System (ADS)

Sachdeva, Himani; Barma, Mustansir; Rao, Madan

2016-12-01

A central issue in cell biology is the physico-chemical basis of organelle biogenesis in intracellular trafficking pathways, its most impressive manifestation being the biogenesis of Golgi cisternae. At a basic level, such morphologically and chemically distinct compartments should arise from an interplay between the molecular transport and chemical maturation. Here, we formulate analytically tractable, minimalist models, that incorporate this interplay between transport and chemical progression in physical space, and explore the conditions for de novo biogenesis of distinct cisternae. We propose new quantitative measures that can discriminate between the various models of transport in a qualitative manner-this includes measures of the dynamics in steady state and the dynamical response to perturbations of the kind amenable to live-cell imaging.

Lateral Hypothalamus Contains Two Types of Palatability-Related Taste Responses with Distinct Dynamics

PubMed Central

Yoshida, Takashi; Monk, Kevin J.; Katz, Donald B.

2013-01-01

The taste of foods, in particular the palatability of these tastes, exerts a powerful influence on our feeding choices. Although the lateral hypothalamus (LH) has long been known to regulate feeding behavior, taste processing in LH remains relatively understudied. Here, we examined single-unit LH responses in rats subjected to a battery of taste stimuli that differed in both chemical composition and palatability. Like neurons in cortex and amygdala, LH neurons produced a brief epoch of nonspecific responses followed by a protracted period of taste-specific firing. Unlike in cortex, however, where palatability-related information only appears 500 ms after the onset of taste-specific firing, taste specificity in LH was dominated by palatability-related firing, consistent with LH's role as a feeding center. Upon closer inspection, taste-specific LH neurons fell reliably into one of two subtypes: the first type showed a reliable affinity for palatable tastes, low spontaneous firing rates, phasic responses, and relatively narrow tuning; the second type showed strongest modulation to aversive tastes, high spontaneous firing rates, protracted responses, and broader tuning. Although neurons producing both types of responses were found within the same regions of LH, cross-correlation analyses suggest that they may participate in distinct functional networks. Our data shed light on the implementation of palatability processing both within LH and throughout the taste circuit, and may ultimately have implications for LH's role in the formation and maintenance of taste preferences and aversions. PMID:23719813

Lateral hypothalamus contains two types of palatability-related taste responses with distinct dynamics.

PubMed

Li, Jennifer X; Yoshida, Takashi; Monk, Kevin J; Katz, Donald B

2013-05-29

The taste of foods, in particular the palatability of these tastes, exerts a powerful influence on our feeding choices. Although the lateral hypothalamus (LH) has long been known to regulate feeding behavior, taste processing in LH remains relatively understudied. Here, we examined single-unit LH responses in rats subjected to a battery of taste stimuli that differed in both chemical composition and palatability. Like neurons in cortex and amygdala, LH neurons produced a brief epoch of nonspecific responses followed by a protracted period of taste-specific firing. Unlike in cortex, however, where palatability-related information only appears 500 ms after the onset of taste-specific firing, taste specificity in LH was dominated by palatability-related firing, consistent with LH's role as a feeding center. Upon closer inspection, taste-specific LH neurons fell reliably into one of two subtypes: the first type showed a reliable affinity for palatable tastes, low spontaneous firing rates, phasic responses, and relatively narrow tuning; the second type showed strongest modulation to aversive tastes, high spontaneous firing rates, protracted responses, and broader tuning. Although neurons producing both types of responses were found within the same regions of LH, cross-correlation analyses suggest that they may participate in distinct functional networks. Our data shed light on the implementation of palatability processing both within LH and throughout the taste circuit, and may ultimately have implications for LH's role in the formation and maintenance of taste preferences and aversions.

Occurrence of contaminants of emerging concern along the California coast (2009-10) using passive sampling devices.

PubMed

Alvarez, David A; Maruya, Keith A; Dodder, Nathan G; Lao, Wenjian; Furlong, Edward T; Smalling, Kelly L

2014-04-30

Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Comparing the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site. Published by Elsevier Ltd.

Occurrence of contaminants of emerging concern along the California coast (2009-10) using passive sampling devices

USGS Publications Warehouse

Alvarez, David A.; Maruya, Keith A.; Dodder, Nathan G.; Lao, Wenjian; Furlong, Edward T.; Smalling, Kelly L.

2014-01-01

Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Comparing the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site.

Wetting-Dewetting and Dispersion-Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix.

PubMed

Martin, Tyler B; Mongcopa, Katrina Irene S; Ashkar, Rana; Butler, Paul; Krishnamoorti, Ramanan; Jayaraman, Arthi

2015-08-26

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

Towards high resolution analysis of metabolic flux in cells and tissues.

PubMed

Sims, James K; Manteiga, Sara; Lee, Kyongbum

2013-10-01

Metabolism extracts chemical energy from nutrients, uses this energy to form building blocks for biosynthesis, and interconverts between various small molecules that coordinate the activities of cellular pathways. The metabolic state of a cell is increasingly recognized to determine the phenotype of not only metabolically active cell types such as liver, muscle, and adipose, but also other specialized cell types such as neurons and immune cells. This review focuses on methods to quantify intracellular reaction flux as a measure of cellular metabolic activity, with emphasis on studies involving cells of mammalian tissue. Two key areas are highlighted for future development, single cell metabolomics and noninvasive imaging, which could enable spatiotemporally resolved analysis and thereby overcome issues of heterogeneity, a distinctive feature of tissue metabolism. Copyright © 2013 Elsevier Ltd. All rights reserved.

Towards High Resolution Analysis of Metabolic Flux in Cells and Tissues

PubMed Central

Sims, James K; Manteiga, Sara; Lee, Kyongbum

2013-01-01

Metabolism extracts chemical energy from nutrients, uses this energy to form building blocks for biosynthesis, and interconverts between various small molecules that coordinate the activities of cellular pathways. The metabolic state of a cell is increasingly recognized to determine the phenotype of not only metabolically active cell types such as liver, muscle, and adipose, but also other specialized cell types such as neurons and immune cells. This review focuses on methods to quantify intracellular reaction flux as a measure of cellular metabolic activity, with emphasis on studies involving cells of mammalian tissue. Two key areas are highlighted for future development, single cell metabolomics and noninvasive imaging, which could enable spatiotemporally resolved analysis and thereby overcome issues of heterogeneity, a distinctive feature of tissue metabolism. PMID:23906926

Soil-vegetation relationships on a banded ironstone 'island', Carajás Plateau, Brazilian Eastern Amazonia.

PubMed

Nunes, Jaquelina A; Schaefer, Carlos E G R; Ferreira Júnior, Walnir G; Neri, Andreza V; Correa, Guilherme R; Enright, Neal J

2015-01-01

Vegetation and soil properties of an iron-rich canga (laterite) island on the largest outcrop of banded-iron formation in Serra de Carajás (eastern Amazonia, Brazil) were studied along a topographic gradient (738-762 m asl), and analyzed to test the hypothesis that soil chemical and physical attributes play a key role in the structure and floristic composition of these plant communities. Soil and vegetation were sampled in eight replicate plots within each of the four vegetation types. Surface (0-10 cm) soil samples from each plot were analyzed for basic cations, N, P and plant species density for all species was recorded. CCA ordination analysis showed a strong separation between forest and non-forest sites on the first axis, and between herbaceous and shrubby campo rupestre on the second axis. The four vegetation types shared few plant species, which was attributed to their distinctive soil environments and filtering of their constituent species by chemical, physical and hydrological constraints. Thus, we can infer that Edaphic (pedological) factors are crucial in explaining the types and distributions of campo rupestre vegetation associated with ferruginous ironstone uplands (Canga) in Carajás, eastern Amazonia, therefore the soil properties are the main drivers of vegetation composition and structure on these ironstone islands.

Using X-ray absorption to probe sulfur oxidation states in complex molecules

NASA Astrophysics Data System (ADS)

Vairavamurthy, A.

1998-10-01

X-ray absorption near-edge structure (XANES) spectroscopy offers an important non-destructive tool for determining oxidation states and for characterizing chemical speciation. The technique was used to experimentally verify the oxidation states of sulfur in different types of complex molecules because there are irregularities and uncertainties in assigning the values traditionally. The usual practice of determining oxidation states involves using a set of conventional rules. The oxidation state is an important control in the chemical speciation of sulfur, ranging from -2 to +6 in its different compounds. Experimental oxidation-state values for various types of sulfur compounds, using their XANES peak-energy positions, were assigned from a scale in which elemental sulfur and sulfate are designated as 0 and +6, respectively. Because these XANES-based values differed considerably from conventionally determined oxidation states for most sulfur compounds, a new term 'oxidation index' was coined to describe them. The experimental values were closer to those conventional values obtained by assigning shared electrons to the more electronegative atoms than to those based on other customary rules for assigning them. Because the oxidation index is distinct and characteristic for each different type of sulfur functionality, it becomes an important parameter for characterizing sulfur species, and for experimentally verifying uncertain oxidation states.

Analysis of the nutritional status of algae by Fourier transform infrared chemical imaging

NASA Astrophysics Data System (ADS)

Hirschmugl, Carol J.; Bayarri, Zuheir-El; Bunta, Maria; Holt, Justin B.; Giordano, Mario

2006-09-01

A new non-destructive method to study the nutritional status of algal cells and their environments is demonstrated. This approach allows rapid examination of whole cells without any or little pre-treatment providing a large amount of information on the biochemical composition of cells and growth medium. The method is based on the analysis of a collection of infrared (IR) spectra for individual cells; each spectrum describes the biochemical composition of a portion of a cell; a complete set of spectra is used to reconstruct an image of the entire cell. To obtain spatially resolved information synchrotron radiation was used as a bright IR source. We tested this method on the green flagellate Euglena gracilis; a comparison was conducted between cells grown in nutrient replete conditions (Type 1) and on cells allowed to deplete their medium (Type 2). Complete sets of spectra for individual cells of both types were analyzed with agglomerative hierarchical clustering, leading to distinct clusters representative of the two types of cells. The average spectra for the clusters confirmed the similarities between the clusters and the types of cells. The clustering analysis, therefore, allows the distinction of cells of the same species, but with different nutritional histories. In order to facilitate the application of the method and reduce manipulation (washing), we analyzed the cells in the presence of residual medium. The results obtained showed that even with residual medium the outcome of the clustering analysis is reliable. Our results demonstrate the applicability FTIR microspectroscopy for ecological and ecophysiological studies.

Multivariate soil fertility relationships for predicting the environmental persistence of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-tricyclohexane (RDX) among taxonomically distinct soils.

PubMed

Katseanes, Chelsea K; Chappell, Mark A; Hopkins, Bryan G; Durham, Brian D; Price, Cynthia L; Porter, Beth E; Miller, Lesley F

2017-12-01

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed overcoming this problem by considering the environmental persistence of these munition constituents (MC) as multivariate mathematical functions over a variety of taxonomically distinct soil types, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments where the disappearance kinetics of TNT and RDX were measured over a >300 h period in taxonomically distinct soils. Classical fertility-based soil measurements were log-transformed, statistically decomposed, and correlated to TNT and RDX disappearance rates (k -TNT and k -RDX ) using multivariate dimension-reduction and correlation techniques. From these efforts, we generated multivariate linear functions for k parameters across different soil types based on a statistically reduced set of their chemical and physical properties: Calculations showed that the soil properties exhibited strong covariance, with a prominent latent structure emerging as the basis for relative comparisons of the samples in reduced space. Loadings describing TNT degradation were largely driven by properties associated with alkaline/calcareous soil characteristics, while the degradation of RDX was attributed to the soil organic matter content - reflective of an important soil fertility characteristic. In spite of the differing responses to the munitions, batch data suggested that the overall nutrient dynamics were consistent for each soil type, as well as readily distinguishable from the other soil types used in this study. Thus, we hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished "soil types" may provide the means for potentially predicting complex phenomena in soils. Published by Elsevier Ltd.

Identification of helix capping and β-turn motifs from NMR chemical shifts

PubMed Central

Shen, Yang; Bax, Ad

2012-01-01

We present an empirical method for identification of distinct structural motifs in proteins on the basis of experimentally determined backbone and 13Cβ chemical shifts. Elements identified include the N-terminal and C-terminal helix capping motifs and five types of β-turns: I, II, I′, II′ and VIII. Using a database of proteins of known structure, the NMR chemical shifts, together with the PDB-extracted amino acid preference of the helix capping and β-turn motifs are used as input data for training an artificial neural network algorithm, which outputs the statistical probability of finding each motif at any given position in the protein. The trained neural networks, contained in the MICS (motif identification from chemical shifts) program, also provide a confidence level for each of their predictions, and values ranging from ca 0.7–0.9 for the Matthews correlation coefficient of its predictions far exceed that attainable by sequence analysis. MICS is anticipated to be useful both in the conventional NMR structure determination process and for enhancing on-going efforts to determine protein structures solely on the basis of chemical shift information, where it can aid in identifying protein database fragments suitable for use in building such structures. PMID:22314702

Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift† †Electronic supplementary information (ESI) available: Experimental and computational details, NMR spectra, results of NMR calculations and NCS analysis, graphical representation of shielding tensors, molecular orbital diagrams of selected compounds, optimized structures for all calculated species. See DOI: 10.1039/c7sc05039a

PubMed Central

Gordon, Christopher P.; Yamamoto, Keishi; Searles, Keith; Shirase, Satoru

2018-01-01

Metal alkylidenes, which are key organometallic intermediates in reactions such as olefination or alkene and alkane metathesis, are typically generated from metal dialkyl compounds [M](CH2R)2 that show distinctively deshielded chemical shifts for their α-carbons. Experimental solid-state NMR measurements combined with DFT/ZORA calculations and a chemical shift tensor analysis reveal that this remarkable deshielding originates from an empty metal d-orbital oriented in the M–Cα–Cα′ plane, interacting with the Cα p-orbital lying in the same plane. This π-type interaction inscribes some alkylidene character into Cα that favors alkylidene generation via α-H abstraction. The extent of the deshielding and the anisotropy of the alkyl chemical shift tensors distinguishes [M](CH2R)2 compounds that form alkylidenes from those that do not, relating the reactivity to molecular orbitals of the respective molecules. The α-carbon chemical shifts and tensor orientations thus predict the reactivity of metal alkyl compounds towards alkylidene generation. PMID:29675237

Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses.

PubMed

Kumpiene, Jurate; Robinson, Ryan; Brännvall, Evelina; Nordmark, Désirée; Bjurström, Henrik; Andreas, Lale; Lagerkvist, Anders; Ecke, Holger

2011-01-01

Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Vaccine-driven pharmacodynamic dissection and mitigation of fenethylline psychoactivity

NASA Astrophysics Data System (ADS)

Wenthur, Cody J.; Zhou, Bin; Janda, Kim D.

2017-08-01

Fenethylline, also known by the trade name Captagon, is a synthetic psychoactive stimulant that has recently been linked to a substance-use disorder and ‘pharmacoterrorism’ in the Middle East. Although fenethylline shares a common phenethylamine core with other amphetamine-type stimulants, it also incorporates a covalently linked xanthine moiety into its parent structure. These independently active pharmacophores are liberated during metabolism, resulting in the release of a structurally diverse chemical mixture into the central nervous system. Although the psychoactive properties of fenethylline have been reported to differ from those of other synthetic stimulants, the in vivo chemical complexity it manifests upon ingestion has impeded efforts to unambiguously identify the specific species responsible for these effects. Here we develop a ‘dissection through vaccination’ approach, called DISSECTIV, to mitigate the psychoactive effects of fenethylline and show that its rapid-onset and distinct psychoactive properties are facilitated by functional synergy between theophylline and amphetamine. Our results demonstrate that incremental vaccination against a single chemical species within a multi-component mixture can be used to uncover emergent properties arising from polypharmacological activity. We anticipate that DISSECTIV will be used to expose unidentified active chemical species and resolve pharmacodynamic interactions within other chemically complex systems, such as those found in counterfeit or illegal drug preparations, post-metabolic tissue samples and natural product extracts.

Vaccine-driven pharmacodynamic dissection and mitigation of fenethylline psychoactivity.

PubMed

Wenthur, Cody J; Zhou, Bin; Janda, Kim D

2017-08-24

Fenethylline, also known by the trade name Captagon, is a synthetic psychoactive stimulant that has recently been linked to a substance-use disorder and 'pharmacoterrorism' in the Middle East. Although fenethylline shares a common phenethylamine core with other amphetamine-type stimulants, it also incorporates a covalently linked xanthine moiety into its parent structure. These independently active pharmacophores are liberated during metabolism, resulting in the release of a structurally diverse chemical mixture into the central nervous system. Although the psychoactive properties of fenethylline have been reported to differ from those of other synthetic stimulants, the in vivo chemical complexity it manifests upon ingestion has impeded efforts to unambiguously identify the specific species responsible for these effects. Here we develop a 'dissection through vaccination' approach, called DISSECTIV, to mitigate the psychoactive effects of fenethylline and show that its rapid-onset and distinct psychoactive properties are facilitated by functional synergy between theophylline and amphetamine. Our results demonstrate that incremental vaccination against a single chemical species within a multi-component mixture can be used to uncover emergent properties arising from polypharmacological activity. We anticipate that DISSECTIV will be used to expose unidentified active chemical species and resolve pharmacodynamic interactions within other chemically complex systems, such as those found in counterfeit or illegal drug preparations, post-metabolic tissue samples and natural product extracts.

Identification of siRNA delivery enhancers by a chemical library screen.

PubMed

Gilleron, Jerome; Paramasivam, Prasath; Zeigerer, Anja; Querbes, William; Marsico, Giovanni; Andree, Cordula; Seifert, Sarah; Amaya, Pablo; Stöter, Martin; Koteliansky, Victor; Waldmann, Herbert; Fitzgerald, Kevin; Kalaidzidis, Yannis; Akinc, Akin; Maier, Martin A; Manoharan, Muthiah; Bickle, Marc; Zerial, Marino

2015-09-18

Most delivery systems for small interfering RNA therapeutics depend on endocytosis and release from endo-lysosomal compartments. One approach to improve delivery is to identify small molecules enhancing these steps. It is unclear to what extent such enhancers can be universally applied to different delivery systems and cell types. Here, we performed a compound library screen on two well-established siRNA delivery systems, lipid nanoparticles and cholesterol conjugated-siRNAs. We identified fifty-one enhancers improving gene silencing 2-5 fold. Strikingly, most enhancers displayed specificity for one delivery system only. By a combination of quantitative fluorescence and electron microscopy we found that the enhancers substantially differed in their mechanism of action, increasing either endocytic uptake or release of siRNAs from endosomes. Furthermore, they acted either on the delivery system itself or the cell, by modulating the endocytic system via distinct mechanisms. Interestingly, several compounds displayed activity on different cell types. As proof of principle, we showed that one compound enhanced siRNA delivery in primary endothelial cells in vitro and in the endocardium in the mouse heart. This study suggests that a pharmacological approach can improve the delivery of siRNAs in a system-specific fashion, by exploiting distinct mechanisms and acting upon multiple cell types. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

NMR crystallography of campho[2,3-c]pyrazole (Z' = 6): combining high-resolution 1H-13C solid-state MAS NMR spectroscopy and GIPAW chemical-shift calculations.

PubMed

Webber, Amy L; Emsley, Lyndon; Claramunt, Rosa M; Brown, Steven P

2010-09-30

(1)H-(13)C two-dimensional magic-angle spinning (MAS) solid-state NMR correlation spectra, recorded with the MAS-J-HMQC experiment, are presented for campho[2,3-c]pyrazole. For each (13)C moiety, there are six resonances associated with the six distinct molecules in the asymmetric unit cell (Z' = 6). The one-bond C-H correlations observed in the 2D (1)H-(13)C MAS-J-HMQC spectra allow the experimental determination of the (1)H and (13)C chemical shifts associated with the separate CH, CH(2), and CH(3) groups. (1)H and (13)C chemical shifts calculated by using the GIPAW (Gauge Including Projector Augmented Waves) plane-wave pseudopotential approach are presented. Calculations for the whole unit cell (12 × 29 = 348 atoms, with geometry optimization of all atoms) allow the assignment of the experimental (1)H and (13)C chemical shifts to the six distinct molecules. The calculated chemical shifts for the full crystal structure are compared with those for isolated molecules as extracted from the geometry-optimized crystal structure. In this way, the effect of intermolecular interactions on the observed chemical shifts is quantified. In particular, the calculations are sufficiently precise to differentiate the small (<1 ppm) differences between the (1)H chemical shifts of the six resonances associated with each distinct CH or CH(2) moiety.

Enzyme catalysis: a new definition accounting for noncovalent substrate- and product-like states.

PubMed

Purich, D L

2001-07-01

Biological catalysis frequently causes changes in noncovalent bonding. By building on Pauling's assertion that any long-lived, chemically distinct interaction is a chemical bond, this article redefines enzyme catalysis as the facilitated making and/or breaking of chemical bonds, not just of covalent bonds. It is also argued that nearly every ATPase or GTPase is misnamed as a hydrolase and actually belongs to a distinct class of enzymes, termed here 'energases'. By transducing covalent bond energy into mechanical work, energases mediate such fundamental processes as protein folding, self-assembly, G-protein interactions, DNA replication, chromatin remodeling and even active transport.

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

Liu, Xing-Wu; Cao, Zhi; Zhao, Shu

As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2C and ε’-Fe 2.2C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe xC, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectramore » for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2C has six sets of chemically distinct Fe atoms.« less

Differentiation of commercial vermiculite based on statistical analysis of bulk chemical data: Fingerprinting vermiculite from Libby, Montana U.S.A

USGS Publications Warehouse

Gunter, M.E.; Singleton, E.; Bandli, B.R.; Lowers, H.A.; Meeker, G.P.

2005-01-01

Major-, minor-, and trace-element compositions, as determined by X-ray fluorescence (XRF) analysis, were obtained on 34 samples of vermiculite to ascertain whether chemical differences exist to the extent of determining the source of commercial products. The sample set included ores from four deposits, seven commercially available garden products, and insulation from four attics. The trace-element distributions of Ba, Cr, and V can be used to distinguish the Libby vermiculite samples from the garden products. In general, the overall composition of the Libby and South Carolina deposits appeared similar, but differed from the South Africa and China deposits based on simple statistical methods. Cluster analysis provided a good distinction of the four ore types, grouped the four attic samples with the Libby ore, and, with less certainty, grouped the garden samples with the South Africa ore.

[FeFe]- and [NiFe]-hydrogenase diversity, mechanism, and maturation.

PubMed

Peters, John W; Schut, Gerrit J; Boyd, Eric S; Mulder, David W; Shepard, Eric M; Broderick, Joan B; King, Paul W; Adams, Michael W W

2015-06-01

The [FeFe]- and [NiFe]-hydrogenases catalyze the formal interconversion between hydrogen and protons and electrons, possess characteristic non-protein ligands at their catalytic sites and thus share common mechanistic features. Despite the similarities between these two types of hydrogenases, they clearly have distinct evolutionary origins and likely emerged from different selective pressures. [FeFe]-hydrogenases are widely distributed in fermentative anaerobic microorganisms and likely evolved under selective pressure to couple hydrogen production to the recycling of electron carriers that accumulate during anaerobic metabolism. In contrast, many [NiFe]-hydrogenases catalyze hydrogen oxidation as part of energy metabolism and were likely key enzymes in early life and arguably represent the predecessors of modern respiratory metabolism. Although the reversible combination of protons and electrons to generate hydrogen gas is the simplest of chemical reactions, the [FeFe]- and [NiFe]-hydrogenases have distinct mechanisms and differ in the fundamental chemistry associated with proton transfer and control of electron flow that also help to define catalytic bias. A unifying feature of these enzymes is that hydrogen activation itself has been restricted to one solution involving diatomic ligands (carbon monoxide and cyanide) bound to an Fe ion. On the other hand, and quite remarkably, the biosynthetic mechanisms to produce these ligands are exclusive to each type of enzyme. Furthermore, these mechanisms represent two independent solutions to the formation of complex bioinorganic active sites for catalyzing the simplest of chemical reactions, reversible hydrogen oxidation. As such, the [FeFe]- and [NiFe]-hydrogenases are arguably the most profound case of convergent evolution. This article is part of a Special Issue entitled: Fe/S proteins: Analysis, structure, function, biogenesis and diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

Economic feasibility of biochemical processes for the upgrading of crudes and the removal of sulfur, nitrogen, and trace metals from crude oil -- Benchmark cost establishment of biochemical processes on the basis of conventional downstream technologies. Final report FY95

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

Premuzic, E.T.

1996-08-01

During the past several years, a considerable amount of work has been carried out showing that microbially enhanced oil recovery (MEOR) is promising and the resulting biotechnology may be deliverable. At Brookhaven National Laboratory (BNL), systematic studies have been conducted which dealt with the effects of thermophilic and thermoadapted bacteria on the chemical and physical properties of selected types of crude oils at elevated temperatures and pressures. Current studies indicate that during the biotreatment several chemical and physical properties of crude oils are affected. The oils are (1) emulsified; (2) acidified; (3) there is a qualitative and quantitative change inmore » light and heavy fractions of the crudes; (4) there are chemical changes in fractions containing sulfur compounds; (5) there is an apparent reduction in the concentration of trace metals; and (6) the qualitative and quantitative changes appear to be microbial species dependent; and (7) there is a distinction between biodegraded and biotreated oils. The downstream biotechnological crude oil processing research performed thus far is of laboratory scale and has focused on demonstrating the technical feasibility of downstream processing with different types of biocatalysts under a variety of processing conditions. Quantitative economic analysis is the topic of the present project which investigates the economic feasibility of the various biochemical downstream processes which hold promise in upgrading of heavy crudes, such as those found in California, e.g., Monterey-type, Midway Sunset, Honda crudes, and others.« less

Structure-mechanism-based engineering of chemical regulators targeting distinct pathological factors in Alzheimer's disease

NASA Astrophysics Data System (ADS)

Beck, Michael W.; Derrick, Jeffrey S.; Kerr, Richard A.; Oh, Shin Bi; Cho, Woo Jong; Lee, Shin Jung C.; Ji, Yonghwan; Han, Jiyeon; Tehrani, Zahra Aliakbar; Suh, Nayoung; Kim, Sujeong; Larsen, Scott D.; Kim, Kwang S.; Lee, Joo-Yong; Ruotolo, Brandon T.; Lim, Mi Hee

2016-10-01

The absence of effective therapeutics against Alzheimer's disease (AD) is a result of the limited understanding of its multifaceted aetiology. Because of the lack of chemical tools to identify pathological factors, investigations into AD pathogenesis have also been insubstantial. Here we report chemical regulators that demonstrate distinct specificity towards targets linked to AD pathology, including metals, amyloid-β (Aβ), metal-Aβ, reactive oxygen species, and free organic radicals. We obtained these chemical regulators through a rational structure-mechanism-based design strategy. We performed structural variations of small molecules for fine-tuning their electronic properties, such as ionization potentials and mechanistic pathways for reactivity towards different targets. We established in vitro and/or in vivo efficacies of the regulators for modulating their targets' reactivities, ameliorating toxicity, reducing amyloid pathology, and improving cognitive deficits. Our chemical tools show promise for deciphering AD pathogenesis and discovering effective drugs.

Structure-mechanism-based engineering of chemical regulators targeting distinct pathological factors in Alzheimer's disease.

PubMed

Beck, Michael W; Derrick, Jeffrey S; Kerr, Richard A; Oh, Shin Bi; Cho, Woo Jong; Lee, Shin Jung C; Ji, Yonghwan; Han, Jiyeon; Tehrani, Zahra Aliakbar; Suh, Nayoung; Kim, Sujeong; Larsen, Scott D; Kim, Kwang S; Lee, Joo-Yong; Ruotolo, Brandon T; Lim, Mi Hee

2016-10-13

The absence of effective therapeutics against Alzheimer's disease (AD) is a result of the limited understanding of its multifaceted aetiology. Because of the lack of chemical tools to identify pathological factors, investigations into AD pathogenesis have also been insubstantial. Here we report chemical regulators that demonstrate distinct specificity towards targets linked to AD pathology, including metals, amyloid-β (Aβ), metal-Aβ, reactive oxygen species, and free organic radicals. We obtained these chemical regulators through a rational structure-mechanism-based design strategy. We performed structural variations of small molecules for fine-tuning their electronic properties, such as ionization potentials and mechanistic pathways for reactivity towards different targets. We established in vitro and/or in vivo efficacies of the regulators for modulating their targets' reactivities, ameliorating toxicity, reducing amyloid pathology, and improving cognitive deficits. Our chemical tools show promise for deciphering AD pathogenesis and discovering effective drugs.

Structures and functions of insect arylalkylamine N-acetyltransferase (iaaNAT); a key enzyme for physiological and behavioral switch in arthropods

PubMed Central

Hiragaki, Susumu; Suzuki, Takeshi; Mohamed, Ahmed A. M.; Takeda, Makio

2015-01-01

The evolution of N-acetyltransfeases (NATs) seems complex. Vertebrate arylalkylamine N-acetyltransferase (aaNAT) has been extensively studied since it leads to the synthesis of melatonin, a multifunctional neurohormone prevalent in photoreceptor cells, and is known as a chemical token of the night. Melatonin also serves as a scavenger for reactive oxygen species. This is also true with invertebrates. NAT therefore has distinct functional implications in circadian function, as timezymes (aaNAT), and also xenobiotic reactions (arylamine NAT or simply NAT). NATs belong to a broader enzyme group, the GCN5-related N-acetyltransferase superfamily. Due to low sequence homology and a seemingly fast rate of structural differentiation, the nomenclature for NATs can be confusing. The advent of bioinformatics, however, has helped to classify this group of enzymes; vertebrates have two distinct subgroups, the timezyme type and the xenobiotic type, which has a wider substrate range including imidazolamine, pharmacological drugs, environmental toxicants and even histone. Insect aaNAT (iaaNAT) form their own clade in the phylogeny, distinct from vertebrate aaNATs. Arthropods are unique, since the phylum has exoskeleton in which quinones derived from N-acetylated monoamines function in coupling chitin and arthropodins. Monoamine oxidase (MAO) activity is limited in insects, but NAT-mediated degradation prevails. However, unexpectedly iaaNAT occurs not only among arthropods but also among basal deuterostomia, and is therefore more apomorphic. Our analyses illustrate that iaaNATs has unique physiological roles but at the same time it plays a role in a timezyme function, at least in photoperiodism. Photoperiodism has been considered as a function of circadian system but the detailed molecular mechanism is not well understood. We propose a molecular hypothesis for photoperiodism in Antheraea pernyi based on the transcription regulation of NAT interlocked by the circadian system. Therefore, the enzyme plays both unique and universal roles in insects. The unique role of iaaNATs in physiological regulation urges the targeting of this system for integrated pest management (IPM). We indeed showed a successful example of chemical compound screening with reconstituted enzyme and further attempts seem promising. PMID:25918505

Structures and functions of insect arylalkylamine N-acetyltransferase (iaaNAT); a key enzyme for physiological and behavioral switch in arthropods.

PubMed

Hiragaki, Susumu; Suzuki, Takeshi; Mohamed, Ahmed A M; Takeda, Makio

2015-01-01

The evolution of N-acetyltransfeases (NATs) seems complex. Vertebrate arylalkylamine N-acetyltransferase (aaNAT) has been extensively studied since it leads to the synthesis of melatonin, a multifunctional neurohormone prevalent in photoreceptor cells, and is known as a chemical token of the night. Melatonin also serves as a scavenger for reactive oxygen species. This is also true with invertebrates. NAT therefore has distinct functional implications in circadian function, as timezymes (aaNAT), and also xenobiotic reactions (arylamine NAT or simply NAT). NATs belong to a broader enzyme group, the GCN5-related N-acetyltransferase superfamily. Due to low sequence homology and a seemingly fast rate of structural differentiation, the nomenclature for NATs can be confusing. The advent of bioinformatics, however, has helped to classify this group of enzymes; vertebrates have two distinct subgroups, the timezyme type and the xenobiotic type, which has a wider substrate range including imidazolamine, pharmacological drugs, environmental toxicants and even histone. Insect aaNAT (iaaNAT) form their own clade in the phylogeny, distinct from vertebrate aaNATs. Arthropods are unique, since the phylum has exoskeleton in which quinones derived from N-acetylated monoamines function in coupling chitin and arthropodins. Monoamine oxidase (MAO) activity is limited in insects, but NAT-mediated degradation prevails. However, unexpectedly iaaNAT occurs not only among arthropods but also among basal deuterostomia, and is therefore more apomorphic. Our analyses illustrate that iaaNATs has unique physiological roles but at the same time it plays a role in a timezyme function, at least in photoperiodism. Photoperiodism has been considered as a function of circadian system but the detailed molecular mechanism is not well understood. We propose a molecular hypothesis for photoperiodism in Antheraea pernyi based on the transcription regulation of NAT interlocked by the circadian system. Therefore, the enzyme plays both unique and universal roles in insects. The unique role of iaaNATs in physiological regulation urges the targeting of this system for integrated pest management (IPM). We indeed showed a successful example of chemical compound screening with reconstituted enzyme and further attempts seem promising.

The Tuscarora Au-Ag district: Eocene volcanic-hosted epithermal deposits in the Carlin gold region, Nevada

USGS Publications Warehouse

Castor, S.B.; Boden, D.R.; Henry, C.D.; Cline, J.S.; Hofstra, A.H.; McIntosh, W.C.; Tosdal, R.M.; Wooden, J.P.

2003-01-01

The Tuscarora mining district contains the oldest and the only productive Eocene epithermal deposits in Nevada. The district is a particularly clear example of association of low-sulfidation deposits with igneous activity and structure, and it is unusual in that it consists of two adjoining but physically and chemically distinct types of low-sulfidation deposits. Moreover, Tuscarora deposits are of interest because they formed contemporaneously with nearby, giant Carlin-type gold deposits. The Tuscarora deposits formed within the 39.9 to 39.3 Ma Tuscarora volcanic field, along and just outside the southeastern margin of the caldera-like Mount Blitzen volcanic center. Both deposit types formed at 39.3 Ma, contemporaneous with the only major intrusive activity in the volcanic field. No deposits are known to have formed during any of the intense volcanic phases of the field. Intrusions were the apparent heat source, and structures related to the Mount Blitzen center were conduits for hydrothermal circulation. The ore-forming fluids interacted dominantly with Eocene igneous rocks. The two deposit types occur in a northern silver-rich zone that is characterized by relatively high Ag/Au ratios (110-150), narrow alteration zones, and quartz and carbonate veins developed mostly in intrusive dacite, and in a southern gold-rich zone that is typified by relatively low Ag/Au ratios (4-14), more widespread alteration, and quartz-fissure and stockwork veins commonly developed in tuffaceous sedimentary rocks. The deposit types have similar fluid inclusion and Pb and S isotope characteristics but different geochemical signatures. Quartz veins from both zones have similar thermal and paragenetic histories and contain fluid inclusions that indicate that fluids cooled from between 260?? and 230??C to less than 200??C. Fluid boiling may have contributed to precious-metal deposition. Veins in both zones have relatively high As and Sb and low Bi, Te, and W. The silver zone has high Ca, Pb, Mn, Zn, Cd, Tl, and Se. The gold zone has high Hg and Mo. A few samples from an area of overlap between the two zones share chemical characteristics of both deposit types. The deposit types could represent a single zoned or evolving system in which hydrothermal fluids rose along structures within the silver zone, preferentially deposited Ag and base metals, and then spread into the gold zone. Alternatively, the deposit types could represent two distinct but temporally indistinguishable hydrothermal cells that only narrowly overlapped spatially. As noted in previous studies, the hydrothermal fluids that generated the Tuscarora and other epithermal deposits could have evolved from Carlin-type fluids by boiling and mixing with meteoric water. If so, the Tuscarora deposit may represent epithermal conditions above Carlin-type deposits, and Carlin-type deposits may lie beneath the district.

Bubble Jet agent release cartridge for chemical single cell stimulation.

PubMed

Wangler, N; Welsche, M; Blazek, M; Blessing, M; Vervliet-Scheebaum, M; Reski, R; Müller, C; Reinecke, H; Steigert, J; Roth, G; Zengerle, R; Paust, N

2013-02-01

We present a new method for the distinct specific chemical stimulation of single cells and small cell clusters within their natural environment. By single-drop release of chemical agents with droplets in size of typical cell diameters (d <30 μm) on-demand micro gradients can be generated for the specific manipulation of single cells. A single channel and a double channel agent release cartridge with integrated fluidic structures and integrated agent reservoirs are shown, tested, and compared in this publication. The single channel setup features a fluidic structure fabricated by anisotropic etching of silicon. To allow for simultaneous release of different agents even though maintaining the same device size, the second type comprises a double channel fluidic structure, fabricated by photolithographic patterning of TMMF. Dispensed droplet volumes are V = 15 pl and V = 10 pl for the silicon and the TMMF based setups, respectively. Utilizing the agent release cartridges, the application in biological assays was demonstrated by hormone-stimulated premature bud formation in Physcomitrella patens and the individual staining of one single L 929 cell within a confluent grown cell culture.

Different Models Used to Interpret Chemical Changes: Analysis of a Curriculum and Its Impact on French Students' Reasoning

ERIC Educational Resources Information Center

Kermen, Isabelle; Meheut, Martine

2009-01-01

We present an analysis of the new French curriculum on chemical changes describing the underlying models and highlighting their relations to the empirical level. The authors of the curriculum introduced a distinction between the chemical change of a chemical system and the chemical reactions that account for it. We specify the different roles of…

Giant Peak Voltage of Thermopower Waves Driven by the Chemical Potential Gradient of Single-Crystalline Bi2 Te3.

PubMed

Singh, Swati; Mun, Hyeona; Lee, Sanghoon; Kim, Sung Wng; Baik, Seunghyun

2017-09-01

The self-propagating exothermic chemical reaction with transient thermovoltage, known as the thermopower wave, has received considerable attention recently. A greater peak voltage and specific power are still demanded, and materials with greater Seebeck coefficients have been previously investigated. However, this study employs an alternative mechanism of transient chemical potential gradient providing an unprecedentedly high peak voltage (maximum: 8 V; average: 2.3 V) and volume-specific power (maximum: 0.11 W mm -3 ; average: 0.04 W mm -3 ) using n-type single-crystalline Bi 2 Te 3 substrates. A mixture of nitrocellulose and sodium azide is used as a fuel, and ultraviolet photoelectron spectroscopy reveals a significant downshift in Fermi energy (≈5.09 eV) of the substrate by p-doping of the fuel. The induced electrical potential by thermopower waves has two distinct sources: the Seebeck effect and the transient chemical potential gradient. Surprisingly, the Seebeck effect contribution is less than 2.5% (≈201 mV) of the maximum peak voltage. The right combination of substrate, fuel doping, and anisotropic substrate geometry results in an order of magnitude greater transient chemical potential gradient (≈5.09 eV) upon rapid removal of fuel by exothermic chemical reaction propagation. The role of fuel doping and chemical potential gradient can be viewed as a key mechanism for enhanced heat to electric conversion performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The phytochemical and genetic survey of common and dwarf juniper (Juniperus communis and Juniperus nana) identifies chemical races and close taxonomic identity of the species.

PubMed

Filipowicz, Natalia; Piotrowski, Arkadiusz; Ochocka, J Renata; Asztemborska, Monika

2006-07-01

Juniperus communis L. (= J. communis var. communis) and Juniperus nana Willd. (= J. communis var. SAXATILIS) are subspecies of juniper. J. communis grows widely in both hemispheres, primarily in lower elevations while J. nana is mainly observed in high mountains. Although they can be distinguished by morphological features, it is not known whether they are genetically and phytochemically distinct entities. We aimed to check whether it is possible to distinguish these two plants (i) by pharmaceutically important chemical traits and (ii) on the basis of intraspecifically highly polymorphic fragment of chloroplast DNA. We used GC with achiral as well as with enantioselective stationary phase columns to identify the main monoterpenes of the essential oil. Sequence analysis of the TRNL (UAA)- TRNF (GAA) intergenic spacer of the chloroplast genome was used as a genetic marker of taxonomic identity between these two subspecies. The chromatographic analysis showed the existence of three chemical races - the alpha-pinene type, the sabinene type and one with intermediate contents of these terpenes among both J. communis and J. nana. Surprisingly, sequence analysis of TRNL (UAA)- TRNF (GAA) revealed 100 % similarity between the common and the dwarf juniper. Thus, the monoterpene pattern is related to geographical origin, and not to the species identity. We suggest that the three chemical races identified in the present study should be considered as separate sources of pharmaceutical raw material. Our results demonstrate that the contents of alpha-pinene and sabinene may be applied as a quick diagnostic test for preliminary evaluation of plant material.

Growing Actin Networks Form Lamellipodium and Lamellum by Self-Assembly

PubMed Central

Huber, Florian; Käs, Josef; Stuhrmann, Björn

2008-01-01

Many different cell types are able to migrate by formation of a thin actin-based cytoskeletal extension. Recently, it became evident that this extension consists of two distinct substructures, designated lamellipodium and lamellum, which differ significantly in their kinetic and kinematic properties as well as their biochemical composition. We developed a stochastic two-dimensional computer simulation that includes chemical reaction kinetics, G-actin diffusion, and filament transport to investigate the formation of growing actin networks in migrating cells. Model parameters were chosen based on experimental data or theoretical considerations. In this work, we demonstrate the system's ability to form two distinct networks by self-organization. We found a characteristic transition in mean filament length as well as a distinct maximum in depolymerization flux, both within the first 1–2 μm. The separation into two distinct substructures was found to be extremely robust with respect to initial conditions and variation of model parameters. We quantitatively investigated the complex interplay between ADF/cofilin and tropomyosin and propose a plausible mechanism that leads to spatial separation of, respectively, ADF/cofilin- or tropomyosin-dominated compartments. Tropomyosin was found to play an important role in stabilizing the lamellar actin network. Furthermore, the influence of filament severing and annealing on the network properties is explored, and simulation data are compared to existing experimental data. PMID:18708450

Chemical Engineering Students: A Distinct Group among Engineers

ERIC Educational Resources Information Center

Godwin, Allison; Potvin, Geoff

2013-01-01

This paper explores differences between chemical engineering students and students of other engineering disciplines, as identified by their intended college major. The data used in this analysis was taken from the nationally representative Sustainability and Gender in Engineering (SaGE) survey. Chemical engineering students differ significantly…

Authentication and chemical study of isodonis herba and isodonis extracts.

PubMed

Maruyama, Takuro; Sugimoto, Naoki; Kuroyanagi, Masanori; Kim, Ik Hwi; Kamakura, Hiroyuki; Kawasaki, Takeshi; Fujita, Masao; Shimada, Hiroshi; Yamamoto, Yutaka; Tada, Atsuko; Yamazaki, Takeshi; Goda, Yukihiro

2007-11-01

Isodonis Herba is used as a Japanese dietary supplement and folk medicine. The extract of the herb (Isodonis extract) is also used as a food additive whose major compound is enmein (1). Here we compared internal transcribed spacer sequences of nuclear ribosomal DNA from Isodonis Herba available on the Japanese and Chinese crude drug markets, and found that the former derived from Isodon japonicus and Isodon trichocarpus, while the latter derived from distinct species such as Isodon eriocalyx. The liquid chromatography/mass spectrometry profiles of Isodonis Herba were classified into four chemotypes (A to D) according to the ratio of the major constituents. Types B and C contained 1 and oridonin (2) as major components, respectively. An intermediate (or mixed) form of types B and C in various ratios was designed type A. Type D contained eriocalyxin B (3) as its major component. Japanese herba were types A-C, while Chinese herba were types C and D. The commercial Isodonis extract products tested were classified as type D, suggesting that they originated from Chinese Herba. Understanding the relationship between extract constituents and DNA profiles is important for the official specification of dietary supplements and food additives of plant origin.

Direct chemical evidence for sphingolipid domains in the plasma membranes of fibroblasts [High-Resolution Chemical Imaging of Sphingolipid Distribution in the Plasma Membrane

DOE PAGES

Frisz, Jessica F.; Lou, Kaiyan; Klitzing, Haley A.; ...

2013-01-28

Sphingolipids play important roles in plasma membrane structure and cell signaling. Yet, their lateral distribution in the plasma membrane is poorly understood. Here we quantitatively analyzed the sphingolipid organization on the entire dorsal surface of intact cells by mapping the distribution of 15N-enriched ions from metabolically labeled 15N-sphingolipids in the plasma membrane using high-resolution imaging mass spectrometry. Many types of control experiments (internal, positive, negative, and fixation temperature), along with parallel experiments involving the imaging of fluorescent sphingolipids$-$both in living cells and during fixation of living cells$-$exclude potential artifacts. Micrometer-scale sphingolipid patches consisting of numerous 15Nsphingolipid microdomains with mean diametersmore » of ~200 nm are always present in the plasma membrane. Depletion of 30% of the cellular cholesterol did not eliminate the sphingolipid domains, but did reduce their abundance and long range organization in the plasma membrane. In contrast, disruption of the cytoskeleton eliminated the sphingolipid domains. These results indicate that these sphingolipid assemblages are not lipid rafts, and are instead a distinctly different type of sphingolipid-enriched plasma membrane domain that depends upon cortical actin.« less

Development of a Digital Meteorite Identification Program at University of New Mexico (UNM) (Institute of Meteoritics) and Southwestern Indian Polytechnic Institute (SIPI)

NASA Technical Reports Server (NTRS)

Gakin, R.; Lewis, K.; Simmons, J.; Gchachu, K.; Karner, J. M.; Newsom, H. E.; Jones, R. H.

2003-01-01

Determining the origin and chemical composition of suspect extra terrestrial specimens has lead to meteorite identification research programs. Such programs, like the University of New Mexico-Southwestern Indian Polytechnic Institute partnership, are being inundated with many non-meteorites (meteor wrongs) sent in by interested individuals from all over the world. This meteorite identification program developed a spreadsheet that aids in identifying the types of minerals in a sample for physical properties, possible meteorite characteristics, minerals and rock properties, and possible man made characteristics. Samples that show meteorite distinctiveness are further analyzed via the Scanning Electron Microprobe (SEM).

IBA investigations of loose garnets from Pietroasa, Apahida and Cluj-Someşeni treasures (5th century AD)

NASA Astrophysics Data System (ADS)

Bugoi, R.; Oanţă-Marghitu, R.; Calligaro, T.

2016-03-01

This paper reports the archaeometric investigations of 418 loose garnets from Pietroasa and Cluj-Someşeni treasures and Apahida II and III princely grave inventories (5th century AD). The chemical composition of the gems was determined by external beam micro-PIXE technique at the AGLAE accelerator of C2RMF, Paris, France. Complementary observations made by Optical Microscopy revealed details on the gemstones cutting and polishing and permitted to identify certain mineral inclusions. The compositional results evidenced several types of garnets from the pyralspite series, suggesting distinct provenances for these Early Medieval gems.

High-Performance Near-Infrared Photodetectors Based on p-type SnX (X=S, Se) Nanowires Grown via Chemical Vapor Deposition.

PubMed

Zheng, Dingshan; Fang, Hehai; Long, Mingsheng; Wu, Feng; Wang, Peng; Gong, Fan; Wu, Xing; Ho, Johnny C; Liao, Lei; Hu, Weida

2018-06-21

Because of the distinct electronic properties and strong interaction with light, quasi-one-dimensional nanowires (NWs) with semiconducting property have been demonstrated with tremendous potential for various technological applications, especially electronics and optoelectronics. However, until now, most of the state-of-the-art NW photodetectors are predominantly based on the N-type NW channel. Here, we successfully synthesized P-type SnSe and SnS NWs via chemical vapor deposition method and fabricated high-performance single SnSe and SnS NW photodetectors. Importantly, these two NW devices exhibit the impressive photodetection performance with the high photoconductive gain of 1.5 × 10 4 (2.8 × 10 4 ), good responsivity of 1.0× 10 4 A W -1 (1.6× 10 4 A W -1 ) as well as excellent detectivity of 3.3 × 10 12 Jones (2.4 × 10 12 Jones) under near-infrared illumination at a bias of 3 V for the SnSe NW (SnS NW) channel. The rise and fall times can be as efficient as 460 and 520 μs (1.2 and 15.1 ms), respectively, for the SnSe NW (SnS NW) device. Moreover, the spatially resolved photocurrent mapping of the devices further reveals the bias-dependent photocurrent generation. All these results evidently demonstrate that the P-type SnSe and SnS NWs have great potential to be applied in next-generation high-performance optoelectronic devices.

Design principles of electrical synaptic plasticity.

PubMed

O'Brien, John

2017-09-08

Essentially all animals with nervous systems utilize electrical synapses as a core element of communication. Electrical synapses, formed by gap junctions between neurons, provide rapid, bidirectional communication that accomplishes tasks distinct from and complementary to chemical synapses. These include coordination of neuron activity, suppression of voltage noise, establishment of electrical pathways that define circuits, and modulation of high order network behavior. In keeping with the omnipresent demand to alter neural network function in order to respond to environmental cues and perform tasks, electrical synapses exhibit extensive plasticity. In some networks, this plasticity can have dramatic effects that completely remodel circuits or remove the influence of certain cell types from networks. Electrical synaptic plasticity occurs on three distinct time scales, ranging from milliseconds to days, with different mechanisms accounting for each. This essay highlights principles that dictate the properties of electrical coupling within networks and the plasticity of the electrical synapses, drawing examples extensively from retinal networks. Copyright © 2017 The Author. Published by Elsevier B.V. All rights reserved.

Evidence of mantle metasomatism in garnet peridotites from V. Grib kimberlite pipe (Arkhangelsk region, Russia)

NASA Astrophysics Data System (ADS)

Shchukina, Elena; Agashev, Alexey; Golovin, Nikolai; Pokhilenko, Nikolai

2013-04-01

We have studied 26 samples of garnet peridotite xenoliths from V.Grib pipe and 17 of them are phlogopite bearing. Studied peridotites have features of two types of modal metasomatism: low-temperature (˜ 1100 C°) and high-temperature (˜ 1100 C°). Low-temperature modal metasomatism: 17 samples contain modal phlogopite, which is present in the form of tabular grains (to 3 mm in size) and rims around pyrope grains. Chemical composition of minerals from phlogopite-garnet peridotites and phlogopite free peridotites is distinctly different. Olivine, garnet, orthopyroxene and clinopyroxene have higher concentration of FeO relative to these minerals in phlogopite free peridotites. Occurrence of phlogopite in peridotites indicates the influence of melt enriched in K2O, H2O, FeO and other incompatible elements. Two types of phlogopite have difference in chemical composition that indicates two different sources. High-temperature modal metasomatism: Reconstructed V.Grib pipe peridotite whole-rocks composition and high Mg# of peridotite olivines indicates that these samples are residues after 30-40 % partial melting of primitive mantle. At those high degree of partial melting all clinopyroxene and probably all garnet should be exhausted from residue. Character of REE patterns in garnets and clinopyroxenes indicates that the most garnets and all clinopyroxene in studied peridotites are of metasomatic origin. We used the method of geochemical modeling of fractional crystallization to establish the source's composition for garnets and clinopyroxenes. For geochemical modeling we used the composition of tholeitic basalts, picrites and carbonatites which occurred in Arkhangelsk diamondiferous province (ADP) and have emplacement ages similar to that of kimberlites. Modeling result indicates that garnets could be crystallized from alkali picrite and tholeite basalts compositions. Peridotites containing garnets equilibrated with picritic melt have a different position in lithospheric mantle section from that of peridotites with tholeitic originated garnets. Two geochemically distinct types of clinopyroxenes could be the products of crystallization of tholeite basalts (type 1) and carbonatites (type 2). Overall, the lithospheric mantle beneath V. Grib kimberlite pipe experienced a complex history including multiply metasomatic events. Metasomatic agents parental to peridotitic garnets and clinopyroxenes are similar in composition to basalts and carbonatites located within the ADP indicating that magmatic events within the province are interconnected.

Mass Spectrometry Imaging and GC-MS Profiling of the Mammalian Peripheral Sensory-Motor Circuit

NASA Astrophysics Data System (ADS)

Rubakhin, Stanislav S.; Ulanov, Alexander; Sweedler, Jonathan V.

2015-06-01

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) has evolved to become an effective discovery tool in science and clinical diagnostics. Here, chemical imaging approaches are applied to well-defined regions of the mammalian peripheral sensory-motor system, including the dorsal root ganglia (DRG) and adjacent nerves. By combining several MSI approaches, analyte coverage is increased and 195 distinct molecular features are observed. Principal component analysis suggests three chemically different regions within the sensory-motor system, with the DRG and adjacent nerve regions being the most distinct. Investigation of these regions using gas chromatography-mass spectrometry corroborate these findings and reveal important metabolic markers related to the observed differences. The heterogeneity of the structurally, physiologically, and functionally connected regions demonstrates the intricate chemical and spatial regulation of their chemical composition.

Rocks of the Columbia Hills

USGS Publications Warehouse

Squyres, S. W.; Arvidson, R. E.; Blaney, D.L.; Clark, B. C.; Crumpler, L.; Farrand, W. H.; Gorevan, S.; Herkenhoff, K. E.; Hurowitz, J.; Kusack, A.; McSween, H.Y.; Ming, D. W.; Morris, R.V.; Ruff, S.W.; Wang, A.; Yen, A.

2006-01-01

The Mars Exploration Rover Spirit has identified five distinct rock types in the Columbia Hills of Gusev crater. Clovis Class rock is a poorly sorted clastic rock that has undergone substantial aqueous alteration. We interpret it to be aqueously altered ejecta deposits formed by impacts into basaltic materials. Wishstone Class rock is also a poorly sorted clastic rock that has a distinctive chemical composition that is high in Ti and P and low in Cr. Wishstone Class rock may be pyroclastic or impact in origin. Peace Class rock is a sedimentary material composed of ultramafic sand grains cemented by significant quantities of Mg- and Ca-sulfates. Peace Class rock may have formed when water briefly saturated the ultramafic sands and evaporated to allow precipitation of the sulfates. Watchtower Class rocks are similar chemically to Wishstone Class rocks and have undergone widely varying degrees of near-isochemical aqueous alteration. They may also be ejecta deposits, formed by impacts into Wishstone-rich materials and altered by small amounts of water. Backstay Class rocks are basalt/trachybasalt lavas that were emplaced in the Columbia Hills after the other rock classes were, either as impact ejecta or by localized volcanic activity. The geologic record preserved in the rocks of the Columbia Hills reveals a period very early in Martian history in which volcanic materials were widespread, impact was a dominant process, and water was commonly present. Copyright 2006 by the American Geophysical Union.

The Rocks of the Columbia Hills

NASA Technical Reports Server (NTRS)

Squyres, Steven W.; Arvidson, Raymond E.; Blaney, Diana L.; Clark, Benton C.; Crumpler, Larry; Farrand, William H.; Gorevan, Stephen; Herkenhoff, Kenneth; Hurowitz, Joel; Kusack, Alastair;

Mitochondrial and Chloroplast Stress Responses Are Modulated in Distinct Touch and Chemical Inhibition Phases1[OPEN

PubMed Central

Ivanova, Aneta; Millar, A. Harvey; Whelan, James

2016-01-01

Previous studies have identified a range of transcription factors that modulate retrograde regulation of mitochondrial and chloroplast functions in Arabidopsis (Arabidopsis thaliana). However, the relative importance of these regulators and whether they act downstream of separate or overlapping signaling cascades is still unclear. Here, we demonstrate that multiple stress-related signaling pathways, with distinct kinetic signatures, converge on overlapping gene sets involved in energy organelle function. The transcription factor ANAC017 is almost solely responsible for transcript induction of marker genes around 3 to 6 h after chemical inhibition of organelle function and is a key regulator of mitochondrial and specific types of chloroplast retrograde signaling. However, an independent and highly transient gene expression phase, initiated within 10 to 30 min after treatment, also targets energy organelle functions, and is related to touch and wounding responses. Metabolite analysis demonstrates that this early response is concurrent with rapid changes in tricarboxylic acid cycle intermediates and large changes in transcript abundance of genes encoding mitochondrial dicarboxylate carrier proteins. It was further demonstrated that transcription factors AtWRKY15 and AtWRKY40 have repressive regulatory roles in this touch-responsive gene expression. Together, our results show that several regulatory systems can independently affect energy organelle function in response to stress, providing different means to exert operational control. PMID:27208304

Functions, Compositions, and Evolution of the Two Types of Carboxysomes: Polyhedral Microcompartments That Facilitate CO2 Fixation in Cyanobacteria and Some Proteobacteria

PubMed Central

Rae, Benjamin D.; Long, Benedict M.; Badger, Murray R.

2013-01-01

SUMMARY Cyanobacteria are the globally dominant photoautotrophic lineage. Their success is dependent on a set of adaptations collectively termed the CO2-concentrating mechanism (CCM). The purpose of the CCM is to support effective CO2 fixation by enhancing the chemical conditions in the vicinity of the primary CO2-fixing enzyme, d-ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO), to promote the carboxylase reaction and suppress the oxygenase reaction. In cyanobacteria and some proteobacteria, this is achieved by encapsulation of RubisCO within carboxysomes, which are examples of a group of proteinaceous bodies called bacterial microcompartments. Carboxysomes encapsulate the CO2-fixing enzyme within the selectively permeable protein shell and simultaneously encapsulate a carbonic anhydrase enzyme for CO2 supply from a cytoplasmic bicarbonate pool. These bodies appear to have arisen twice and undergone a process of convergent evolution. While the gross structures of all known carboxysomes are ostensibly very similar, with shared gross features such as a selectively permeable shell layer, each type of carboxysome encapsulates a phyletically distinct form of RubisCO enzyme. Furthermore, the specific proteins forming structures such as the protein shell or the inner RubisCO matrix are not identical between carboxysome types. Each type has evolutionarily distinct forms of the same proteins, as well as proteins that are entirely unrelated to one another. In light of recent developments in the study of carboxysome structure and function, we present this review to summarize the knowledge of the structure and function of both types of carboxysome. We also endeavor to cast light on differing evolutionary trajectories which may have led to the differences observed in extant carboxysomes. PMID:24006469

The LIM and POU homeobox genes ttx-3 and unc-86 act as terminal selectors in distinct cholinergic and serotonergic neuron types.

PubMed

Zhang, Feifan; Bhattacharya, Abhishek; Nelson, Jessica C; Abe, Namiko; Gordon, Patricia; Lloret-Fernandez, Carla; Maicas, Miren; Flames, Nuria; Mann, Richard S; Colón-Ramos, Daniel A; Hobert, Oliver

2014-01-01

Transcription factors that drive neuron type-specific terminal differentiation programs in the developing nervous system are often expressed in several distinct neuronal cell types, but to what extent they have similar or distinct activities in individual neuronal cell types is generally not well explored. We investigate this problem using, as a starting point, the C. elegans LIM homeodomain transcription factor ttx-3, which acts as a terminal selector to drive the terminal differentiation program of the cholinergic AIY interneuron class. Using a panel of different terminal differentiation markers, including neurotransmitter synthesizing enzymes, neurotransmitter receptors and neuropeptides, we show that ttx-3 also controls the terminal differentiation program of two additional, distinct neuron types, namely the cholinergic AIA interneurons and the serotonergic NSM neurons. We show that the type of differentiation program that is controlled by ttx-3 in different neuron types is specified by a distinct set of collaborating transcription factors. One of the collaborating transcription factors is the POU homeobox gene unc-86, which collaborates with ttx-3 to determine the identity of the serotonergic NSM neurons. unc-86 in turn operates independently of ttx-3 in the anterior ganglion where it collaborates with the ARID-type transcription factor cfi-1 to determine the cholinergic identity of the IL2 sensory and URA motor neurons. In conclusion, transcription factors operate as terminal selectors in distinct combinations in different neuron types, defining neuron type-specific identity features.

Evaluating the influence of chemical weathering on the composition of the continental crust using lithium and its isotopes

NASA Astrophysics Data System (ADS)

Rudnick, R. L.; Liu, X.

2011-12-01

The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" of the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems document the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 8×10^9 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

NASA Astrophysics Data System (ADS)

Rudnick, R. L.; Liu, X. M.

2012-04-01

The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" that is the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems point to the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 1×10^10 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

Bacterial Biofilms as Complex Communities

NASA Astrophysics Data System (ADS)

Vlamakis, Hera

2010-03-01

Many microbial populations form surface-associated multicellular communities known as biofilms. These multicellular communities are encased in a self-produced extracellular matrix composed of polysaccharides and proteins. Division of labor is a key feature of these communities and different cells serve distinct functions. We have found that in biofilms of the bacterium Bacillus subtilis, different cell types including matrix-producing and sporulating cells coexist and localize to distinct regions within the structured community. We were interested in understanding how these different cell types arise. Using fluorescence reporters under the control of promoters that are specific for distinct cell types we were able to follow the dynamics of differentiation throughout biofilm development. We found that a series of extracellular signals leads to differentiation of distinct cell types during biofilm formation. In addition, we found that extracellular matrix functions as a differentiation signal for timely sporulation within a biofilm and mutants unable to produce matrix were delayed in sporulation. Our results indicate that within a biofilm, cell-cell signaling is directional in that one cell type produces a signal that is sensed by another distinct cell type. Furthermore, once differentiated, cells become resistant to the action of other signaling molecules making it possible to maintain distinct cell populations over prolonged periods.

The Mars Science Laboratory (MSL) Bagnold Dunes Campaign, Phase I: Overview and introduction to the special issue

NASA Astrophysics Data System (ADS)

Bridges, Nathan T.; Ehlmann, Bethany L.

2018-01-01

The Bagnold dunes in Gale Crater, Mars, are the first active aeolian dune field explored in situ on another planet. The Curiosity rover visited the Bagnold dune field to understand modern winds, aeolian processes, rates, and structures; to determine dune material composition, provenance, and the extent and type of compositional sorting; and to collect knowledge that informs the interpretation of past aeolian processes that are preserved in the Martian sedimentary rock record. The Curiosity rover conducted a coordinated campaign of activities lasting 4 months, interspersed with other rover activities, and employing all of the rover's science instruments and several engineering capabilities. Described in 13 manuscripts and summarized here, the major findings of the Bagnold Dunes Campaign, Phase I, include the following: the characterization of and explanation for a distinctive, meter-scale size of sinuous aeolian bedform formed in the high kinetic viscosity regime of Mars' thin atmosphere; articulation and evaluation of a grain splash model that successfully explains the occurrence of saltation even at wind speeds below the fluid threshold; determination of the dune sands' basaltic mineralogy and crystal chemistry in comparison with other soils and sedimentary rocks; and characterization of chemically distinctive volatile reservoirs in sand-sized versus dust-sized fractions of Mars soil, including two volatile-bearing types of amorphous phases.

Extraction and characterization of pectins from primary cell walls of edible açaí (Euterpe oleraceae) berries, fruits of a monocotyledon palm.

PubMed

Cantu-Jungles, Thaisa Moro; Iacomini, Marcello; Cipriani, Thales R; Cordeiro, Lucimara M C

2017-02-20

Açaí berries (Euterpe oleracea) are greatly consumed in Brazil and exported to other countries as a nutritional supplement, due to health benefits attributed to its consumption. However, the complete chemical structure of bioactive polysaccharides was not fully elucidated yet. In this work, we characterize pectic polysaccharides from açaí berries through monosaccharide composition, HPSEC, methylation and 13 C and 1 H/ 13 C HSQC-DEPT-NMR analyses. A highly methoxylated homogalacturonan with a DM of 88% and Mw of 22kDa together with small amounts of a mannoglucan were found. Moreover, a type II arabinogalactan (Mw=45kDa) containing a backbone with high portions of 6-O-linked and 3,6-O-linked Galp chains rather than 3-O-linked Galp was also isolated and structurally characterized. The type II arabinogalactan was found as a side chain of a type I rhamnogalacturonan. These findings contribute to correlate the fine chemical structure with the previously reported action of açaí polysaccharides on innate immune response. Moreover, from the taxonomic point of view, the results bring new information about polysaccharide composition of primary cell walls of palms (Arecaceae), that despite being commelinid monocots, have a distinct cell wall composition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Land-use changes influence soil bacterial communities in a meadow grassland in Northeast China

NASA Astrophysics Data System (ADS)

Cao, Chengyou; Zhang, Ying; Qian, Wei; Liang, Caiping; Wang, Congmin; Tao, Shuang

2017-10-01

The conversion of natural grassland into agricultural fields is an intensive anthropogenic perturbation commonly occurring in semiarid regions, and this perturbation strongly affects soil microbiota. In this study, the influences of land-use conversion on the soil properties and bacterial communities in the Horqin Grasslands in Northeast China were assessed. This study aimed to investigate (1) how the abundances of soil bacteria changed across land-use types, (2) how the structure of the soil bacterial community was altered in each land-use type, and (3) how these variations were correlated with soil physical and chemical properties. Variations in the diversities and compositions of bacterial communities and the relative abundances of dominant taxa were detected in four distinct land-use systems, namely, natural meadow grassland, paddy field, upland field, and poplar plantation, through the high-throughput Illumina MiSeq sequencing technique. The results indicated that land-use changes primarily affected the soil physical and chemical properties and bacterial community structure. Soil properties, namely, organic matter, pH, total N, total P, available N and P, and microbial biomass C, N, and P, influenced the bacterial community structure. The dominant phyla and genera were almost the same among the land-use types, but their relative abundances were significantly different. The effects of land-use changes on the structure of soil bacterial communities were more quantitative than qualitative.

Pharmacological Foundations of Cannabis Chemovars.

PubMed

Lewis, Mark A; Russo, Ethan B; Smith, Kevin M

2018-03-01

An advanced Mendelian Cannabis breeding program has been developed utilizing chemical markers to maximize the yield of phytocannabinoids and terpenoids with the aim to improve therapeutic efficacy and safety. Cannabis is often divided into several categories based on cannabinoid content. Type I, Δ 9 -tetrahydrocannabinol-predominant, is the prevalent offering in both medical and recreational marketplaces. In recent years, the therapeutic benefits of cannabidiol have been better recognized, leading to the promotion of additional chemovars: Type II, Cannabis that contains both Δ 9 -tetrahydrocannabinol and cannabidiol, and cannabidiol-predominant Type III Cannabis. While high- Δ 9 -tetrahydrocannabinol and high-myrcene chemovars dominate markets, these may not be optimal for patients who require distinct chemical profiles to achieve symptomatic relief. Type II Cannabis chemovars that display cannabidiol- and terpenoid-rich profiles have the potential to improve both efficacy and minimize adverse events associated with Δ 9 -tetrahydrocannabinol exposure. Cannabis samples were analyzed for cannabinoid and terpenoid content, and analytical results are presented via PhytoFacts, a patent-pending method of graphically displaying phytocannabinoid and terpenoid content, as well as scent, taste, and subjective therapeutic effect data. Examples from the breeding program are highlighted and include Type I, II, and III Cannabis chemovars, those highly potent in terpenoids in general, or single components, for example, limonene, pinene, terpinolene, and linalool. Additionally, it is demonstrated how Type I - III chemovars have been developed with conserved terpenoid proportions. Specific chemovars may produce enhanced analgesia, anti-inflammatory, anticonvulsant, antidepressant, and anti-anxiety effects, while simultaneously reducing sequelae of Δ 9 -tetrahydrocannabinol such as panic, toxic psychosis, and short-term memory impairment. Georg Thieme Verlag KG Stuttgart · New York.

Profiling of anthocyanins in transgenic purple-fleshed sweet potatoes by HPLC-MS/MS.

PubMed

Ge, Jingqiu; Hu, Yijie; Wang, Hongxia; Huang, Yuanshe; Zhang, Peng; Liao, Zhihua; Chen, Min

2017-11-01

Anthocyanins in purple-fleshed sweet potato (PSP) are beneficial to human health. The leaf color (Lc) gene is a transcription factor involved in regulating anthocyanin biosynthesis. The anthocyanin profiles of wild-type PSP of Ayamurasaki and its three Lc-transgenic lines were investigated by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). In vitro antioxidant activities of wild-type and Lc-transgenic lines, including reducing power activity, DPPH radical scavenging activity, hydroxyl radical scavenging activity, linoleic acid autoxidation inhibition activity, ABTS free radical scavenging activity and oxygen radical absorbance capacity activity, were measured. The results showed that the total anthocyanin contents increased 1.5-1.9 times in three transgenic lines compared with that in wild-type PSP. Seventeen anthocyanins were found in wild-type PSP, while 19 in Lc-transgenic lines including cyanidin-based, peonidin-based and pelargonidin-based anthocyanins. Three pelargonidin-based anthocyanins were detected in three Lc-transgenic lines. Among them, the relative contents of cyanidin-based and pelargonidin-based anthocyanins increased 1.9-2.0 and 3.4-4.5 times respectively, while peonidin-based anthocyanins decreased 1.8-1.9 times in Lc-transgenic lines, compared with wild-type PSP. PSP from wild-type Ayamurasaki and three Lc-transgenic lines exhibited potent antioxidant activities, whereas there was no distinct difference among them. The transgene Lc significantly increased the content of total anthocyanins and remarkably changed the anthocyanin profiles in Ayamurasaki. Such novel and high content of anthocyanins obtained in the Lc-transgenic lines with potent antioxidant activities may provide unique functional products with potential helpful for human health. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Pulmonary eosinophilia associated with montelukast

PubMed Central

Franco, J.; Artes, M. J.

1999-01-01

Antileukotriene drugs are new therapeutic agents that have recently been approved for the treatment of asthma. Several cases of eosinophilic conditions including Churg-Strauss syndrome have been reported to be associated with zafirlukast, a cysteinyl leukotriene type 1 receptor antagonist. So far no other leukotriene modifier has been associated with the syndrome. The case history is presented of a man with allergic rhinitis and asthma who had received intermittent pulse therapy with oral corticosteroids. Pulmonary eosinophilia developed while he was receiving treatment with montelukast, a chemically distinct cysteinyl leukotriene type 1 receptor antagonist. After discontinuation of montelukast therapy and administration of systemic corticosteroids the patient's symptoms reversed rapidly and there was prompt resolution of the pulmonary infiltrates. We believe that cysteinyl leukotriene type 1 receptor antagonists are safe and effective drugs for most patients with asthma but caution is needed for those with more severe disease who require systemic corticosteroids, especially if they show characteristics of the atypical allergic diathesis seen in the prodromal phase of Churg-Strauss syndrome.

 PMID:10335014

Vaccine-driven pharmacodynamic dissection and mitigation of Captagon psychoactivity

PubMed Central

Wenthur, Cody J; Zhou, Bin; Janda, Kim D

2017-01-01

SUMMARY PARAGRAPH Fenethylline, also known as Captagon, is a synthetic psychoactive stimulant that has recently been linked to substance use disorder and ‘pharmacoterrorism’ in the Middle East.1–4 Although fenethylline shares a common phenethylamine core with other amphetamine-type stimulants, it additionally incorporates a covalently-linked xanthine moiety into its parent structure.5,6 These independently-active pharmacophores are liberated during metabolism, resulting in a structurally-diverse chemical mixture being deployed to the central nervous system.7–9 Although fenethylline’s psychoactive properties have been reported to differ from other synthetic stimulants, the in vivo chemical complexity it manifests upon ingestion has impeded efforts to unambiguously identify the specific species responsible for these effects.10,11 Here we develop a ‘dissection through vaccination’ approach, called DISSECTIV, to mitigate fenethylline’s psychoactivity and show that its rapid-onset and distinct psychoactive properties are facilitated by functional synergy between theophylline and amphetamine. Our results demonstrate that incremental vaccination against single chemical species within a multi-component mixture can be used to uncover emergent properties arising from polypharmacologic activity. We anticipate that DISSECTIV will be employed to expose unidentified active chemical species and illuminate pharmacodynamic interactions within other chemically complex systems, such as those found in counterfeit or illegal drug preparations, post-metabolic tissue samples, and natural product extracts. PMID:28813419

Applying network analysis and Nebula (neighbor-edges based and unbiased leverage algorithm) to ToxCast data.

PubMed

Ye, Hao; Luo, Heng; Ng, Hui Wen; Meehan, Joe; Ge, Weigong; Tong, Weida; Hong, Huixiao

2016-01-01

ToxCast data have been used to develop models for predicting in vivo toxicity. To predict the in vivo toxicity of a new chemical using a ToxCast data based model, its ToxCast bioactivity data are needed but not normally available. The capability of predicting ToxCast bioactivity data is necessary to fully utilize ToxCast data in the risk assessment of chemicals. We aimed to understand and elucidate the relationships between the chemicals and bioactivity data of the assays in ToxCast and to develop a network analysis based method for predicting ToxCast bioactivity data. We conducted modularity analysis on a quantitative network constructed from ToxCast data to explore the relationships between the assays and chemicals. We further developed Nebula (neighbor-edges based and unbiased leverage algorithm) for predicting ToxCast bioactivity data. Modularity analysis on the network constructed from ToxCast data yielded seven modules. Assays and chemicals in the seven modules were distinct. Leave-one-out cross-validation yielded a Q(2) of 0.5416, indicating ToxCast bioactivity data can be predicted by Nebula. Prediction domain analysis showed some types of ToxCast assay data could be more reliably predicted by Nebula than others. Network analysis is a promising approach to understand ToxCast data. Nebula is an effective algorithm for predicting ToxCast bioactivity data, helping fully utilize ToxCast data in the risk assessment of chemicals. Published by Elsevier Ltd.

Chemical systems for improved oil recovery: Phase behavior, oil recovery, and mobility control studies

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

Llave, F.; Gall, B.; Gao, H., Scott, L., Cook, I.

Selected surfactant systems containing a series of ethoxylated nonionic surfactants in combination with an anionic surfactant system have been studied to evaluate phase behavior as well as oil recovery potential. These experiments were conducted to evaluate possible improved phase behavior and overall oil recovery potential of mixed surfactant systems over a broad range of conditions. Both polyacrylamide polymers and Xanthan biopolymers were evaluated. Studies were initiated to use a chemical flooding simulation program, UTCHEM, to simulate oil recovery for laboratory and field applications and evaluate its use to simulate oil saturation distributions obtained in CT-monitoring of oil recovery experiments. Themore » phase behavior studies focused on evaluating the effect of anionic-nonionic surfactant proportion on overall phase behavior. Two distinct transition behaviors were observed, depending on the dominant surfactant in the overall system. The first type of transition corresponded to more conventional behavior attributed to nonionic-dominant surfactant systems. This behavior is manifested by an oil-water-surfactant system that inverts from a water-external (highly conducting) microemulsion to an oil-external (nonconducting) one, as a function of temperature. The latter type which inverts in an opposite manner can be attributed to the separation of the anionic-nonionic mixtures into water- and oil-soluble surfactants. Both types of transition behavior can still be used to identify relative proximity to optimal areas. Determining these transition ranges provided more insight on how the behavior of these surfactant mixtures was affected by altering component proportions. Efforts to optimize the chemical system for oil displacement experiments were also undertaken. Phase behavior studies with systems formulated with biopolymer in solution were conducted.« less

Oxygen isotopic composition of chondritic interplanetary dust particles: A genetic link between carbonaceous chondrites and comets

NASA Astrophysics Data System (ADS)

Aléon, J.; Engrand, C.; Leshin, L. A.; McKeegan, K. D.

2009-08-01

Oxygen isotopes were measured in four chondritic hydrated interplanetary dust particles (IDPs) and five chondritic anhydrous IDPs including two GEMS-rich particles (Glass embedded with metal and sulfides) by a combination of high precision and high lateral resolution ion microprobe techniques. All IDPs have isotopic compositions tightly clustered around that of solar system planetary materials. Hydrated IDPs have mass-fractionated oxygen isotopic compositions similar to those of CI and CM carbonaceous chondrites, consistent with hydration of initially anhydrous protosolar dust. Anhydrous IDPs have small 16O excesses and depletions similar to those of carbonaceous chondrites, the largest 16O variations being hosted by the two GEMS-rich IDPs. Coarse-grained forsteritic olivine and enstatite in anhydrous IDPs are isotopically similar to their counterparts in comet Wild 2 and in chondrules suggesting a high temperature inner solar system origin. The small variations in the 16O content of GEMS-rich IDPs suggest that most GEMS either do not preserve a record of interstellar processes or the initial interstellar dust is not 16O-rich as expected by self-shielding models, although a larger dataset is required to verify these conclusions. Together with other chemical and mineralogical indicators, O isotopes show that the parent-bodies of carbonaceous chondrites, of chondritic IDPs, of most Antarctic micrometeorites, and comet Wild 2 belong to a single family of objects of carbonaceous chondrite chemical affinity as distinct from ordinary, enstatite, K- and R-chondrites. Comparison with astronomical observations thus suggests a chemical continuum of objects including main belt and outer solar system asteroids such as C-type, P-type and D-type asteroids, Trojans and Centaurs as well as short-period comets and other Kuiper Belt Objects.

A Novel Mechanism for Chemical Sensing Based on Solvent-Fluorophore-Substrate Interaction: Highly Selective Alcohol and Water Sensor with Large Fluorescence Signal Contrast.

PubMed

Chung, Kyeongwoon; Yang, Da Seul; Jung, Jaehun; Seo, Deokwon; Kwon, Min Sang; Kim, Jinsang

2016-10-06

Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.

A Comprehensive Review on Chemical Profiling of Nelumbo Nucifera: Potential for Drug Development.

PubMed

Sharma, Bhesh Raj; Gautam, Lekh Nath S; Adhikari, Deepak; Karki, Rajendra

2017-01-01

Nelumbo nucifera, also known as sacred lotus, has primarily been used as food throughout the Asian continent, and its medicinal values have been described in Ayurvedic and Traditional Chinese Medicine. The purpose of this study is to systematically characterize the chemical profiling and pharmacological activities of N. nucifera. Herein, we critically reviewed and analysed the phytochemical and pharmacological reports of N. nucifera. Our search for the keyword 'Nelumbo nucifera pharmacology' in all databases reported in Web of Science yielded 373 results excluding reviews and abstracts in document types. Two hundred and forty-three spectrum natural compounds from different parts of N. nucifera belonging to diverse chemical groups, including alkaloids, flavonoids, glycosides, terpenoids, steroids, fatty acids, proteins, minerals, and vitamins have been reported. In addition, distinct pharmacological activities, mainly against cancer, microbial infection, diabetes, inflammation, atherosclerosis, and obesity, have been associated with crude extracts, fractions, and isolated compounds. This review highlights potential use of neferine, liensinine, isoliensinine, and nuciferine in clinical trials. In depth, mechanism of the potential chemical entities from N. nucifera via structure activity relationship needs to be explored to guarantee the stability and safety for the clinical use. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

The mineralogical, chemical, and chronological characteristics of the crystalline Apollo 16 impact melt rocks

NASA Technical Reports Server (NTRS)

Reimold, W. U.; Reimold, J. N.

1984-01-01

A comparative review of mineralogical, chemical, and chronological data on crystalline Apollo 16 impact melt rocks is presented. The use of such data to identify distinct impact melt complex is discussed, and 22 distinct impact melt bodies are identified. The recently detected group of feldspathic microporphyritic (FM) melt rocks was tested for chemical and isotopic homogeneity; instrumental neutron activation analysis and new Rb-Sr isotopic whole rock data indicate that FMs were probably not derived from a single impact melt sheet, but might be representative of the Descartes basement. Stratigraphical and chronological concepts for the geological development of the landing site are discussed, and a model is presented for the formation of the Cayley Plains and the Descartes formation.

Stochastic amplification and signaling in enzymatic futile cycles through noise-induced bistability with oscillations

NASA Astrophysics Data System (ADS)

Samoilov, Michael; Plyasunov, Sergey; Arkin, Adam P.

2005-02-01

Stochastic effects in biomolecular systems have now been recognized as a major physiologically and evolutionarily important factor in the development and function of many living organisms. Nevertheless, they are often thought of as providing only moderate refinements to the behaviors otherwise predicted by the classical deterministic system description. In this work we show by using both analytical and numerical investigation that at least in one ubiquitous class of (bio)chemical-reaction mechanisms, enzymatic futile cycles, the external noise may induce a bistable oscillatory (dynamic switching) behavior that is both quantitatively and qualitatively different from what is predicted or possible deterministically. We further demonstrate that the noise required to produce these distinct properties can itself be caused by a set of auxiliary chemical reactions, making it feasible for biological systems of sufficient complexity to generate such behavior internally. This new stochastic dynamics then serves to confer additional functional modalities on the enzymatic futile cycle mechanism that include stochastic amplification and signaling, the characteristics of which could be controlled by both the type and parameters of the driving noise. Hence, such noise-induced phenomena may, among other roles, potentially offer a novel type of control mechanism in pathways that contain these cycles and the like units. In particular, observations of endogenous or externally driven noise-induced dynamics in regulatory networks may thus provide additional insight into their topology, structure, and kinetics. network motif | signal transduction | chemical reaction | synthetic biology | systems biology

Chemical characterization of the fine particle emissions from commercial aircraft engines during the Aircraft Particle Emissions eXperiment (APEX) 1 to 3.

PubMed

Kinsey, J S; Hays, M D; Dong, Y; Williams, D C; Logan, R

2011-04-15

This paper addresses the need for detailed chemical information on the fine particulate matter (PM) generated by commercial aviation engines. The exhaust plumes of seven turbofan engine models were sampled as part of the three test campaigns of the Aircraft Particle Emissions eXperiment (APEX). In these experiments, continuous measurements of black carbon (BC) and particle surface-bound polycyclic aromatic compounds (PAHs) were conducted. In addition, time-integrated sampling was performed for bulk elemental composition, water-soluble ions, organic and elemental carbon (OC and EC), and trace semivolatile organic compounds (SVOCs). The continuous BC and PAH monitoring showed a characteristic U-shaped curve of the emission index (EI or mass of pollutant/mass of fuel burned) vs fuel flow for the turbofan engines tested. The time-integrated EIs for both elemental composition and water-soluble ions were heavily dominated by sulfur and SO(4)(2-), respectively, with a ∼2.4% median conversion of fuel S(IV) to particle S(VI). The corrected OC and EC emission indices obtained in this study ranged from 37 to 83 mg/kg and 21 to 275 mg/kg, respectively, with the EC/OC ratio ranging from ∼0.3 to 7 depending on engine type and test conditions. Finally, the particle SVOC EIs varied by as much as 2 orders of magnitude with distinct variations in chemical composition observed for different engine types and operating conditions.

Predicting long-range transport: a systematic evaluation of two multimedia transport models.

PubMed

Bennett, D H; Scheringer, M; McKone, T E; Hungerbühler, K

2001-03-15

The United Nations Environment Program has recently developed criteria to identify and restrict chemicals with a potential for persistence and long-range transport (persistent organic pollutants or POPs). There are many stakeholders involved, and the issues are not only scientific but also include social, economic, and political factors. This work focuses on one aspect of the POPs debate, the criteria for determining the potential for long-range transport (LRT). Our goal is to determine if current models are reliable enough to support decisions that classify a chemical based on the LRT potential. We examine the robustness of two multimedia fate models for determining the relative ranking and absolute spatial range of various chemicals in the environment. We also consider the effect of parameter uncertainties and the model uncertainty associated with the selection of an algorithm for gas-particle partitioning on the model results. Given the same chemical properties, both models give virtually the same ranking. However, when chemical parameter uncertainties and model uncertainties such as particle partitioning are considered, the spatial range distributions obtained for the individual chemicals overlap, preventing a distinct rank order. The absolute values obtained for the predicted spatial range or travel distance differ significantly between the two models for the uncertainties evaluated. We find that to evaluate a chemical when large and unresolved uncertainties exist, it is more informative to use two or more models and include multiple types of uncertainty. Model differences and uncertainties must be explicitly confronted to determine how the limitations of scientific knowledge impact predictions in the decision-making process.

An Apollo 15 Mare Basalt Fragment and Lunar Mare Provinces

NASA Technical Reports Server (NTRS)

Ryder, Graham; Burling, Trina Cox

1996-01-01

Lunar sample 15474,4 is a tiny fragment of olivine-augite vitrophyre that is a mare basalt. Although petroraphically distinct from all other Apollo 15 samples, it has been ignored since its first brief description. Our new petrographic and mineral chemical data show that the olivines and pyroxenes are distinct from those in other basalts. The basalt cooled and solidified extremely rapidly; some of the olivine might be cumulate or crystallized prior to extrusion. Bulk-chemical data show that the sample is probably similar to an evolved Apollo 15 olivine-normative basalt in major elements but is distinct in its rare earth element pattern. Its chemical composition and petrography both show that 15474,4 cannot be derived from other Apollo 15 mare basalts by shallow-level crystal fractionation. It represents a distinct extrusion of magma. Nonetheless, the chemical features that 15474,4 has in common with other Apollo 15 mare basalts, including the high FeO/Sc, the general similarity of the rare earth element pattern, and the common (and chondritic) TiO2/Sm ratio, emphasize the concept of a geochemical province at the Apollo 15 site that is distinct from basalts and provinces elsewhere. In making a consistent picture for the derivation of all of the Apollo 15 basalts, both the commonalities and the differences among the basalts must be explained. The Apollo 15 commonalities and differences suggest that the sources must have consisted of major silicate phases with the same composition but with varied amounts of a magma trapped from a contemporary magma ocean. They probably had a high olivine/pyroxene ratio and underwent small and reasonably consistent degrees of partial melting to produce the basalts. These inferences may be inconsistent with models that suggest greatly different depths of melting among basalts, primitive sources for the green glasses, or extensive olivine fractionation during ascent. An integrated approach to lunar mare provinces, of which the Apollo 15 mare basalts constitute only one, offers advances in our understanding of the physical and chemical processes of source formation and mare production but has so far not been utilized.

Defensive strategies in Geranium sylvaticum. Part 1: organ-specific distribution of water-soluble tannins, flavonoids and phenolic acids.

PubMed

Tuominen, Anu; Toivonen, Eija; Mutikainen, Pia; Salminen, Juha-Pekka

2013-11-01

A combination of high-resolution mass spectrometry and modern HPLC column technology, assisted by diode array detection, was used for accurate characterization of water-soluble polyphenolic compounds in the pistils, stamens, petals, sepals, stems, leaves, roots and seeds of Geranium sylvaticum. The organs contained a large variety of polyphenols, five types of tannins (ellagitannins, proanthocyanidins, gallotannins, galloyl glucoses and galloyl quinic acids) as well as flavonoids and simple phenolic acids. In all, 59 compounds were identified. Geraniin and other ellagitannins dominated in all the green photosynthetic organs. The other organs seem to produce distinctive polyphenol groups: pistils accumulated gallotannins; petals acetylglucose derivatives of galloylglucoses; stamens kaempferol glycosides, and seeds and roots accumulated proanthocyanidins. The intra-plant distribution of the different polyphenol groups may reflect the different functions and importance of various types of tannins as the defensive chemicals against herbivory. Copyright © 2013 Elsevier Ltd. All rights reserved.

Near-infrared spectroscopy of primitive solar system objects

NASA Technical Reports Server (NTRS)

Luu, Jane; Jewitt, David; Cloutis, Edward

1994-01-01

We have obtained near-infrared (H and K band at lambda/Delta(lambda) is approximately 480 to 600) spectra of a sample of primitive objects including 2 Centaur objects (2060 Chiron and 5145 Pholus) and 16 P- and D-type asteroids. The spectra were obtained at the United Kingdom Infrared Telescope using the cooled grating spectrometer CGS4, and were used to search for chemically diagnostic vibrational features in these primitive objects. Pholus exhibits broad adsorption features at 2.07 and 2.27 micrometers, as well as a weak feature at 1.72 micrometers. The 1.72- and 2.27-micrometer features are similar to those seen in a laboratory tar sand sample. No distinct absorption features are found in other objects, including Chiron, which displays a spectrally neutral continuum. A comparison of the P- and D-type asteroid spectra with laboratory measurements of organic solids shows no compelling evidence for hydrocarbon overtones seen in terrestrial bituminous tar sands.

Fate and Behavior of Gunshot Residue-A Review.

PubMed

Blakey, Lauren S; Sharples, George P; Chana, Kal; Birkett, Jason W

2018-01-01

A review of the literature concerning the fate and behavior of gunshot residue (GSR) is presented. A number of concomitant parameters including firearm and ammunition type, plume and GSR material characteristics, travel distances, chemical composition and GSR morphology are critically discussed in relation to their effects on the distribution and deposition, transfer and persistence processes of GSR. The underlying mechanisms associated with such processes are also considered. Knowledge of these processes on GSR materials could provide valuable information concerning scene preservation and subsequent forensic sampling. The number of GSR particles deposited can vary significantly with each firearm discharge, highlighting the potential to produce distinctive data in each individual case. With the continual development and compositional changes of new ammunition types, further evaluation of the effect these processes may have on GSR evidence and their possible influence on the interpretation of the analytical results should be given due consideration. © 2017 American Academy of Forensic Sciences.

Noncovalent Molecular Electronics.

PubMed

Gryn'ova, G; Corminboeuf, C

2018-05-03

Molecular electronics covers several distinctly different conducting architectures, including organic semiconductors and single-molecule junctions. The noncovalent interactions, abundant in the former, are also often found in the latter, i.e., the dimer junctions. In the present work, we draw the parallel between the two types of noncovalent molecular electronics for a range of π-conjugated heteroaromatic molecules. In silico modeling allows us to distill the factors that arise from the chemical nature of their building blocks and from their mutual arrangement. We find that the same compounds are consistently the worst and the best performers in the two types of electronic assemblies, emphasizing the universal imprint of the underlying chemistry of the molecular cores on their diverse charge transport characteristics. The interplay between molecular and intermolecular factors creates a spectrum of noncovalent conductive architectures, which can be manipulated using the design strategies based upon the established relationships between chemistry and transport.

Room temperature electroluminescence from the n-ZnO/p-GaN heterojunction device grown by MOCVD

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

Yang, T.P.; Zhu, H.C.; Bian, J.M.

2008-12-01

The heterojunction light-emitting diode with n-ZnO/p-GaN structure was grown on (0 0 0 1) sapphire substrate by metalorganic chemical vapor deposition (MOCVD) technique. The heterojunction structure was consisted of an Mg-doped p-type GaN layer with a hole concentration of {approx}10{sup 17} cm{sup -3} and a unintentionally doped n-type ZnO layer with an electron concentration of {approx}10{sup 18} cm{sup -3}. A distinct blue-violet electroluminescence with a dominant emission peak centered at {approx}415 nm was observed at room temperature from the heterojunction structure under forward bias conditions. The origins of the electroluminescence (EL) emissions are discussed in comparison with the photoluminescence spectra,more » and it was supposed to be attributed to a radiative recombination in both n-ZnO and p-GaN sides.« less

Distinctive Solvation Patterns Make Renal Osmolytes Diverse

PubMed Central

Jackson-Atogi, Ruby; Sinha, Prem Kumar; Rösgen, Jörg

2013-01-01

The kidney uses mixtures of five osmolytes to counter the stress induced by high urea and NaCl concentrations. The individual roles of most of the osmolytes are unclear, and three of the five have not yet been thermodynamically characterized. Here, we report partial molar volumes and activity coefficients of glycerophosphocholine (GPC), taurine, and myo-inositol. We derive their solvation behavior from the experimental data using Kirkwood-Buff theory. We also provide their solubility data, including solubility data for scyllo-inositol. It turns out that renal osmolytes fall into three distinct classes with respect to their solvation. Trimethyl-amines (GPC and glycine-betaine) are characterized by strong hard-sphere-like self-exclusion; urea, taurine, and myo-inositol have a tendency toward self-association; sorbitol and most other nonrenal osmolytes have a relatively constant, intermediate solvation that has components of both exclusion and association. The data presented here show that renal osmolytes are quite diverse with respect to their solvation patterns, and they can be further differentiated based on observations from experiments examining their effect on macromolecules. It is expected, based on the available surface groups, that each renal osmolyte has distinct effects on various classes of biomolecules. This likely allows the kidney to use specific combinations of osmolytes independently to fine-tune the chemical activities of several types of molecules. PMID:24209862

Heritability of Nociception IV: Neuropathic pain assays are genetically distinct across methods of peripheral nerve injury

PubMed Central

Young, Erin E.; Costigan, Michael; Herbert, Teri A.; Lariviere, William R.

2013-01-01

Prior genetic correlation analysis of 22 heritable behavioral measures of nociception and hypersensitivity in the mouse identified five genetically distinct pain types. In the present study, we reanalyzed that dataset and included the results of an additional nine assays of nociception and hypersensitivity to: 1) replicate the previously identified five pain types; 2) test whether any of the newly added pain assays represent novel genetically distinct pain types; 3) test the level of genetic relatedness among nine commonly employed neuropathic pain assays. Multivariate analysis of pairwise correlations between assays shows that the newly added zymosan-induced heat hypersensitivity assay does not conform to the two previously identified groups of heat hypersensitivity assays and cyclophosphamide-induced cystitis, the first organ-specific visceral pain model examined, is genetically distinct from other inflammatory assays. The four included mechanical hypersensitivity assays are genetically distinct, and do not comprise a single pain type as previously reported. Among the nine neuropathic pain assays including autotomy, chemotherapy, nerve ligation and spared nerve injury assays, at least four genetically distinct types of neuropathic sensory abnormalities were identified, corresponding to differences in nerve injury method. In addition, two itch assays and Comt genotype were compared to the expanded set of nociception and hypersensitivity assays. Comt genotype was strongly related only to spontaneous inflammatory nociception assays. These results indicate the priority for continued investigation of genetic mechanisms in several assays newly identified to represent genetically distinct pain types. PMID:24071598

Symbiotic Cell Differentiation and Cooperative Growth in Multicellular Aggregates

PubMed Central

Yamagishi, Jumpei F; Saito, Nen; Kaneko, Kunihiko

2016-01-01

As cells grow and divide under a given environment, they become crowded and resources are limited, as seen in bacterial biofilms and multicellular aggregates. These cells often show strong interactions through exchanging chemicals, as evident in quorum sensing, to achieve mutualism and division of labor. Here, to achieve stable division of labor, three characteristics are required. First, isogenous cells differentiate into several types. Second, this aggregate of distinct cell types shows better growth than that of isolated cells without interaction and differentiation, by achieving division of labor. Third, this cell aggregate is robust with respect to the number distribution of differentiated cell types. Indeed, theoretical studies have thus far considered how such cooperation is achieved when the ability of cell differentiation is presumed. Here, we address how cells acquire the ability of cell differentiation and division of labor simultaneously, which is also connected with the robustness of a cell society. For this purpose, we developed a dynamical-systems model of cells consisting of chemical components with intracellular catalytic reaction dynamics. The reactions convert external nutrients into internal components for cellular growth, and the divided cells interact through chemical diffusion. We found that cells sharing an identical catalytic network spontaneously differentiate via induction from cell-cell interactions, and then achieve division of labor, enabling a higher growth rate than that in the unicellular case. This symbiotic differentiation emerged for a class of reaction networks under the condition of nutrient limitation and strong cell-cell interactions. Then, robustness in the cell type distribution was achieved, while instability of collective growth could emerge even among the cooperative cells when the internal reserves of products were dominant. The present mechanism is simple and general as a natural consequence of interacting cells with limited resources, and is consistent with the observed behaviors and forms of several aggregates of unicellular organisms. PMID:27749898

Micrometer- and nanometer-sized platinum group nuggets in micrometeorites from deep-sea sediments of the Indian Ocean

NASA Astrophysics Data System (ADS)

Rudraswami, N. G.; Parashar, K.; Shyam Prasad, M.

2011-03-01

We examined 378 micrometeorites collected from deep-sea sediments of the Indian Ocean of which 175, 180, and 23 are I-type, S-type, and G-type, respectively. Of the 175 I-type spherules, 13 contained platinum group element nuggets (PGNs). The nuggets occur in two distinct sizes and have distinctly different elemental compositions: micrometer (μm)-sized nuggets that are >3 μm contain dominantly Ir, Os, and Ru (iridium-platinum group element or IPGE) and sub-μm (or nanometer)-sized (<1 μm) nuggets, which contain dominantly Pt, Rh, and Pd (palladium—PGE or PPGE). The μm-sized nuggets are found only one per spherule in the cross section observed and are usually found at the edge of the spherule. By contrast, there are hundreds of nanometer-sized nuggets distributed dominantly in the magnetite phases of the spherules, and rarely in the wüstite phases. Both the nugget types are found as separate entities in the same spherule and apparently, nugget formation is a common phenomenon among I-type micrometeorites. However, the μm-sized nuggets are seen in fewer specimens (˜2.5% of the observed I-type spherules). In all, we analyzed four nuggets of μm size and 213 nanometer-sized nuggets from 13 I-type spherules for platinum group elements. Chemically, the μm-sized PGNs contain chondritic ratios of Os/Ir, but are depleted in the more volatile PGE (Pt, Rh, and Pd) relative to chondritic ratios. On the other hand, the nanometer-sized nuggets contain dominantly Pt and Rh. Importantly, the refractory PGEs are conspicuous by their absence in these nanometer nuggets. Palladium, the most volatile PGE is highly depleted (<1.1%) with respect to chondritic ratios in the μm-sized PGNs, and is observed in only 17 of 213 nanometer nuggets with concentrations that are just above the detection limit (≥0.2%). Distinct fractionation of the PGE into IPGE (Ir, Os, Ru) and PPGE seems to take place during the short span of atmospheric entry. These observations suggest several implications: (1) The observation of fractionated PGE in an Fe-Ni system gives rise to the possibility that Earth’s core could contain fractionated PGE. (2) The present data support the processes suggested for the fractionated PGE patterns observed in the ejecta of ancient meteorite impacts. (3) Meteoric metals released in the troposphere could contain fractionated PGNs in large numbers.

Chemistry supports the identification of gender-specific reproductive tissue in Tyrannosaurus rex

PubMed Central

Schweitzer, Mary Higby; Zheng, Wenxia; Zanno, Lindsay; Werning, Sarah; Sugiyama, Toshie

2016-01-01

Medullary bone (MB), an estrogen-dependent reproductive tissue present in extant gravid birds, is texturally, histologically and compositionally distinct from other bone types. Phylogenetic proximity led to the proposal that MB would be present in non-avian dinosaurs, and recent studies have used microscopic, morphological, and regional homologies to identify this reproductive tissue in both theropod and ornithischian dinosaurs. Here, we capitalize on the unique chemical and histological fingerprint of MB in birds to characterize, at the molecular level, MB in the non-avian theropod Tyrannosaurus rex (MOR 1125), and show that the retention of original molecular components in fossils allows deeper physiological and evolutionary questions to be addressed. PMID:26975806

Discovery of Novel Tricyclic Heterocycles as Potent and Selective DPP-4 Inhibitors for the Treatment of Type 2 Diabetes

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

Wu, Wen-Lian; Hao, Jinsong; Domalski, Martin

In our efforts to develop second generation DPP-4 inhibitors, we endeavored to identify distinct structures with long-acting (once weekly) potential. Taking advantage of X-ray cocrystal structures of sitagliptin and other DPP-4 inhibitors, such as alogliptin and linagliptin bound to DPP-4, and aided by molecular modeling, we designed several series of heterocyclic compounds as initial targets. During their synthesis, an unexpected chemical transformation provided a novel tricyclic scaffold that was beyond our original design. Capitalizing on this serendipitous discovery, we have elaborated this scaffold into a very potent and selective DPP-4 inhibitor lead series, as highlighted by compound 17c.

Chemistry supports the identification of gender-specific reproductive tissue in Tyrannosaurus rex.

PubMed

Schweitzer, Mary Higby; Zheng, Wenxia; Zanno, Lindsay; Werning, Sarah; Sugiyama, Toshie

2016-03-15

Medullary bone (MB), an estrogen-dependent reproductive tissue present in extant gravid birds, is texturally, histologically and compositionally distinct from other bone types. Phylogenetic proximity led to the proposal that MB would be present in non-avian dinosaurs, and recent studies have used microscopic, morphological, and regional homologies to identify this reproductive tissue in both theropod and ornithischian dinosaurs. Here, we capitalize on the unique chemical and histological fingerprint of MB in birds to characterize, at the molecular level, MB in the non-avian theropod Tyrannosaurus rex (MOR 1125), and show that the retention of original molecular components in fossils allows deeper physiological and evolutionary questions to be addressed.

Tunable Quantum Spin Liquidity in the 1 /6 th-Filled Breathing Kagome Lattice

NASA Astrophysics Data System (ADS)

Akbari-Sharbaf, A.; Sinclair, R.; Verrier, A.; Ziat, D.; Zhou, H. D.; Sun, X. F.; Quilliam, J. A.

2018-06-01

We present measurements on a series of materials, Li2 In1 -xScx Mo3 O8 , that can be described as a 1 /6 th-filled breathing kagome lattice. Substituting Sc for In generates chemical pressure which alters the breathing parameter nonmonotonically. Muon spin rotation experiments show that this chemical pressure tunes the system from antiferromagnetic long range order to a quantum spin liquid phase. A strong correlation with the breathing parameter implies that it is the dominant parameter controlling the level of magnetic frustration, with increased kagome symmetry generating the quantum spin liquid phase. Magnetic susceptibility measurements suggest that this is related to distinct types of charge order induced by changes in lattice symmetry, in line with the theory of Chen et al. [Phys. Rev. B 93, 245134 (2016), 10.1103/PhysRevB.93.245134]. The specific heat for samples at intermediate Sc concentration, which have the minimum breathing parameter, show consistency with the predicted U (1 ) quantum spin liquid.

Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment

DOE PAGES

Liu, Xing-Wu; Cao, Zhi; Zhao, Shu; ...

2017-09-11

As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2C and ε’-Fe 2.2C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe xC, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectramore » for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2C has six sets of chemically distinct Fe atoms.« less

Quantitative and qualitative shifts in defensive metabolites define chemical defense investment during leaf development in Inga, a genus of tropical trees.

PubMed

Wiggins, Natasha L; Forrister, Dale L; Endara, María-José; Coley, Phyllis D; Kursar, Thomas A

2016-01-01

Selective pressures imposed by herbivores are often positively correlated with investments that plants make in defense. Research based on the framework of an evolutionary arms race has improved our understanding of why the amount and types of defenses differ between plant species. However, plant species are exposed to different selective pressures during the life of a leaf, such that expanding leaves suffer more damage from herbivores and pathogens than mature leaves. We hypothesize that this differential selective pressure may result in contrasting quantitative and qualitative defense investment in plants exposed to natural selective pressures in the field. To characterize shifts in chemical defenses, we chose six species of Inga, a speciose Neotropical tree genus. Focal species represent diverse chemical, morphological, and developmental defense traits and were collected from a single site in the Amazonian rainforest. Chemical defenses were measured gravimetrically and by characterizing the metabolome of expanding and mature leaves. Quantitative investment in phenolics plus saponins, the major classes of chemical defenses identified in Inga, was greater for expanding than mature leaves (46% and 24% of dry weight, respectively). This supports the theory that, because expanding leaves are under greater selective pressure from herbivores, they rely more upon chemical defense as an antiherbivore strategy than do mature leaves. Qualitatively, mature and expanding leaves were distinct and mature leaves contained more total and unique metabolites. Intraspecific variation was greater for mature leaves than expanding leaves, suggesting that leaf development is canalized. This study provides a snapshot of chemical defense investment in a speciose genus of tropical trees during the short, few-week period of leaf development. Exploring the metabolome through quantitative and qualitative profiling enables a more comprehensive examination of foliar chemical defense investment.

Shining light on the differences in molecular structural chemical makeup and the cause of distinct degradation behavior between malting- and feed-type barley using synchrotron FTIR microspectroscopy: a novel approach.

PubMed

Yu, Peiqiang; Doiron, Kevin; Liu, Dasen

2008-05-14

The objective of this study was to use advanced synchrotron-sourced FTIR microspectroscopy (SFTIRM) as a novel approach to identify the differences in protein and carbohydrate molecular structure (chemical makeup) between these two varieties of barley and illustrate the exact causes for their significantly different degradation kinetics. Items assessed included (1) molecular structural differences in protein amide I to amide II intensities and their ratio within cellular dimensions, (2) molecular structural differences in protein secondary structure profile and their ratios, and (3) molecular structural differences in carbohydrate component peak profile. Our hypothesis was that molecular structure (chemical makeup) affects barley quality, fermentation, and degradation behavior in both humans and animals. Using SFTIRM, the protein and carbohydrate molecular structural chemical makeup of barley was revealed and identified. The protein molecular structural chemical makeup differed significantly between the two varieties of barleys. No difference in carbohydrate molecular structural chemical makeup was detected. Harrington was lower than Valier in protein amide I, amide II, and protein amide I to amide II ratio, while Harrington was relatively higher in model-fitted protein alpha-helix and beta-sheet, but lower in the others (beta-turn and random coil). These results indicated that it is the molecular structure of protein (chemical makeup) that may play a major role in the different degradation kinetics between the two varieties of barleys (not the molecular structure of carbohydrate). It is believed that use of the advanced synchrotron technology will make a significant step and an important contribution to research in examining the molecular structure (chemical makeup) of plant, feed, and seeds.

Cp[prime]M(NO)R[sub 2]: 16-electron piano-stool molecules of molybdenum and tungsten

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

Legzdins, P.; Veltheer, J.E.

1993-02-01

A long-term goal of this research program is the development of organometallic nitrosyl complexes as specific reactants or selective catalysts for organic or organometallic transformations of practical significance. To attain this goal specifically with Cp[prime]M(NO)R[sub 2] system the authors developed new methods for their synthesis, established their characteristic physical and chemical properties, and are currently endeavoring to exploit those properties which are unique to the complexes. During our investigations, the authors have discovered that the Cp[prime]M(NO)R[sub 2] complexes react with a variety of small molecules, often in an unprecedented manner. The authors have also established several unique transformations that aremore » not exhibited by all members of this group of complexes. Indeed, the authors found that the chemical properties of these systems are often dependent on the metal, the nature of the R groups, and the type of Cp[prime] ligand. In this Account the authors summarize the synthesis, characterization, comparative reactivity, and distinctive chemical properties of the 16-electron Cp[prime]M(NO)R[sub 2] complexes known to date. 35 refs., 7 figs.« less

The Crystal-Chemical Effect of REE Separation in Minerals: Causes and Practical Values

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.

2018-03-01

Contrast variations in the type of REE distribution from a distinctly negative mode to a positive mode is revealed in zonal fluorites of Eastern Transbaikal, with a pronounced decrease in the Ce/Y ratios in successive zones of increasing Y accompanied by a gradual decrease in the temperature and salinity of fluid inclusions in the fluorites. It is assumed that these facts are caused by the appearance of nm-size phases of REE minerals characterized by various crystalline structures and demonstrating selective concentrations of lanthanides, i.e., exhibiting a crystal-chemical differentiation of REEs that is widespread in the processes of mineral formation. Based on this natural mechanism, the development of a procedure of selective REE extraction from the concentrates is proposed. The primary laboratory experiments resulted in the discovery of the difference in REE concentrations in the sediment and filtrate with the separation coefficient varying by a factor of 76. The results obtained allow one to expect a true separation possibility for Nd along with the medium and heavy REEs. In view of the data obtained, the crystalline-chemical separation of REEs has some advantages compared to the processes currently used, especially extraction.

A mineralogical study in contrasts: highly mineralized whale rostrum and human enamel

NASA Astrophysics Data System (ADS)

Li, Zhen; Ai-Jawad, Maisoon; Siddiqui, Samera; Pasteris, Jill D.

2015-11-01

The outermost enamel of the human tooth and the rostrum of the whale Mesoplodon densirostris are two highly mineralized tissues that contain over 95 wt.% mineral, i.e., bioapatite. However, the same mineral type (carbonated hydroxylapatite) does not yield the same material properties, as revealed by Raman spectroscopy, scanning electron microscopy, electron microprobe analysis, and synchrotron X-ray diffraction analysis. Overall, the outermost enamel of a tooth has more homogeneous physical and chemical features than the rostrum. Chemical comparison of rostrum and enamel shows bioapatite in the rostrum to be enriched in Na, Mg, CO3, and S, whereas the outermost enamel shows only a slightly enriched Cl concentration. Morphologically, mineral rods (at tens of μm scale), crystallites and prisms (at μm and sub-μm scale), and platelets (at tens of nm scale) all demonstrate less organized texture in the rostrum than in enamel. Such contrasts between two mineralized tissues suggest distinct pathways of biomineralization, e.g., the nature of the equilibrium between mineral and body fluid. This study illustrates the remarkable flexibility of the apatite mineral structure to match its chemical and physical properties to specific biological needs within the same animal or between species.

Chemical synapses without synaptic vesicles: Purinergic neurotransmission through a CALHM1 channel-mitochondrial signaling complex.

PubMed

Romanov, Roman A; Lasher, Robert S; High, Brigit; Savidge, Logan E; Lawson, Adam; Rogachevskaja, Olga A; Zhao, Haitian; Rogachevsky, Vadim V; Bystrova, Marina F; Churbanov, Gleb D; Adameyko, Igor; Harkany, Tibor; Yang, Ruibiao; Kidd, Grahame J; Marambaud, Philippe; Kinnamon, John C; Kolesnikov, Stanislav S; Finger, Thomas E

2018-05-08

Conventional chemical synapses in the nervous system involve a presynaptic accumulation of neurotransmitter-containing vesicles, which fuse with the plasma membrane to release neurotransmitters that activate postsynaptic receptors. In taste buds, type II receptor cells do not have conventional synaptic features but nonetheless show regulated release of their afferent neurotransmitter, ATP, through a large-pore, voltage-gated channel, CALHM1. Immunohistochemistry revealed that CALHM1 was localized to points of contact between the receptor cells and sensory nerve fibers. Ultrastructural and super-resolution light microscopy showed that the CALHM1 channels were consistently associated with distinctive, large (1- to 2-μm) mitochondria spaced 20 to 40 nm from the presynaptic membrane. Pharmacological disruption of the mitochondrial respiratory chain limited the ability of taste cells to release ATP, suggesting that the immediate source of released ATP was the mitochondrion rather than a cytoplasmic pool of ATP. These large mitochondria may serve as both a reservoir of releasable ATP and the site of synthesis. The juxtaposition of the large mitochondria to areas of membrane displaying CALHM1 also defines a restricted compartment that limits the influx of Ca 2+ upon opening of the nonselective CALHM1 channels. These findings reveal a distinctive organelle signature and functional organization for regulated, focal release of purinergic signals in the absence of synaptic vesicles. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Cannabis - from cultivar to chemovar.

PubMed

Hazekamp, A; Fischedick, J T

2012-01-01

The medicinal use of Cannabis is increasing as countries worldwide are setting up official programs to provide patients with access to safe sources of medicinal-grade Cannabis. An important question that remains to be answered is which of the many varieties of Cannabis should be made available for medicinal use. Drug varieties of Cannabis are commonly distinguished through the use of popular names, with a major distinction being made between Indica and Sativa types. Although more than 700 different cultivars have already been described, it is unclear whether such classification reflects any relevant differences in chemical composition. Some attempts have been made to classify Cannabis varieties based on chemical composition, but they have mainly been useful for forensic applications, distinguishing drug varieties, with high THC content, from the non-drug hemp varieties. The biologically active terpenoids have not been included in these approaches. For a clearer understanding of the medicinal properties of the Cannabis plant, a better classification system, based on a range of potentially active constituents, is needed. The cannabinoids and terpenoids, present in high concentrations in Cannabis flowers, are the main candidates. In this study, we compared cultivars obtained from multiple sources. Based on the analysis of 28 major compounds present in these samples, followed by principal component analysis (PCA) of the quantitative data, we were able to identify the Cannabis constituents that defined the samples into distinct chemovar groups. The study indicates the usefulness of a PCA approach for chemotaxonomic classification of Cannabis varieties. Copyright © 2012 John Wiley & Sons, Ltd.

Formation and Preservation of the Depleted and Enriched Shergottite Isotopic Reservoirs in a Convecting Martian Mantle

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Jones, John H.

2015-01-01

There is compelling isotopic and crater density evidence for geologically recent volcanism on Mars, in the last 100-200 million years and possibly in the last 50 million years. This volcanism is due to adiabatic decompression melting and thus requires some type of present-day convective upwelling in the martian mantle. On the other hand, martian meteorites preserve evidence for at least 3 distinct radiogenic isotopic reservoirs. Anomalies in short-lived isotopic systems (Sm-146, Nd-142, Hf-182, W-182) require that these reservoirs must have developed in the first 50 to 100 million years of Solar System history. The long-term preservation of chemically distinct reservoirs has sometimes been interpreted as evidence for the absence of mantle convection and convective mixing on Mars for most of martian history, a conclusion which is at odds with the evidence for young volcanism. This apparent paradox can be resolved by recognizing that a variety of processes, including both inefficient mantle mixing and geographic separation of isotopic reservoirs, may preserve isotopic heterogeneity on Mars in an actively convecting mantle. Here, we focus on the formation and preservation of the depleted and enriched isotopic and trace element reservoirs in the shergottites. In particular, we explore the possible roles of processes such as chemical diffusion and metasomatism in dikes and magma chambers for creating the isotopically enriched shergottites. We also consider processes that may preserve the enriched reservoir against convective mixing for most of martian history.

A diversity-oriented synthesis strategy enabling the combinatorial-type variation of macrocyclic peptidomimetic scaffolds.

PubMed

Isidro-Llobet, Albert; Hadje Georgiou, Kathy; Galloway, Warren R J D; Giacomini, Elisa; Hansen, Mette R; Méndez-Abt, Gabriela; Tan, Yaw Sing; Carro, Laura; Sore, Hannah F; Spring, David R

2015-04-21

Macrocyclic peptidomimetics are associated with a broad range of biological activities. However, despite such potentially valuable properties, the macrocyclic peptidomimetic structural class is generally considered as being poorly explored within drug discovery. This has been attributed to the lack of general methods for producing collections of macrocyclic peptidomimetics with high levels of structural, and thus shape, diversity. In particular, there is a lack of scaffold diversity in current macrocyclic peptidomimetic libraries; indeed, the efficient construction of diverse molecular scaffolds presents a formidable general challenge to the synthetic chemist. Herein we describe a new, advanced strategy for the diversity-oriented synthesis (DOS) of macrocyclic peptidomimetics that enables the combinatorial variation of molecular scaffolds (core macrocyclic ring architectures). The generality and robustness of this DOS strategy is demonstrated by the step-efficient synthesis of a structurally diverse library of over 200 macrocyclic peptidomimetic compounds, each based around a distinct molecular scaffold and isolated in milligram quantities, from readily available building-blocks. To the best of our knowledge this represents an unprecedented level of scaffold diversity in a synthetically derived library of macrocyclic peptidomimetics. Cheminformatic analysis indicated that the library compounds access regions of chemical space that are distinct from those addressed by top-selling brand-name drugs and macrocyclic natural products, illustrating the value of our DOS approach to sample regions of chemical space underexploited in current drug discovery efforts. An analysis of three-dimensional molecular shapes illustrated that the DOS library has a relatively high level of shape diversity.

PROGRAM FOR THE IDENTIFICATION AND REPLACEMENT OF ENDOCRINE DISRUPTING CHEMICALS

EPA Science Inventory

A computer software program is being developed to aid in the identification and replacement of endocrine disrupting chemicals (EDC). This program will be comprised of two distinct areas of research: identification of potential EDC nd suggstions for replacing those potential EDC. ...

Investigation of Thermophysical Properties of Thermal Degraded Biodiesels

NASA Astrophysics Data System (ADS)

Regatieri, H. R.; Savi, E. L.; Lukasievicz, G. V. B.; Sehn, E.; Herculano, L. S.; Astrath, N. G. C.; Malacarne, L. C.

2018-06-01

Biofuels are an alternative to fossil fuels and can be made from many different raw materials. The use of distinct catalyst and production processes, feedstocks, and types of alcohol results in biofuels with different physical and chemical properties. Even though these diverse options for biodiesel production are considered advantageous, they may pose a setback when quality specifications are considered, since different properties are subject to different reactions during usage, storage and handling. In this work, we present a systematic characterization of biodiesels to investigate how accelerated thermal degradation affects fuel properties. Two different types of biodiesel, commercially obtained from distinct feedstocks, were tested. The thermal degradation process was performed by maintaining the temperature of the sample at 140°C under constant air flux for different times: 0 h, 3 h, 6 h, 9 h, 12 h, 24 h and 36 h. Properties such as density, viscosity, activation energy, volumetric thermal expansion coefficient, gross caloric value, acid value, infrared absorption, and temperature coefficient of the refractive index were used to study the thermal degradation of the biodiesel samples. The results show a significant difference in fuel properties before and after the thermal degradation process suggesting the formation of undesirable compounds. All the properties mentioned above were found to be useful to determine whether a biodiesel sample underwent thermal degradation. Moreover, viscosity and acid value were found to be the most sensitive characteristics to detect the thermal degradation process.

Two distinct factors are required for induction of T-cell growth.

PubMed

Larsson, E L; Iscove, N N; Coutinho, A

1980-02-14

The molecular and cellular basis of T-lymphocyte activation remains a central question in immunology. The growth of already proliferating T cells is known to depend on T-cell growth factor (TCGF), a physiological mitogen. Noncycling T lymphocytes, however, are not sensitive to TCGF. They require a short contact with mitogenic lectins, such as concanavalin A (Con A) or leukoagglutinin to bind and respond to TCGF, and will thereafter maintain exponential growth for long periods provided that TCGF is not limiting. While the induction of TCGF reactivity results from the direct contact of Con A with resting T cells, the lectin-dependent production of TCGF is known to involve two cell types, both present in mouse spleen. One consists of I-A-negative cells, most of which are Thy-1-positive T lymphocytes, and the other consists of I-A-positive, immunoglobulin-negative, Thy-1-negative cells, most of which are macrophages. The nature of the respective contributions of the two cell types, and in particular the cellular origin of TCGF, has not yet been established. We have now established the I-A-negative population as the source of TCGF and show here that macrophages are required to supply a 20,000-molecular weight factor, chemically and functionally distinct from TCGF, which supports the production of TCGF by the I-A-negative cells.

Petrology, geochemistry and LA-ICP-MS U-Pb geochronology of Paleoproterozoic basement rocks in Bangladesh: An evaluation of calc-alkaline magmatism and implication for Columbia supercontinent amalgamation

NASA Astrophysics Data System (ADS)

Hossain, Ismail; Tsunogae, Toshiaki; Tsutsumi, Yukiyasu; Takahashi, Kazuki

2018-05-01

The Paleoproterozoic (1.7 Ga) basement rocks from Maddhapara, Bangladesh show a large range of chemical variations (e.g. SiO2 = 50.7-74.7%) and include diorite, quartz diorite, monzodiorite, quartz monzonite and granite. The pluton overall displays metaluminous, calc-alkaline orogenic suite; mostly I-type suites formed within subduction-related magmatism. The observed major elements show general trends for fractional crystallization. Trace element contents also indicate the possibility of a fractionation or assimilation; explain the entire variation from diorite to monzonite, even granite. The pluton may have evolved the unique chemical features by a process that included partial melting of calc-alkaline lithologies and mixing of mantle-derived magmas, followed by fractional crystallization, and by assimilation of country rocks. The pluton shows evidence of crystal fractionation involving largely plagioclase, amphibole and possibly biotite. Some of the fractionated magmas may have mixed with more potassic melts from distinct parts of the continental lithosphere to produce granites and/or pegmatites. New geochronological results of granitic pegmatite (1722 ± 10 Ma) are indisputably consistent with diorite and tonalite and those data showing credible geochronological sequence (i.e., diorite - tonalite - granitic pegmatite). Identical Paleoproterozoic age (1.7 Ga) with distinctive magmatism of the Maddhapara basement rocks have agreeable relationship with the CITZ, India. The consistent magmatism is also common in the Transamazonian of South America, Trans-Hudson orogeny in North America, Bohemian Massif and the Svecofennian, Poland, have identified the sequential growth of the continent through the amalgamation of juvenile terrains, succeeded by a major collisional orogeny. Such Paleoproterozoic subduction-related orogens in Australia have similar counterparts in Antarctica and other part of the world. These types of Paleoproterozoic magmatism dominantly contributed to assemble, amalgamation and breakup of the enormous Columbia supercontinent.

Recommended nomenclature for zeolite minerals: report of the subcommittee on zeolites of the International Mineralogical Association, Commission of New Minerals and Mineral Names

USGS Publications Warehouse

Coombs, D.S.; Alberti, A.; Armbruster, T.; Artioli, G.; Colella, C.; Galli, E.; Grice, Joel D.; Liebau, F.; Mandarino, J.A.; Minato, H.; Nickel, E.H.; Passaglia, E.; Peacor, D.R.; Quartieri, S.; Rinaldi, R.; Ross, M.; Sheppard, R.A.; Tillmanns, E.; Vezzalini, G.

1998-01-01

This report embodies recommendations on zeolite nomenclature approved by the International Mineralogical Association Commission of New Minerals and Mineral Names. In a working definition of a zeolite mineral used for review, interrupted tetrahedral framework structures are accepted where other zeolitic properties prevail, and complete substitution by elements other than Si and Al is allowed. Separate species are recognized in topologically distinctive compositional series in which different extra-framework cations are the most abundance in atomic proportions. To name these, the appropriate chemical symbol is attached by a hyphen to the series name as a suffix except for the names harmotome, pollucite and wairakite in the phillipsite and analcime series. Differences in space-group symmetry and in order-disorder relationships in zeolites having the same topologically distinctive framework do not in general provide adequate grounds for recognition of separate species. Zeolite species are not to be distinguished solely on Si:Al ratio except for heulandite (Si:Al < 4.0) and clinoptilolite (Si:Al ??? 4.0). Dehydration, partial hydration, and over-hydration are not sufficient grounds for the recognition of separate species of zeolites. Use of the term 'ideal formula' should be avoided in referring to a simplified or averaged formula of a zeolite. Newly recognized species in compositional series are as follows: brewsterite-Sr.-Ba: chabazite-Ca.-Na.-K; clinoptilolite-K, -Na, -Ca: dachiardite-Ca, -Na; erionite-K, -Ca: faujasite-Na, -Ca, -Na: paulingite-K. -Ca; phillipsite-Na, -Ca, -Ka; stilbite-Ca, -Na. Key references, type locality, origin of name, chemical data. IZA structure-type symbols, space-group symmetry; unit-cell dimensions, and comments on structure are listed for 13 compositional series, 82 accepted zeolite mineral species, and three of doubtful status. Herschelite, leonhardite, svetlozarite, and wellsite are discredited as mineral species names. Obsolete and discredited names are listed.

Digital image processing based identification of nodes and internodes of chopped biomass stems

USDA-ARS?s Scientific Manuscript database

Chemical composition of biomass feedstock is an important parameter for optimizing the yield and economics of various bioconversion pathways. Although understandably, the chemical composition of biomass varies among species, varieties, and plant components, there is distinct variation even among ste...

30 CFR 70.2 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... designated area. (m) Quartz means crystalline silicon dioxide (SiO2) not chemically combined with other... produced and routine day-to-day activities are occurring in the DA. Quartz. Crystalline silicon dioxide (SiO2) not chemically combined with other substances and having a distinctive physical structure...

Charting Biologically Relevant Spirocyclic Compound Space.

PubMed

Müller, Gerhard; Berkenbosch, Tim; Benningshof, Jorg C J; Stumpfe, Dagmar; Bajorath, Jürgen

2017-01-12

Spirocycles frequently occur in natural products and experience increasing interest in drug discovery, given their richness in sp 3 centers and distinct three-dimensionality. We have systematically explored chemical space populated with currently available bioactive spirocycles. Compounds containing spiro systems were classified and their scaffolds and spirocyclic ring combinations analyzed. Nearly 47 000 compounds were identified that contained spirocycles in different structural contexts and were active against roughly 200 targets, among which several pharmaceutically relevant members of the G protein-coupled receptor (GPCR) family were identified. Spirocycles and corresponding compounds displayed notable scaffold diversity but contained only limited numbers of combinations of differently sized rings. These observations indicate that there should be significant potential to further expand spirocyclic chemical space for drug discovery, exploiting the privileged substructure concept. Inspired by those findings, we embarked on the design and chemical synthesis of three distinct novel spirocyclic scaffolds that qualify for downstream library synthesis, thus exploring principally new chemical space with high potential for pharmaceutical research. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seeking the chemical roots of darwinism: bridging between chemistry and biology.

PubMed

Pross, Addy

2009-08-24

Chemistry and biology are intimately connected sciences yet the chemistry-biology interface remains problematic and central issues regarding the very essence of living systems remain unresolved. In this essay we build on a kinetic theory of replicating systems that encompasses the idea that there are two distinct kinds of stability in nature-thermodynamic stability, associated with "regular" chemical systems, and dynamic kinetic stability, associated with replicating systems. That fundamental distinction is utilized to bridge between chemistry and biology by demonstrating that within the parallel world of replicating systems there is a second law analogue to the second law of thermodynamics, and that Darwinian theory may, through scientific reductionism, be related to that second law analogue. Possible implications of these ideas to the origin of life problem and the relationship between chemical emergence and biological evolution are discussed.

Ionotropic and metabotropic mechanisms in chemoreception: 'chance or design'?

PubMed

Silbering, Ana Florencia; Benton, Richard

2010-03-01

Chemosensory receptors convert an enormous diversity of chemical signals from the external world into a common language of electrical activity in the brain. Mammals and insects use several families of transmembrane receptor proteins to recognize distinct classes of volatile and non-volatile chemicals that are produced by conspecifics or other environmental sources. A comparison of the signalling mechanisms of mammalian and insect receptors has revealed an unexpected functional distinction: mammals rely almost exclusively on metabotropic ligand-binding receptors, which use second messenger signalling cascades to indirectly activate ion channels, whereas insects use ionotropic receptors, which are gated directly by chemical stimuli, thereby leading to neuronal depolarization. In this review, we consider possible reasons for this dichotomy, taking into account biophysical, cell biological, ecological and evolutionary influences on how information is extracted from chemosensory cues by these animal classes.

Ionotropic and metabotropic mechanisms in chemoreception: ‘chance or design'?

PubMed Central

Silbering, Ana Florencia; Benton, Richard

2010-01-01

Chemosensory receptors convert an enormous diversity of chemical signals from the external world into a common language of electrical activity in the brain. Mammals and insects use several families of transmembrane receptor proteins to recognize distinct classes of volatile and non-volatile chemicals that are produced by conspecifics or other environmental sources. A comparison of the signalling mechanisms of mammalian and insect receptors has revealed an unexpected functional distinction: mammals rely almost exclusively on metabotropic ligand-binding receptors, which use second messenger signalling cascades to indirectly activate ion channels, whereas insects use ionotropic receptors, which are gated directly by chemical stimuli, thereby leading to neuronal depolarization. In this review, we consider possible reasons for this dichotomy, taking into account biophysical, cell biological, ecological and evolutionary influences on how information is extracted from chemosensory cues by these animal classes. PMID:20111052

The look of royalty: visual and odour signals of reproductive status in a paper wasp

PubMed Central

Tannure-Nascimento, Ivelize C; Nascimento, Fabio S; Zucchi, Ronaldo

2008-01-01

Reproductive conflicts within animal societies occur when all females can potentially reproduce. In social insects, these conflicts are regulated largely by behaviour and chemical signalling. There is evidence that presence of signals, which provide direct information about the quality of the reproductive females would increase the fitness of all parties. In this study, we present an association between visual and chemical signals in the paper wasp Polistes satan. Our results showed that in nest-founding phase colonies, variation of visual signals is linked to relative fertility, while chemical signals are related to dominance status. In addition, experiments revealed that higher hierarchical positions were occupied by subordinates with distinct proportions of cuticular hydrocarbons and distinct visual marks. Therefore, these wasps present cues that convey reliable information of their reproductive status. PMID:18682372

The look of royalty: visual and odour signals of reproductive status in a paper wasp.

PubMed

Tannure-Nascimento, Ivelize C; Nascimento, Fabio S; Zucchi, Ronaldo

2008-11-22

Reproductive conflicts within animal societies occur when all females can potentially reproduce. In social insects, these conflicts are regulated largely by behaviour and chemical signalling. There is evidence that presence of signals, which provide direct information about the quality of the reproductive females would increase the fitness of all parties. In this study, we present an association between visual and chemical signals in the paper wasp Polistes satan. Our results showed that in nest-founding phase colonies, variation of visual signals is linked to relative fertility, while chemical signals are related to dominance status. In addition, experiments revealed that higher hierarchical positions were occupied by subordinates with distinct proportions of cuticular hydrocarbons and distinct visual marks. Therefore, these wasps present cues that convey reliable information of their reproductive status.

Phylogenetic and structural comparisons of the three types of methyl-coenzyme M reductase from Methanococcales and Methanobacteriales.

PubMed

Wagner, Tristan; Wegner, Carl-Eric; Kahnt, Jörg; Ermler, Ulrich; Shima, Seigo

2017-05-30

The phylogenetically diverse family of methanogenic archaea universally use methyl-coenzyme M reductase (MCR) for catalyzing the final methane-forming reaction step of the methanogenic energy metabolism. Some methanogens of the orders Methanobacteriales and Methanococcales contain two isoenzymes. Comprehensive phylogenetic analyses on the basis of all three subunits grouped MCRs from Methanobacteriales, Methanococcales and Methanopyrales into three distinct types: (1) MCRs from Methanobacteriales, (2) MCRs from Methanobacteriales and Methanococcales and (3) MCRs from Methanococcales. The first and second types contain MCR isoenzyme I and II from Methanothermobacter marburgensis , respectively; therefore, they were designated as MCR type I and type II and accordingly, the third one was designated as MCR type III. For comparison with the known MCR type I and type II structures, we determined the structure of MCR type III from Methanotorris formicicus and Methanothermococcus thermolithotrophicus As predicted, the three MCR types revealed highly similar overall structures and a virtually identical active site architecture reflecting the chemically challenging mechanism of methane formation. Pronounced differences were found at the protein surface with respect to loop geometries and electrostatic properties, which also involve the entrance of the active site funnel. In addition, the C-terminal end of the γ-subunit is prolonged by an extra helix after helix γ8 in MCR type II and type III, which is, however, differently arranged in the two MCR types. MCR types I, II and III share most of the post-translational modifications which appear to fine-tune the enzymatic catalysis. Interestingly, MCR type III lacks the methyl-cysteine but possesses in subunit α of M. formicicus a 6-hydroxy-tryptophan, which has been, so far, only found in the α-amanitin toxin peptide but not in proteins. IMPORTANCE Methyl-coenzyme M reductase (MCR) represents a prime target for the mitigation of methane releases. Phylogenetic analyses of MCR suggested several distinct sequence clusters; those from Methanobacteriales and Methanococcales were subdivided into three types: MCR type I from Methanobacteriales, MCR type II from Methanobacteriales and Methanococcales and the newly designated MCR type III exclusively from Methanococcales. We determined the first X-ray structures for an MCR type III. Detailed analyses only revealed substantial differences between the three types in the peripheral region. Identified subtle modifications and electrostatic profiles suggested enhanced substrate binding for MCR type III. In addition, MCR type III from Methanotorris formicicus contains 6-hydroxy-tryptophan, a new post-translational modification that was, so far, only found in the α-amanitin toxin. Copyright © 2017 American Society for Microbiology.

CHEMICAL TAGGING OF THREE DISTINCT POPULATIONS OF RED GIANTS IN THE GLOBULAR CLUSTER NGC 6752

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

Carretta, E.; Bragaglia, A.; Gratton, R. G.

2012-05-01

We present aluminum, magnesium, and silicon abundances in the metal-poor globular cluster NGC 6752 for a sample of more than 130 red giants with homogeneous oxygen and sodium abundances. We find that [Al/Fe] shows a spread of about 1.4 dex among giants in NGC 6752 and is anticorrelated with [Mg/Fe] and [O/Fe] and correlated with [Na/Fe] and [Si/Fe]. These relations are not continuous in nature, but the distribution of stars is clearly clustered around three distinct Al values, low, intermediate, and high. These three groups nicely correspond to the three distinct sequences previously detected using Stroemgren photometry along the redmore » giant branch. These two independent findings strongly indicate the existence of three distinct stellar populations in NGC 6752. Comparing the abundances of O and Mg, we find that the population with intermediate chemical abundances cannot originate from material with the same composition of the most O- and Mg-poor population, diluted by material with that of the most O- and Mg-rich one. This calls for different polluters.« less

Distinct Chemical Contrast in Adhesion Force Images of Hydrophobic-Hydrophilic Patterned Surfaces Using Multiwalled Carbon Nanotube Probe Tips

NASA Astrophysics Data System (ADS)

Azehara, Hiroaki; Kasanuma, Yuka; Ide, Koichiro; Hidaka, Kishio; Tokumoto, Hiroshi

2008-05-01

In this paper, we describe a fabrication procedure for large-diameter carbon nanotube probe tips (CNT tips) for atomic force microscopy, the tip-end chemistry of the CNT tips, and their advantage drawn from the study of adhesion force imaging in an ambient atmosphere on a patterned hydrophobic and hydrophilic self-assembled monolayer, which has been prepared by a microcontact printing method. Force titration measurements in phosphate buffer solutions reveal that the CNT tip has retained carboxyl groups at its end. In adhesion force imaging, a distinct chemical contrast is obtained for the patterned surfaces as compared to a case using a silicon nitride tip. The origin of the distinct contrast is discussed in terms of the tip-end chemistry featured by carboxyl groups and a possible weakening of capillary forces of water caused at around the tip-sample interface because of the intrinsically hydrophobic nature of CNTs.

Mechanical vibrations from tadpoles' flapping tails transform salamander's carnivorous morphology.

PubMed

Michimae, Hirofumi; Nishimura, Kinya; Wakahara, Masami

2005-03-22

Some prey or predator organisms exhibit striking rapid morphological plastic changes with distinct morphology under the condition of predator or prey presence. Remote chemicals propagating from the inducing agents are the prevalent induction cues for most examples of induction of distinct morphs. Sonic and visual cues, as well as chemical cues, are known as triggers for induction of behavioural plasticity. Here we show that hydraulic vibration originating from flapping tails of anuran tadpoles is a key cue in relation to induction of a distinct carnivorous morphology, a broad-headed morph, in larval salamander Hynobius retardatus, which is able to efficiently capture and handle prey. This result was further supported by the fact that simple mechanical vibrations of tail-like vinyl fins were able to induce the morph without any biological cues. Induction of the morph triggered by hydraulic vibration provides a novel concept for understanding the proximate mechanisms of induction of morphological changes.

A proposition for the classification of carbonaceous chondritic micrometeorites

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.

1994-01-01

Classification of interplanetary dust particles (IDP's) should be unambiguous and, if possible, provide an opportunity to interrelate these ultrafine IDP's with the matrices of undifferentiated meteorites. I prefer a scheme of chemical groupings and petrologic classes that is based on primary IDP properties that can be determined without prejudice by individual investigators. For IDP's of 2-50 microns these properties are bulk elemental chemistry, morphology, shape, and optical properties. The two major chemical groups are readily determined by energy dispersive spectroscopic analysis using the scanning or analytical electron microscope. Refinement of chondritic IDP classification is possible using the dominant mineral species, e.g. olivine, pyroxene, and layer silicates, and is readily inferred from FTIR, and automated chemical analysis. Petrographic analysis of phyllosilicate-rich IDP's will identify smectite-rich and serpentine-rich particles. Chondritic IDP's are also classified according to morphology, viz., CP and CF IDP's are aggregate particles that differ significantly in porosity, while the dense CS IDP's have a smooth surface. The CP IDP's are characterized by an anhydrous silicate mineralogy, but small amounts of layer silicates may be present. Distinction between the CP and CF IDP's is somewhat ambiguous, but the unique CP IDP's are fluffy, or porous, ultrafine-grained aggregates. The CP IDP's, which may contain silicate whiskers, are the most carbon-rich extraterrestrial material presently known. The CF IDP's are much less porous that CP IDP's. Using particle type definitions, CP IDP's in the NASA JSC Cosmic Dust Catalogs are approx. 15 percent of all IDP's that include nonchondritic spheres. Most aggregate particles are of the CF type.

Production of arrays of chemically distinct nanolitre plugs via repeated splitting in microfluidic devices.

PubMed

Adamson, David N; Mustafi, Debarshi; Zhang, John X J; Zheng, Bo; Ismagilov, Rustem F

2006-09-01

This paper reports a method for the production of arrays of nanolitre plugs with distinct chemical compositions. One of the primary constraints on the use of plug-based microfluidics for large scale biological screening is the difficulty of fabricating arrays of chemically distinct plugs on the nanolitre scale. Here, using microfluidic devices with several T-junctions linked in series, a single input array of large (approximately 320 nL) plugs was split to produce 16 output arrays of smaller (approximately 20 nL) plugs; the composition and configuration of these arrays were identical to that of the input. This paper shows how the passive break-up of plugs in T-junction microchannel geometries can be used to produce a set of smaller-volume output arrays useful for chemical screening from a single large-volume array. A simple theoretical description is presented to describe splitting as a function of the Capillary number, the capillary pressure, the total pressure difference across the channel, and the geometric fluidic resistance. By accounting for these considerations, plug coalescence and plug-plug contamination can be eliminated from the splitting process and the symmetry of splitting can be preserved. Furthermore, single-outlet splitting devices were implemented with both valve- and volume-based methods for coordinating the release of output arrays. Arrays of plugs containing commercial sparse matrix screens were obtained from the presented splitting method and these arrays were used in protein crystallization trials. The techniques presented in this paper may facilitate the implementation of high-throughput chemical and biological screening.

The New Element Berkelium (Atomic Number 97)

DOE R&D Accomplishments Database

Seaborg, G. T.; Thompson, S. G.; Ghiorso, A.

1950-04-26

An isotope of the element with atomic number 97 has been discovered as a product of the helium-ion bombardment of americium. The name berkelium, symbol Bk, is proposed for element 97. The chemical separation of element 97 from the target material and other reaction products was made by combinations of precipitation and ion exchange adsorption methods making use of its anticipated (III) and (IV) oxidation states and its position as a member of the actinide transition series. The distinctive chemical properties made use of in its separation and the equally distinctive decay properties of the particular isotope constitute the principal evidence for the new element.

Identification of nodes and internodes of chopped biomass stems by Image analysis

USDA-ARS?s Scientific Manuscript database

Separating the morphological components of biomass leads to better handling, more efficient processing as well as value added product generation, as these components vary in their chemical composition and can be preferentially utilized. Nodes and internodes of biomass stems have distinct chemical co...

Water sorption-desorption in conifer cuticles: The role of lignin.

PubMed

Reina, José J.; Domínguez, Eva; Heredia, Antonio

2001-07-01

Current information on the type and amount of biopolymers present in the epidermis of conifer species is still insufficient. This work presents the detailed morphology and chemical composition of Araucaria bidwillii cuticle after selective treatments to remove the different types of biopolymers. After removal of the waxes, cutin and polar hydrolyzable components, a lignin-like fraction, which makes up 25% of the initial cuticle weight, was identified by GC-MS and infrared spectroscopy. The isolated lignin is of G type, mainly formed by guaiacyl units. This composition indicates that the conifer cuticle investigated here has similar composition to other conifer-isolated cuticles. Water sorption and desorption by the isolated cuticle and the different cuticle fractions, including lignin, were studied. The analysis of the isotherms, following distinct physicochemical models, gave useful information on the structural and physiological role of the different biopolymers present in the cuticle. Lignin fraction showed both a high water sorption and capability of retaining it in comparision to other cuticle components. Hysteresis effect on water sorption-desorption cycle and water cluster formations has also been studied, and their physiological role discussed.

An assessment of Wx microsatellite allele, alkali degradation and differentiation of chloroplast DNA in traditional black rice (Oryza sativa L.) from Thailand and Lao PDR.

PubMed

Prathepha, Preecha

2007-01-15

Thailand and Lao PDR are the country's rich rice diversity. To contribute a significant knowledge for development new rice varieties, a collection of 142 black rice (Oryza sativa) accessions were determined for variation of physico-chemical properties, Wx microsatellite allele, Wx allele and chloroplast DNA type. The results showed that amylose content of black rice accessions were ranged from 1.9 to 6.8%. All of the alkali disintegration types (high, intermediate and low) was observed in these rice with average of 1.75 on the 1-3 digestibility scale. The unique Wx microsatellite allele (CT)17 was found in these samples and all black rice strains carried Wx(b) allele. In addition, all black rice accessions were found the duplication of the 23 bp sequence motif in the exon 2 of the wx gene. This evidence is a common phenomenon in glutinous rice. Based on two growing condition for black rice, rainfed lowland and rainfed upland, chloroplast DNA type was distinct from each other. All rice strains from rainfed lowland was deletion plastotype, but all other rainfed upland strains were non-deletion types.

Identification of a Drosophila glucose receptor using Ca2+ imaging of single chemosensory neurons.

PubMed

Miyamoto, Tetsuya; Chen, Yan; Slone, Jesse; Amrein, Hubert

2013-01-01

Evaluation of food compounds by chemosensory cells is essential for animals to make appropriate feeding decisions. In the fruit fly Drosophila melanogaster, structurally diverse chemicals are detected by multimeric receptors composed of members of a large family of Gustatory receptor (Gr) proteins. Putative sugar and bitter receptors are expressed in distinct subsets of Gustatory Receptor Neurons (GRN) of taste sensilla, thereby assigning distinct taste qualities to sugars and bitter tasting compounds, respectively. Here we report a Ca(2+) imaging method that allows association of ligand-mediated responses to a single GRN. We find that different sweet neurons exhibit distinct response profiles when stimulated with various sugars, and likewise, different bitter neurons exhibit distinct response profiles when stimulated with a set of bitter chemicals. These observations suggest that individual neurons within a taste modality are represented by distinct repertoires of sweet and bitter taste receptors, respectively. Furthermore, we employed this novel method to identify glucose as the primary ligand for the sugar receptor Gr61a, which is not only expressed in sweet sensing neurons of classical chemosensory sensilla, but also in two supersensitive neurons of atypical taste sensilla. Thus, single cell Ca(2+) imaging can be employed as a powerful tool to identify ligands for orphan Gr proteins.

An Informatics Approach to Evaluating Combined Chemical Exposures from Consumer Products: A Case Study of Asthma-Associated Chemicals and Potential Endocrine Disruptors.

PubMed

Gabb, Henry A; Blake, Catherine

2016-08-01

Simultaneous or sequential exposure to multiple environmental stressors can affect chemical toxicity. Cumulative risk assessments consider multiple stressors but it is impractical to test every chemical combination to which people are exposed. New methods are needed to prioritize chemical combinations based on their prevalence and possible health impacts. We introduce an informatics approach that uses publicly available data to identify chemicals that co-occur in consumer products, which account for a significant proportion of overall chemical load. Fifty-five asthma-associated and endocrine disrupting chemicals (target chemicals) were selected. A database of 38,975 distinct consumer products and 32,231 distinct ingredient names was created from online sources, and PubChem and the Unified Medical Language System were used to resolve synonymous ingredient names. Synonymous ingredient names are different names for the same chemical (e.g., vitamin E and tocopherol). Nearly one-third of the products (11,688 products, 30%) contained ≥ 1 target chemical and 5,229 products (13%) contained > 1. Of the 55 target chemicals, 31 (56%) appear in ≥ 1 product and 19 (35%) appear under more than one name. The most frequent three-way chemical combination (2-phenoxyethanol, methyl paraben, and ethyl paraben) appears in 1,059 products. Further work is needed to assess combined chemical exposures related to the use of multiple products. The informatics approach increased the number of products considered in a traditional analysis by two orders of magnitude, but missing/incomplete product labels can limit the effectiveness of this approach. Such an approach must resolve synonymy to ensure that chemicals of interest are not missed. Commonly occurring chemical combinations can be used to prioritize cumulative toxicology risk assessments. Gabb HA, Blake C. 2016. An informatics approach to evaluating combined chemical exposures from consumer products: a case study of asthma-associated chemicals and potential endocrine disruptors. Environ Health Perspect 124:1155-1165; http://dx.doi.org/10.1289/ehp.1510529.

Characterization of Chemically-Induced Bacterial Ghosts (BGs) Using Sodium Hydroxide-Induced Vibrio parahaemolyticus Ghosts (VPGs).

PubMed

Park, Hyun Jung; Oh, Sung; Vinod, Nagarajan; Ji, Seongmi; Noh, Han Byul; Koo, Jung Mo; Lee, Su Hyeong; Kim, Sei Chang; Lee, Ki-Sung; Choi, Chang Won

2016-11-15

Acellular bacterial ghosts (BGs) are empty non-living bacterial cell envelopes, commonly generated by controlled expression of the cloned lysis gene E of bacteriophage PhiX174. In this study, Vibrio parahaemolyticus ghosts (VPGs) were generated by chemically-induced lysis and the method is based on minimum inhibitory concentration (MIC) of sodium hydroxide (NaOH), acetic acid, boric acid, citric acid, maleic acid, hydrochloric acid, and sulfuric acid. The MIC values of the respective chemicals were 3.125, 6.25, <50.0, 25.0, 6.25, 1.56, and 0.781 mg/mL. Except for boric acid, the lysis efficiency reached more than 99.99% at 5 min after treatment of all chemicals. Among those chemicals, NaOH-induced VPGs appeared completely DNA-free, which was confirmed by quantitative real-time PCR. Besides, lipopolysaccharides (LPS) extracted from the NaOH-induced VPGs showed no distinctive band on SDS-PAGE gel after silver staining. On the other hand, LPS extracted from wild-type bacterial cells, as well as the organic acids-induced VPGs showed triple major bands and LPS extracted from the inorganic acids-induced VPGs showed double bands. It suggests that some surface structures in LPS of the NaOH-induced VPGs may be lost, weakened, or modified by the MIC of NaOH. Nevertheless, Limulus amoebocyte lysate assay revealed that there is no significant difference in endotoxic activity between the NaOH-induced VPGs and wild-type bacterial cells. Macrophages exposed to the NaOH-induced VPGs at 0.5 × 10⁶ CFU/mL showed cell viability of 97.9%, however, the MIC of NaOH did not reduce the cytotoxic effect of wild-type bacterial cells. Like Escherichia coli LPS, the NaOH-induced VPGs are an excellent activator of pro-inflammatory cytokines (IL-1β and iNOS), anti-inflammatory cytokine (IL-10), and dual activities (IL-6) in the stimulated macrophage cells. On the other hand, the induction of TNF-α mRNA was remarkable in the macrophages exposed with wild-type cells. Scanning electron microscopy showed the formation of trans-membrane lysis tunnel structures in the NaOH-induced VPGs. SDS-PAGE and agarose gel electrophoresis also confirmed that cytoplasmic proteins and genomic DNA released from the VPGs to culture medium through the lysis tunnel structures. Taken together, all these data indicate that the NaOH-induced VPGs show the potency of a safe, economical, and effective inactivated bacterial vaccine candidate.

'Nosing Around' the human skin: what information is concealed in skin odour?

PubMed

Kippenberger, Stefan; Havlíček, Jan; Bernd, August; Thaçi, Diamant; Kaufmann, Roland; Meissner, Markus

2012-09-01

In today's world, natural body odour is mostly considered as being unpleasant and combated by intensive cleansing, deodorants and perfumes. However, there is evidence that volatile body compounds provide the recipient with important information. Here, we present the chemical identity of odorous compounds derived from odourless precursors within sweat and sebum. Moreover, distinct volatile markers may be relevant for the clinical diagnosis of disease. Interestingly, ageing seems to correlate with the appearance of specific compounds that convey the so-called old man smell. Finally, it is discussed if human skin odour has the quality to act as pheromone transmitting information between individuals in terms of major histocompatibility complex type or reproductive status. © 2012 John Wiley & Sons A/S.

Meteoritic parent bodies - Nature, number, size and relation to present-day asteroids

NASA Technical Reports Server (NTRS)

Lipschutz, Michael E.; Gaffey, Michael J.; Pellas, Paul

1989-01-01

The relationship between meteoritic parent bodies and the present-day asteroids is discussed. Results on oxygen isotopic signatures and chemical distinctions among meteorite classes indicate that meteorites derive from a small number of parent bodies relative to the number of asteroids. The spectral properties of the ordinary chondrites and similar inclusions in meteoritic breccias differ from those of the abundant S asteroids (with no process known that can account for these differences); the closest spectral analogs of these chondrites are the rare near-earth Q-type asteroids. These facts lead to the question of why abundant meteorites have rare asteroidal analogs, while the abundant asteroids have rare meteoritic analogs. This question constitutes a prime topic for future studies.

Vaginal eroticism: a replication study.

PubMed

Alzate, H

1985-12-01

Vaginal eroticism was investigated in a group of 27 coitally experienced volunteers by means of systematic digital stimulation of both vaginal walls. Erogenous zones were found in all subjects, mainly located on the upper anterior wall and the lower posterior one. An orgasmic response was elicited by stimulation of these zones in 89% of the subjects. This study supports previous findings regarding vaginal eroticism. It does not support the existence of the discrete anatomical structure called the Grafenberg spot. It supports the contention that there are two distinct types of female orgasm, vaginally evoked and clitorally evoked. It also supports the finding that some women expel a fluid through the urethra at the time of orgasm. In this particular case the fluid was chemically indistinguishable from urine.

Multivariate functions for predicting the sorption of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-tricyclohexane (RDX) among taxonomically distinct soils.

PubMed

Katseanes, Chelsea K; Chappell, Mark A; Hopkins, Bryan G; Durham, Brian D; Price, Cynthia L; Porter, Beth E; Miller, Lesley F

2016-11-01

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed a new solution for modeling the sorption and persistence of these munition constituents as multivariate mathematical functions correlating soil attribute data over a variety of taxonomically distinct soil types to contaminant behavior, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments measuring the sorption of TNT and RDX on taxonomically different soil types that were extensively physical and chemically characterized. Statistical decomposition of the log-transformed, and auto-scaled soil characterization data using the dimension-reduction technique PCA (principal component analysis) revealed a strong latent structure based in the multiple pairwise correlations among the soil properties. TNT and RDX sorption partitioning coefficients (KD-TNT and KD-RDX) were regressed against this latent structure using partial least squares regression (PLSR), generating a 3-factor, multivariate linear functions. Here, PLSR models predicted KD-TNT and KD-RDX values based on attributes contributing to endogenous alkaline/calcareous and soil fertility criteria, respectively, exhibited among the different soil types: We hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished soil types may provide the means for potentially predicting complex phenomena in soils. The development of predictive multivariate models tuned to a local soil's taxonomic designation would have direct benefit to military range managers seeking to anticipate the environmental risks of training activities on impact sites. Published by Elsevier Ltd.

A Cluster Analytic Study of Clinical Orientations among Chemical Dependency Counselors.

ERIC Educational Resources Information Center

Thombs, Dennis L.; Osborn, Cynthia J.

2001-01-01

Three distinct clinical orientations were identified in a sample of chemical dependency counselors (N=406). Based on cluster analysis, the largest group, identified and labeled as "uniform counselors," endorsed a simple, moral-disease model with little interest in psychosocial interventions. (Contains 50 references and 4 tables.) (GCP)

High-Flow Asymmetric Reverse-Osmosis Membranes

NASA Technical Reports Server (NTRS)

Katz, M. C.; Wydeven, T. J.

1984-01-01

Water-soluble polymer membrane insolubilized by transition-metal salt. Thin layer of lower permeability material joined with thicker layer of highpermeability material. Two layers chemically identical or chemically distinct. They differ in density, compactness or other respects. Used to purify or desalinate seawater, brackish water, or industrial or domestic wastewater.

3D spectral imaging with synchrotron Fourier transform infrared spectro-microtomography

Treesearch

Michael C. Martin; Charlotte Dabat-Blondeau; Miriam Unger; Julia Sedlmair; Dilworth Y. Parkinson; Hans A. Bechtel; Barbara Illman; Jonathan M. Castro; Marco Keiluweit; David Buschke; Brenda Ogle; Michael J. Nasse; Carol J. Hirschmugl

2013-01-01

We report Fourier transform infrared spectro-microtomography, a nondestructive three-dimensional imaging approach that reveals the distribution of distinctive chemical compositions throughout an intact biological or materials sample. The method combines mid-infrared absorption contrast with computed tomographic data acquisition and reconstruction to enhance chemical...

Developmental exposure to a mixture of two mechanistically distinct antiandrogens results in cumulative adverse reproductive effects in adult male rats

EPA Science Inventory

Typically, toxicological studies have focused on the adverse effects from exposure to single chemicals. However, endocrine disrupting chemicals (EDCs) are detected in the environment as mixtures. Empirical evidence suggests that mixtures of EDCs with the same mechanism of action...

Polluted Dust Classification and Its Optical Properties Analysis Using CALIPSO Data and Simulation

NASA Astrophysics Data System (ADS)

Ding, J.; Yang, P.; Holz, R.; Vaughan, M. A.; Hu, Y.

2015-12-01

In CALIPSO Level 2 aerosol data, dust particles are classified into two subtypes, namely, pure dust and polluted dust based on lidar backscatter, depolarization ratio and surface types. In this research, the polluted dust subtype is found to have two distinct modes in terms of integrated depolarization ratio (IDR) and integrated total color ratio (ICR). Dust with smaller IDR and ICR occurs mainly over areas with strong smoke emissions such as industrial cities. This kind of polluted dust originating from East Asia is also found over the Pacific Ocean. In contrast, the other type originating from the Saharan desert with larger IDR and ICR occurs mainly over the Atlantic Ocean. The disparities of IDR and ICR may result from different pollutants. The polluted dust with smaller ICR and IDR should have stronger absorption of light and may contain black carbon. Other chemical compounds such as sea salts may account for polluted dust with larger ICR and IDR. To further separate the types of polluted dust, cluster analysis is applied to determine the centroid of each type in terms of IDR and ICR. Furthermore, scattering models of dust mixed with various pollutants are constructed to be included in a CALIPSO simulator. The simulated IDR and ICR values are compared with data to retrieve the chemical compositions of polluted dust. The difference of polluted dust over the Pacific and Atlantic Ocean provides new evidence about long-range transport of Asian dust to North America. The distribution of dust polluted by black carbon is determined, which can improve knowledge about the effect of black carbon on the earth's radiation budget.

Chemical mixtures: Evaluation of risk for child-specific exposures in a multi-stressor environment

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

Pohl, H.R.; Abadin, H.G.

Evaluating the health impact from exposure to chemical mixtures is multifaceted. One component is exposure. Exposure, and consequently risk assessment for mixtures and chemicals in general, are often viewed in terms of a given exposure to a given population at a given location over a given time period. However, environmental exposures are present throughout human lifetime. As a result, an evaluation of risk must include the distinctive characteristics related to chemical exposures which will impact risk depending upon the particular life stage where exposure occurs. Risks to offspring may be associated with unique exposures in utero, during infancy, childhood, ormore » adolescent periods. For example, exposure of infants to anthropogenic chemicals via breast milk may be of concern. The Agency for Toxic Substances and Disease Registry's (ATSDR's) approach to evaluating risks associated with exposure to mixtures of chemicals is presented. In addition to the breast milk issues, indoor exposure to combined air pollutants, drinking water contaminants, and soil and dust contaminants are discussed. The difference between a mixture's risk evaluation for children and adults is in the distinct exposure scenarios resulting from variations in behavior, physiology, and/or pharmacokinetics between adults and children rather than in the method for the specific mixtures evaluation per se.« less

Application of DRIFTS, NMR, and py-MBMS to characterize the effects of soil science oxidation assays on soil organic matter composition in a Mollic Xerofluvent

USDA-ARS?s Scientific Manuscript database

To evaluate whether commonly employed chemical treatments remove structurally distinct fractions of soil organic matter (SOM), a Mollic Xerofluvent under agricultural use was subjected to three distinct oxidation treatments: potassium permanganate (KMnO4), sodium hypochlorite (NaOCl), and hydrogen p...

Chemical assessment and in vitro antioxidant capacity of Ficus carica latex.

PubMed

Oliveira, Andreia P; Silva, Luís R; Ferreres, Federico; Guedes de Pinho, Paula; Valentão, Patrícia; Silva, Branca M; Pereira, José A; Andrade, Paula B

2010-03-24

Ficus species possess latex-like material within their vasculatures, affording protection and self-healing from physical attacks. In this work, metabolite profiling was performed on Ficus carica latex. Volatiles profile was determined by HS-SPME/GC-IT-MS, with 34 compounds being identified, distributed by distinct chemical classes: 5 aldehydes, 7 alcohols, 1 ketone, 9 monoterpenes, 9 sesquiterpenes and 3 other compounds. Sesquiterpenes constituted the most abundant class in latex (ca. 91% of total identified compounds). Organic acids composition was also characterized, by HPLC-UV, and oxalic, citric, malic, quinic, shikimic and fumaric acids were determined. Malic and shikimic acids were present in higher amounts (ca. 26%, each). The antioxidant potential of this material was checked by distinct in vitro chemical assays. A concentration-dependent activity was noticed against DPPH, nitric oxide and superoxide radicals. Additionally, acetylcholinesterase inhibitory capacity was evaluated, but a weak effect was found.

A new stylolite classification scheme to estimate compaction and local permeability variations

NASA Astrophysics Data System (ADS)

Koehn, D.; Rood, M. P.; Beaudoin, N.; Chung, P.; Bons, P. D.; Gomez-Rivas, E.

2016-12-01

We modeled the geometrical roughening of bedding-parallel, mainly layer-dominated stylolites in order to understand their structural evolution, to present an advanced classification of stylolite shapes and to relate this classification to chemical compaction and permeability variations at stylolites. Stylolites are rough dissolution seams that develop in sedimentary basins during chemical compaction. In the Zechstein 2 carbonate units, an important lean gas reservoir in the southern Permian Zechstein basin in Germany, stylolites influence local fluid flow, mineral replacement reactions and hence the permeability of the reservoir. Our simulations demonstrate that layer-dominated stylolites can grow in three distinct stages: an initial slow nucleation phase, a fast layer-pinning phase and a final freezing phase if the layer is completely dissolved during growth. Dissolution of the pinning layer and thus destruction of the stylolite's compaction tracking capabilities is a function of the background noise in the rock and the dissolution rate of the layer itself. Low background noise needs a slower dissolving layer for pinning to be successful but produces flatter teeth than higher background noise. We present an advanced classification based on our simulations and separate stylolites into four classes: (1) rectangular layer type, (2) seismogram pinning type, (3) suture/sharp peak type and (4) simple wave-like type. Rectangular layer type stylolites are the most appropriate for chemical compaction estimates because they grow linearly and record most of the actual compaction (up to 40 mm in the Zechstein example). Seismogram pinning type stylolites also provide good tracking capabilities, with the largest teeth tracking most of the compaction. Suture/sharp peak type stylolites grow in a non-linear fashion and thus do not record most of the actual compaction. However, when a non-linear growth law is used, the compaction estimates are similar to those making use of the rectangular layer type stylolites. Simple wave-like stylolites are not useful for compaction estimates, since their growth is highly non-linear with a very low growth exponent. In the case where sealing material is collected at the tooth during dissolution, stylolites can act as barriers for local fluid flow as they intensify sealing capabilities of pinning layers. However, the development of teeth and spikes offsets and thus destroys continuous stylolite seams so that the permeability across the stylolite becomes very heterogeneous and they are no continuous barriers. This behavior is best shown in rectangular layer and seismogram pinning type stylolites that develop efficient fluid barriers at teeth tips but destroy sealing capabilities of layers by offsetting them at the flank, leading to a permeability anisotropy along 2-D stylolite planes. Suture/sharp peak stylolites can create fluid barriers if they collect enough sealing material. However, if the collecting material does not seal or if spikes offset the sealing material the stylolite leaks. We propose that our classification can be used to realistically estimate chemical compaction in reservoirs and gives an indication on how heterogeneous the permeability of stylolites can be.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

Effect of intrinsic electronic defect states on the morphology and optoelectronic properties of Sn-rich SnS particles

NASA Astrophysics Data System (ADS)

Singh, Chetan C.; Panda, Emila

2018-05-01

A small variation in the elemental composition of a chemical compound can cause the formation of additional electronic defect states in the material, thereby altering the overall microstructure and thus induced properties. In this work, we observed chemical constitution-induced modification in the morphology and optoelectronic properties of SnS. To this end, SnS particles were prepared using the solution chemical route and were characterized using a wide range of experimental techniques, such as x-ray diffractometry, field emission scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive spectroscopy (EDS), x-ray photoelectron spectroscopy (XPS), UV-Vis spectrophotometry, and scanning tunneling spectroscopy (STS). All these SnS particles are found to be Sn-rich and p-type. However, distinctly different morphologies (i.e., flower-like and aggregated ones) are observed. These are then correlated with the electronic defect states, which are induced because of the presence of Sn vacancies, Sn antisites, and/or Sn interstitials. A combination of EDS, XPS, and STS data confirmed the presence of a higher concentration of Sn vacancies along with lower quantities of Sn interstitials and/or antisites in the SnS particles with flower-like morphologies giving rise to higher hole concentration, which subsequently leads to reduced transport, optical band gaps, and barrier heights.

Integrative taxonomy: Combining morphological, molecular and chemical data for species delineation in the parthenogenetic Trhypochthonius tectorum complex (Acari, Oribatida, Trhypochthoniidae)

PubMed Central

2011-01-01

Background There is a long-standing controversial about how parthenogenetic species can be defined in absence of a generally accepted species concept for this reproductive mode. An integrative approach was suggested, combining molecular and morphological data to identify distinct monophyletic entities. Using this approach, speciation of parthenogenetic lineages was recently demonstrated for groups of bdelloid rotifers and oribatid mites. Trhypochthonius tectorum, an oribatid mite from the entirely parthenogenetic desmonomatan family Trhypochthoniidae, is traditionally treated as a single species in Central Europe. However, two new morphological lineages were recently proposed for some Austrian populations of T. tectorum, and were described as novel subspecies (T. silvestris europaeus) or form (T. japonicus forma occidentalis). We used the morphological and morphometrical data which led to this separation, and added mitochondrial and nuclear DNA sequences and the chemical composition of complex exocrine oil gland secretions to test this taxonomical hypothesis. This is the first attempt to combine these three types of data for integrative taxonomical investigations of oribatid mites. Results We show that the previous European species T. tectorum represents a species complex consisting of three distinct lineages in Austria (T.tectorum, T. silvestris europaeus and T. japonicus forma occidentalis), each clearly separated by morphology, oil gland secretion profiles and mitochondrial cox1 sequences. This diversification happened in the last ten million years. In contrast to these results, no variation among the lineages was found in the nuclear 18S rDNA. Conclusions Our approach combined morphological, molecular and chemical data to investigate diversity and species delineation in a parthenogenetic oribatid mite species complex. To date, hypotheses of a general oribatid mite phylogeny are manifold, and mostly based on single-method approaches. Probably, the integrative approach proposed here can be used to uncover further hidden biodiversity of glandulate Oribatida and help to build up more stable phylogenetic hypotheses in the future. PMID:21303503

Zinc Isotopic Signatures of the Upper Continental Crust

NASA Astrophysics Data System (ADS)

Xia, Y.; Zhang, X.; Zhang, H.; Huang, F.

2016-12-01

To examine the Zn isotope systematics within the Upper Continental Crust (UCC), and isotope fractionation during chemical weathering in large spatial and temporal scales, we analyzed Zn isotopic compositions of loess, glacial diamictites, river sediments, and igneous rocks (samples in total 77). The Zn isotopic compositions (δ66Zn relative to JMC-Lyon) of loess display a limited variation (0.17‰ to 0.29‰), which is negatively correlated with Zn content and proxies for chemical weathering (e.g. CIA values), reflect the impact of chemical weathering. Glacial diamictites have more variable δ66Zn (0.09‰ to 0.48‰), but the average δ66Zn (0.29±0.03‰, 2SD) is similar to loess. δ66Zn of glacial diamictites correlate roughly negatively with CIA values, but have no correlation with Zn content, implying source heterogeneity and effect from chemical weathering. δ66Zn of A-type (0.39‰ to 0.45‰) and S-type (0.28‰ to 0.35‰) granites are both homogeneous, but the latter have systematically lighter δ66Zn. This may reflect no Zn isotopic fractionation during magmatic processes and involvement of isotopically light meta-sedimentary into the sources of S-type granites. Furthermore, δ66Zn in riverine sediments display a small variation from 0.23‰ to 0.37‰, while δ66Zn of the the shales vary from 0.14‰ to 0.53‰, which could result from a combination of processes, such as biological cycling and chemical weathering. Overall, our data suggest that incipient chemical weathering can fractionate Zn isotopes significantly, meanwhile, during this process, heavy Zn are released preferentially. The UCC is estimated to have an average δ66Zn of 0.30 ±0.03‰ (2SD) with data collected in this study, which is similar to the estimated value of Bulk Silicate Earth (0.28±0.05‰)[1] and mean dissolved riverine flux (0.33‰)[2], but distinctly lighter than the bulk composition of dissolved Zn in the ocean (0.51‰)[2]. [1] Chen et al., Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth. Earth and Planetary Science Letters 369, 34-42 (2013). [2] Little et al., The oceanic mass balance of copper and zinc isotopes, investigated by analysis of their inputs, and outputs to ferromanganese oxide sediments. Geochimica et Cosmochimica Acta 125, 673-693 (2014).

Apollo 17 KREEPy basalts - Evidence for nonuniformity of KREEP

NASA Technical Reports Server (NTRS)

Salpas, Peter A.; Taylor, Lawrence A.; Lindstrom, Marilyn M.

1987-01-01

Breccia 72275 contains pristine KREEPy basalt clasts that are not found among other samples collected at Apollo 17. These basalts occur as discrete clasts and as clasts enclosed within basaltic microbreccias. Mineral and whole-rock chemical analyses reveal that the microbreccias are compositionally indistinguishable from the basalt clasts. Samples of the 72275 matrix also have the same compositions as the basalts and the basaltic microbreccias. 72275 was assembled in situ from a single flow or series of closely related flows of Apollo 17 KREEPy basalt before it was transported to the Apollo 17 site. As a rock type, Apollo 17 KREEPy basalts are distinct from Apollo 15 KREEP basalts. The Apollo 17 samples have lower REE concentrations, steeper negative slopes of the HREE, and are less magnesian than the Apollo 15 samples. The two basalt types cannot be related by fractional crystallization, partial melting, or assimilation. This is evidence for the compositional nonuniformity of KREEP as a function of geography.

Personalized anticancer therapy selection using molecular landscape topology and thermodynamics.

PubMed

Rietman, Edward A; Scott, Jacob G; Tuszynski, Jack A; Klement, Giannoula Lakka

2017-03-21

Personalized anticancer therapy requires continuous consolidation of emerging bioinformatics data into meaningful and accurate information streams. The use of novel mathematical and physical approaches, namely topology and thermodynamics can enable merging differing data types for improved accuracy in selecting therapeutic targets. We describe a method that uses chemical thermodynamics and two topology measures to link RNA-seq data from individual patients with academically curated protein-protein interaction networks to select clinically relevant targets for treatment of low-grade glioma (LGG). We show that while these three histologically distinct tumor types (astrocytoma, oligoastrocytoma, and oligodendroglioma) may share potential therapeutic targets, the majority of patients would benefit from more individualized therapies. The method involves computing Gibbs free energy of the protein-protein interaction network and applying a topological filtration on the energy landscape to produce a subnetwork known as persistent homology. We then determine the most likely best target for therapeutic intervention using a topological measure of the network known as Betti number. We describe the algorithm and discuss its application to several patients.

Classification and Distribution of Mars Pathfinder Rocks Using Quantitative Morphologic Indices

NASA Technical Reports Server (NTRS)

Yingst, R. A.; Biederman, K. L.; Monhead, A. M.; Haldemann, A. F. C.; Kowalczyk, M. R.

2004-01-01

The Mars Pathfinder (MPF) landing site was predicted to contain a broad sampling of rock types varying in mineralogical, physical, mechanical and geochemical characteristics. Although rocks have been divided into several spectral categories based on Imager for Mars Pathfinder visible/near-infrared spectra, it has not been fully determined which of these stem from intrinsic mineralogical differences between rocks or rock surfaces, and which result from factors such as physical or chemical weathering. This has made isolation of unique mineralogy's difficult. Efforts in isolating and classifying spectral units among MPF rocks and soils have met with varying degrees of success, and the current understanding is such that many factors influencing spectral signatures cannot be quantified to a sufficient level so they may be removed. The result is that fundamental questions regarding information needed to reveal the present and past interactions between the rocks and rock surfaces and the Martian environment remain unanswered. But it is possible to approach the issue of identifying distinct rock and rock surface types from a different angle.

A sex-inducing pheromone triggers cell cycle arrest and mate attraction in the diatom Seminavis robusta

PubMed Central

Moeys, Sara; Frenkel, Johannes; Lembke, Christine; Gillard, Jeroen T. F.; Devos, Valerie; Van den Berge, Koen; Bouillon, Barbara; Huysman, Marie J. J.; De Decker, Sam; Scharf, Julia; Bones, Atle; Brembu, Tore; Winge, Per; Sabbe, Koen; Vuylsteke, Marnik; Clement, Lieven; De Veylder, Lieven; Pohnert, Georg; Vyverman, Wim

2016-01-01

Although sexual reproduction is believed to play a major role in the high diversification rates and species richness of diatoms, a mechanistic understanding of diatom life cycle control is virtually lacking. Diatom sexual signalling is controlled by a complex, yet largely unknown, pheromone system. Here, a sex-inducing pheromone (SIP+) of the benthic pennate diatom Seminavis robusta was identified by comparative metabolomics, subsequently purified, and physicochemically characterized. Transcriptome analysis revealed that SIP+ triggers the switch from mitosis-to-meiosis in the opposing mating type, coupled with the transcriptional induction of proline biosynthesis genes, and the release of the proline-derived attraction pheromone. The induction of cell cycle arrest by a pheromone, chemically distinct from the one used to attract the opposite mating type, highlights the existence of a sophisticated mechanism to increase chances of mate finding, while keeping the metabolic losses associated with the release of an attraction pheromone to a minimum. PMID:26786712

Lunar highland rocks - Element partitioning among minerals. II - Electron microprobe analyses of Al, P, Ca, Ti, Cr, Mn and Fe in olivine

NASA Technical Reports Server (NTRS)

Smith, J. V.; Hansen, E. C.; Steele, I. M.

1980-01-01

Lunar olivines from anorthosites, granulitic impactites, and rocks in the Mg-rich plutonic trend were subjected to electron probe measurements for Al, P, Ca, Ti, Cr and Mn, which show that the FeO/MnO ratio for lunar olivines lies between 80 and 110 with little difference among the rock types. The low values of Ca in lunar olivines indicate slow cooling to subsolidus temperatures, with blocking temperatures of about 750 C for 67667 and 1000 C for 60255,73-alpha determined by the Finnerty and Boyd (1978) experiments. An important paradox is noted in the low Ti content of Fe-rich olivines from anorthosites, although both Ti and Fe tend to become enriched in liquid during fractional distillation. Except for Ca and Mn, olivine from anorthosites has lower minor element values than other rock types. Formation from a chemically distinct system is therefore implied.

Molecular epidemiology of methicillin-resistant Staphylococcus aureus isolated in serial cultures from the respiratory tract of children with cystic fibrosis.

PubMed

Al-Zubeidi, Duha; Hogan, Patrick G; Boyle, Mary; Burnham, Carey-Ann D; Fritz, Stephanie A

2014-06-01

Little is known about strain relatedness of methicillin-resistant Staphyloccocus aureus (MRSA) isolated at serial time points from the respiratory tract of patients with cystic fibrosis (CF). The objectives are to interrogate the genetic diversity of MRSA recovered in serial cultures from children with CF and to correlate strain relatedness with clinical characteristics. We performed a retrospective analysis of children with CF from whom MRSA was isolated from serial respiratory cultures from 2005 to 2011. Within individual patients, relatedness of isolated strains was determined by repetitive-sequence polymerase chain reaction, and the staphylococcal cassette chromosome mec type of each isolate was characterized. Medical records corresponding to the MRSA cultures were reviewed. We identified 54 CF patients with serial MRSA cultures (145 distinct cultures). Over time, 45 (83%) patients maintained the same strain type and 9 (17%) possessed at least 2 distinct strain types. A total of 91 pairs of isolates were analyzed for strain relatedness. Of these, 81 (89%) were identical and 10 (11%) were distinct strain types. About 117 (83%) isolates were staphylococcal cassette chromosome mec type II, 24 (17%) were staphylococcal cassette chromosome mec type IV and 4 were other types not resolvable with our assay. Clinical factors, including time interval and prescription of antibiotics effective against MRSA between positive cultures, did not correlate with acquisition of a distinct MRSA strain by individual patients. Our data suggest that sustained presence of MRSA in CF patients is most commonly attributable to identical strain types. Acquisition of distinct MRSA strains in the airway is infrequent.

Vitellogenin and vitellogenin receptor gene expression profiles in Spodoptera exigua are related to host plant suitability.

PubMed

Zhao, Jing; Sun, Yang; Xiao, Liubin; Tan, Yongan; Jiang, Yiping; Bai, Lixin

2018-04-01

The beet armyworm Spodoptera exigua, a worldwide phytophagous pest, causes considerable economic agricultural losses. Understanding the relationship between its fecundity and the host plant is a basic and important component of early forecasting of beet armyworm outbreaks. However, little is known about the molecular mechanism by which distinct hosts affect S. exigua fecundity. In this study, key life-history parameters of S. exigua reared on distinct hosts were investigated; the host plants could be ranked as lettuce > shallot > tomato > celery in their order of suitability. Full-length S. exigua vitellogenin receptor (SeVgR) cDNA was cloned, and sex-, stage- and tissue-specific expression characteristics were assessed. Spodoptera exigua vitellogenin (SeVg) and SeVgR expression levels were markedly modulated by host nutrients (P < 0.05). SeVg and SeVgR expression levels were significantly higher in S. exigua reared on lettuce, the most preferred and most nutritive host, than in those reared on tomato and celery. Interestingly, significant linear regression correlations were found between SeVg and SeVgR expression levels and key S. exigua life-history parameters, especially life span, pupa weight, and female fecundity (P < 0.01). Host plant type and suitability could affect the expression pattern of SeVg and SeVgR, which influenced S. exigua fecundity. Vg and VgR have the potential to be used as molecular markers of S. exigua fecundity and for forecasting outbreaks of S. exigua on different hosts. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Establishing the solubility and local structure(s) of Amorphous Calcium Carbonate (ACC): Toward an understanding of invertebrate biomineralization

NASA Astrophysics Data System (ADS)

Mergelsberg, S. T.; Ulrich, R. N.; Michel, F. M.; Dove, P. M.

2017-12-01

Recent advances in high-resolution imaging show the widespreadd occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015, Science). For example, carbonate biomineralization often involves precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that subsequently transforms to crystalline products with diverse structures. Although current carbonate mineral proxies are based upon the composition of final crystalline products, the final signatures may be recording the properties of the initial amorphous phase. Thus, it is critical to establish the physical properties of ACC and understand the factors that influence its evolution to final products at conditions that approximate biological environments. This disconnect limits our ability to build a process-based understanding of when/how minor and trace elements are recorded in mineral composition proxies. In this experimental study, we quantified the chemical and physical properties of ACC and its evolution to final products. We first determined ACC solubility under controlled chemical conditions using a new type of flow-through reactor developed by our research group (Blue and Dove, 2015, GCA; Blue et al., 2017, GCA). The experimental design varied Mg concentration and total alkalinity while maintaining a mild pH that approximates biological environments. ACC solubility was measured at specific time points during the precipitation (from super- and undersaturated conditions) and during its subsequent evolution. Parallel experiments characterized the structure of the corresponding amorphous products using in situ pair distribution function (PDF) and small-angle x-ray scattering (SAXS) analyses. The measurements demonstrate at least two types of ACC can be produced by tuning Mg concentration and alkalinity. Each "phase" exhibits distinct short-range ordering that demonstrates structure-specific solubility. We also find temporal changes in the short-range order of each type of ACC that are dependent upon Mg content. Insights from this study hold promise for quantifying the chemical and structural properties of ACC and reconcile discrepancies in the literature.

Defective aquaporin-2 trafficking in nephrogenic diabetes insipidus and correction by chemical chaperones.

PubMed Central

Tamarappoo, B K; Verkman, A S

1998-01-01

Five single-point aquaporin-2 (AQP2) mutations that cause non-X-linked nephrogenic diabetes insipidus (NDI) were characterized to establish the cellular defect and to develop therapeutic strategies. In Xenopus oocytes expressing AQP2 cRNAs, single-channel water permeabilities of mutants L22V, T126M, and A147T were similar to that of wild-type AQP2, whereas R187C and C181W were nonfunctional. In [35S]methionine pulse-chase experiments in transiently transfected CHO cells, half-times for AQP2 degradation were approximately 4 h for wild-type AQP2 and L22V, and mildly decreased for T126M (2.7 h), C181W (2.4 h), R187C (2.0 h), and A147T (1.8 h). Immunofluorescence showed three distinct AQP2-staining patterns: plasma membrane and endosomal staining (wild-type, L22V), endoplasmic reticulum (ER) staining (T126M > A147T approximately R187C), or a mixed pattern of reticular and perinuclear vesicular staining. Immunoblot of fractionated vesicles confirmed primary ER localization of T126M, R187C, and A147T. To determine if the AQP2-trafficking defect is correctable, cells were incubated with the "chemical chaperone" glycerol for 48 h. Immunoblot showed that glycerol produced a nearly complete redistribution of AQP2 (T126M, A147T, and R187C) from ER to membrane/endosome fractions. Immunofluorescence confirmed the cellular redistribution. Redistribution of AQP2 mutants was also demonstrated in transfected MDCK cells, and using the chaperones TMAO and DMSO in place of glycerol in CHO cells. Water permeability measurements indicated that functional correction was achieved. These results indicate defective mammalian cell processing of mutant AQP2 water channels in NDI, and provide evidence for pharmacological correction of the processing defect by chemical chaperones. PMID:9593782

Chemo-stratigraphy in the Murray Formation Using ChemCam

NASA Astrophysics Data System (ADS)

Blaney, D. L.; Anderson, R. B.; Bridges, N.; Bridges, J.; Calef, F. J., III; Clegg, S. M.; Le Deit, L.; Fisk, M. R.; Forni, O.; Gasnault, O.; Kah, L. C.; Kronyak, R. E.; Lanza, N.; Lasue, J.; Mangold, N.; Maurice, S.; Milliken, R.; Ming, D. W.; Nachon, M.; Newsom, H. E.; Rapin, W.; Stack, K.; Sumner, D. Y.; Wiens, R. C.

2015-12-01

Curiosity has completed a detailed chemo-stratigraphy analysis at the Pahrump exposure of the Murray formation. In total >570 chemical measurements and supporting remote micro images to classify texturally were collected. Chemical trends with both stratigraphic position and with texture were evaluated. From these data emerges a complex aqueous history where sediments have interacted with fluids with variable chemistry in distinct episodes. The ChemCam data collected at the nearby "Garden City" (GC) vein complex provides constraints on the chemical evolution of the Pahrump. GC is thought be stratigraphically above the Pahrump outcrop. Fluids producing the veins likely also migrated through the Pahrump sediments. Multiple episodes of fluids are evident at GC, forming distinct Ca sulfate, F-rich, enhanced MgO, and FeO-rich veins. These different fluid chemistries could be the result of distinct fluids migrating through the section from a distance with a pre-established chemical signature, fluids locally evolved from water rock interactions, or both. Texturally rocks have been classified into two distinct categories: fine grained or as cross-bedded sandstones. The sandstones have significantly lower SiO2, Al2O3, and K2O and higher FeO, and CaO. Fine grained rocks have further been sub-classified as resistant and recessive with other textural features such as laminations and pits noted.The strongest chemical trend in the fine-grained sandstones shows enhancements in MgO and FeO in erosion-resistant materials compared to fine grained recessive units, suggesting that increased abundance of Mg- and/or iron-rich cements may provide additional strength. The MgO and FeO variations with texture are independent of stratigraphic locations (e.g resistant material at both the bottom and top of the outcrop both are enhanced in MgO and FeO). The presence of the GC MgO and FeO rich veins provides additional evidence for fluids rich in these elements were present in the outcrop. Other elemental trends results including SiO2, Al2O3, K2O and Na2O will be explored in addition to key trace element signatures such as Li, Cr and F to understand the chemical evolution of the outcrop.

Arsenic, manganese and aluminum contamination in groundwater resources of Western Amazonia (Peru).

PubMed

de Meyer, Caroline M C; Rodríguez, Juan M; Carpio, Edward A; García, Pilar A; Stengel, Caroline; Berg, Michael

2017-12-31

This paper presents a first integrated survey on the occurrence and distribution of geogenic contaminants in groundwater resources of Western Amazonia in Peru. An increasing number of groundwater wells have been constructed for drinking water purposes in the last decades; however, the chemical quality of the groundwater resources in the Amazon region is poorly studied. We collected groundwater from the regions of Iquitos and Pucallpa to analyze the hydrochemical characteristics, including trace elements. The source aquifer of each well was determined by interpretation of the available geological information, which identified four different aquifer types with distinct hydrochemical properties. The majority of the wells in two of the aquifer types tap groundwater enriched in aluminum, arsenic, or manganese at levels harmful to human health. Holocene alluvial aquifers along the main Amazon tributaries with anoxic, near pH-neutral groundwater contained high concentrations of arsenic (up to 700μg/L) and manganese (up to 4mg/L). Around Iquitos, the acidic groundwater (4.2≤pH≤5.5) from unconfined aquifers composed of pure sand had dissolved aluminum concentrations of up to 3.3mg/L. Groundwater from older or deeper aquifers generally was of good chemical quality. The high concentrations of toxic elements highlight the urgent need to assess the groundwater quality throughout Western Amazonia. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of groundwater and soil quality degradation using multivariate and geostatistical analyses, Dakhla Oasis, Egypt

NASA Astrophysics Data System (ADS)

Masoud, Alaa A.; El-Horiny, Mohamed M.; Atwia, Mohamed G.; Gemail, Khaled S.; Koike, Katsuaki

2018-06-01

Salinization of groundwater and soil resources has long been a serious environmental hazard in arid regions. This study was conducted to investigate and document the factors controlling such salinization and their inter-relationships in the Dakhla Oasis (Egypt). To accomplish this, 60 groundwater samples and 31 soil samples were collected in February 2014. Factor analysis (FA) and hierarchical cluster analysis (HCA) were integrated with geostatistical analyses to characterize the chemical properties of groundwater and soil and their spatial patterns, identify the factors controlling the pattern variability, and clarify the salinization mechanism. Groundwater quality standards revealed emergence of salinization (av. 885.8 mg/L) and extreme occurrences of Fe2+ (av. 17.22 mg/L) and Mn2+ (av. 2.38 mg/L). Soils were highly salt-affected (av. 15.2 dS m-1) and slightly alkaline (av. pH = 7.7). Evaporation and ion-exchange processes governed the evolution of two main water types: Na-Cl (52%) and Ca-Mg-Cl (47%), respectively. Salinization leads the chemical variability of both resources. Distinctive patterns of slight salinization marked the northern part and intense salinization marked the middle and southern parts. Congruence in the resources clusters confirmed common geology, soil types, and urban and agricultural practices. Minimizing the environmental and socioeconomic impacts of the resources salinization urges the need for better understanding of the hydrochemical characteristics and prediction of quality changes.

Effects of dietary fibre on subjective appetite, energy intake and body weight: a systematic review of randomized controlled trials.

PubMed

Wanders, A J; van den Borne, J J G C; de Graaf, C; Hulshof, T; Jonathan, M C; Kristensen, M; Mars, M; Schols, H A; Feskens, E J M

2011-09-01

Dietary fibres are believed to reduce subjective appetite, energy intake and body weight. However, different types of dietary fibre may affect these outcomes differently. The aim of this review was to systematically investigate the available literature on the relationship between dietary fibre types, appetite, acute and long-term energy intake, and body weight. Fibres were grouped according to chemical structure and physicochemical properties (viscosity, solubility and fermentability). Effect rates were calculated as the proportion of all fibre-control comparisons that reduced appetite (n = 58 comparisons), acute energy intake (n = 26), long-term energy intake (n = 38) or body weight (n = 66). For appetite, acute energy intake, long-term energy intake and body weight, there were clear differences in effect rates depending on chemical structure. Interestingly, fibres characterized as being more viscous (e.g. pectins, β-glucans and guar gum) reduced appetite more often than those less viscous fibres (59% vs. 14%), which also applied to acute energy intake (69% vs. 30%). Overall, effects on energy intake and body weight were relatively small, and distinct dose-response relationships were not observed. Short- and long-term effects of dietary fibres appear to differ and multiple mechanisms relating to their different physicochemical properties seem to interplay. This warrants further exploration. © 2011 The Authors. obesity reviews © 2011 International Association for the Study of Obesity.

Atomic force microscopy investigation of chemically stabilized pericardium tissue.

PubMed

Jastrzebska, M; Barwinski, B; Mróz, I; Turek, A; Zalewska-Rejdak, J; Cwalina, B

2005-04-01

Native and chemically stabilized porcine pericardium tissue was imaged by the contact mode atomic force microscopy (AFM), in air. Chemically stabilized pericardium is used as a tissue-derived biomaterial in various fields of the reconstructive and replacement surgery. Collagen type I is the main component of the fibrous layer of the pericardium tissue. In this study, the surface topography of collagen fibrils in their native state in tissue and after chemical stabilization with different cross-linking reagents: glutaraldehyde (GA), dimethyl suberimidate (DMS) and tannic acid (TA) was investigated. It has been found that chemical stabilization causes considerable changes in the surface topography of collagen fibrils as well as in the spatial organization of the fibrils within the tissue. The observed changes in the D-spacing pattern of the collagen fibril correspond to the formation of intrafibrilar cross-links, whereas formation of interfibrilar cross-links is mainly responsible for the observed tangled spatial arrangement of fibrils and crimp structure of the tissue surface. The crimp structure was distinctly seen for the GA cross-linked tissue. Surface heterogeneity of the cross-linking process was observed for the DMS-stabilized tissue. SDS-PAGE electrophoresis was performed in order to evaluate the stabilization effect of the tissues treated with the cross-linking reagents. It has been found that stabilization with DMS, GA or TA enhances significantly the tissue resistance to SDS/NaCl extraction. The relation between the tissue stability and changes in the topography of the tissue surface was interpreted in terms of different nature of cross-links formed by DMS, GA and TA with collagen.

Individual Distinctiveness in Call Types of Wild Western Female Gorillas

PubMed Central

Salmi, Roberta; Hammerschmidt, Kurt; Doran-Sheehy, Diane M.

2014-01-01

Individually distinct vocalizations play an important role in animal communication, allowing call recipients to respond differentially based on caller identity. However, which of the many calls in a species' repertoire should have more acoustic variability and be more recognizable is less apparent. One proposed hypothesis is that calls used over long distances should be more distinct because visual cues are not available to identify the caller. An alternative hypothesis proposes that close calls should be more recognizable because of their importance in social interactions. To examine which hypothesis garners more support, the acoustic variation and individual distinctiveness of eight call types of six wild western gorilla (Gorilla gorilla) females were investigated. Acoustic recordings of gorilla calls were collected at the Mondika Research Center (Republic of Congo). Acoustic variability was high in all gorilla calls. Similar high inter-individual variation and potential for identity coding (PIC) was found for all call types. Discriminant function analyses confirmed that all call types were individually distinct (although for call types with lowest sample size - hum, grumble and scream - this result cannot be generalized), suggesting that neither the distance at which communication occurs nor the call social function alone can explain the evolution of identity signaling in western gorilla communication. PMID:25029238

Type I and II β-turns prediction using NMR chemical shifts.

PubMed

Wang, Ching-Cheng; Lai, Wen-Chung; Chuang, Woei-Jer

2014-07-01

A method for predicting type I and II β-turns using nuclear magnetic resonance (NMR) chemical shifts is proposed. Isolated β-turn chemical-shift data were collected from 1,798 protein chains. One-dimensional statistical analyses on chemical-shift data of three classes β-turn (type I, II, and VIII) showed different distributions at four positions, (i) to (i + 3). Considering the central two residues of type I β-turns, the mean values of Cο, Cα, H(N), and N(H) chemical shifts were generally (i + 1) > (i + 2). The mean values of Cβ and Hα chemical shifts were (i + 1) < (i + 2). The distributions of the central two residues in type II and VIII β-turns were also distinguishable by trends of chemical shift values. Two-dimensional cluster analyses on chemical-shift data show positional distributions more clearly. Based on these propensities of chemical shift classified as a function of position, rules were derived using scoring matrices for four consecutive residues to predict type I and II β-turns. The proposed method achieves an overall prediction accuracy of 83.2 and 84.2% with the Matthews correlation coefficient values of 0.317 and 0.632 for type I and II β-turns, indicating that its higher accuracy for type II turn prediction. The results show that it is feasible to use NMR chemical shifts to predict the β-turn types in proteins. The proposed method can be incorporated into other chemical-shift based protein secondary structure prediction methods.

Chemical profiling of two congeneric sea mat corals along the Brazilian coast: adaptive and functional patterns.

PubMed

Costa-Lotufo, L V; Carnevale-Neto, F; Trindade-Silva, A E; Silva, R R; Silva, G G Z; Wilke, D V; Pinto, F C L; Sahm, B D B; Jimenez, P C; Mendonça, J N; Lotufo, T M C; Pessoa, O D L; Lopes, N P

2018-02-20

Metabolomic profiles were explored to understand environmental and taxonomic influences on the metabolism of two congeneric zoanthids, Palythoa caribaeorum and P. variabilis, collected across distinct geographical ranges. Integrated mass spectrometry data suggested the major influence of geographical location on chemical divergence when compared to species differentiation.

Non-transferable signals on ant queen eggs

NASA Astrophysics Data System (ADS)

D'Ettorre, Patrizia; Tofilski, Adam; Heinze, Jürgen; Ratnieks, Francis L. W.

2006-03-01

How biological systems resolve internal conflicts is a major evolutionary question. Social insect workers cooperate but also pursue individual interests, such as laying male eggs. The rewards of this individual selfishness can be reduced by policing, such as by killing worker-laid eggs. However, selfish individuals may evade policing. What factors prevent individuals from being able to evade policing? In the ant Pachycondyla inversa, workers kill (police) worker-laid eggs. Because the colony keeps eggs in piles and worker-laid and queen-laid eggs are chemically distinct, worker-laid eggs might become more acceptable once placed in the egg pile by odour transfer from touching queen-laid eggs. Here, we show that such “cue scrambling” does not occur. Worker-laid eggs that were sandwiched between three queen-laid eggs for 45 min were not more acceptable in a policing bioassay than control worker-laid eggs. Chemical analyses also showed that the surface hydrocarbon profile of these eggs was unchanged. Policing, therefore, is stable against this potential cheating mechanism probably because queen-laid eggs are made chemically distinct using chemicals, that are not easily transferred by physical contact.

Non-transferable signals on ant queen eggs.

PubMed

D'Ettorre, Patrizia; Tofilski, Adam; Heinze, Jürgen; Ratnieks, Francis L W

2006-03-01

How biological systems resolve internal conflicts is a major evolutionary question. Social insect workers cooperate but also pursue individual interests, such as laying male eggs. The rewards of this individual selfishness can be reduced by policing, such as by killing worker-laid eggs. However, selfish individuals may evade policing. What factors prevent individuals from being able to evade policing? In the ant Pachycondyla inversa, workers kill (police) worker-laid eggs. Because the colony keeps eggs in piles and worker-laid and queen-laid eggs are chemically distinct, worker-laid eggs might become more acceptable once placed in the egg pile by odour transfer from touching queen-laid eggs. Here, we show that such "cue scrambling" does not occur. Worker-laid eggs that were sandwiched between three queen-laid eggs for 45 min were not more acceptable in a policing bioassay than control worker-laid eggs. Chemical analyses also showed that the surface hydrocarbon profile of these eggs was unchanged. Policing, therefore, is stable against this potential cheating mechanism probably because queen-laid eggs are made chemically distinct using chemicals, that are not easily transferred by physical contact.

Remote and in situ sensing products in chemical reaction using a flexible terahertz pipe waveguide.

PubMed

You, Borwen; Lu, Ja-Yu

2016-08-08

The feasibility of remote chemical detection is experimentally demonstrated by using a Teflon pipe as a scanning arm in a continuous-terahertz wave sensing and imaging system. Different tablets with distinct mixed ratios of aluminum and polyethylene powders are well distinguished by measuring the power reflectivities of 0.4 THz wave associated with their distinct terahertz refractive indices. Given its refractive index sensitivity and fast response, the reflective terahertz sensing system can be used to real-time trace and quantitatively analyze the ammonium-chloride aerosols produced by the chemical reaction between hydrochloric acid and ammonia vapors. With a tightly focusing terahertz beam spot, the spatial and concentration distributions of the generated chemical product are successfully mapped out by the 1D scan of the flexible pipe probe. In consideration of the responsitivity, power stability, and focused spot size of the system, its detection limit for the ammonium-chloride aerosol is estimated to be approximately 165 nmol/mm². The reliable and compact terahertz pipe scan system is potentially suitable for practical applications, such as biomedical or industrial fiber endoscopy.

Formation of anodic layers on InAs (111)III. Study of the chemical composition

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

Valisheva, N. A., E-mail: valisheva@thermo.isp.nsc.ru; Tereshchenko, O. E.; Prosvirin, I. P.

2012-04-15

The chemical composition of {approx}20-nm-thick anodic layers grown on InAs (111)III in alkaline and acid electrolytes containing or not containing NH{sub 4}F is studied by X-ray photoelectron spectroscopy. It is shown that the composition of fluorinated layers is controlled by the relation between the concentrations of fluorine and hydroxide ions in the electrolyte and by diffusion processes in the growing layer. Fluorine accumulates at the (anodic layer)/InAs interface. Oxidation of InAs in an acid electrolyte with a low oxygen content and a high NH{sub 4}F content brings about the formation of anodic layers with a high content of fluorine andmore » elemental arsenic and the formation of an oxygen-free InF{sub x}/InAs interface. Fluorinated layers grown in an alkaline electrolyte with a high content of O{sup 2-} and/or OH{sup -} groups contain approximately three times less fluorine and consist of indium and arsenic oxyfluorides. No distinction between the compositions of the layers grown in both types of fluorine-free electrolytes is established.« less

Globular Cluster Contributions to the Galactic Halo

NASA Astrophysics Data System (ADS)

Martell, Sarah; Grebel, Eva; Lai, David

2010-08-01

The goal of this project is to confirm chemically that globular clusters are the source of as much as half the population of the Galactic halo. Using moderate-resolution spectroscopy from the SEGUE survey, we have identified a previously unknown population of halo field giants with distinctly strong CN features. CN variations are typically only observed in globular clusters, so these stars are interpreted as immigrants to the halo that originally formed in globular clusters. In one night of Keck/HIRES time, we will obtain high-quality, high- resolution spectra for five such stars, and determine abundances of O, Na, Mg, Al, alpha, iron-peak and neutron-capture elements. With this information we can state clearly whether these unusual CN-strong halo stars carry the full abundance pattern seen in CN-strong globular cluster stars, with depleted C, O, and Mg and enhanced N, Na, and Al. This type of coarse ``chemical tagging'' will allow a clearer division of the Galactic halo into contributions from globular clusters and from dwarf galaxies, and will place constraints on theoretical models of globular cluster formation and evolution.

Appalachian piedmont regolith: Relations of saprolite and residual soils to rock-type

USGS Publications Warehouse

Pavich, M.J.

1996-01-01

Saprolite is a major product of rock weathering on the Appalachian Piedmont from New Jersey to Alabama. On the Piedmont, it is the primary substrate from which residual soils are developed. Properties of saprolite and residual soils are highly related to their parent rocks. Studies of cores and outcrops illustrate that rock structure and mineralogy control upland regolith zonation. Saprolite develops by in situ chemical alteration of a wide variety of mafic to highly silicic rocks. Thickness of upland saprolite varies from a few meters on mafic rocks to tens of meters on silicic rocks. Saprolite thickness decreases with increasing slope and saprolite is generally thin or absent in valley bottoms. Massive residual subsoils and soils develop by physical and chemical processes that alter the upper few meters of saprolite. The fabric, texture and mineralogy of residual soils are distinctly different from underlying saprolite. The boundary between soil and saprolite is often gradual, and often a zone of low permeability. Geologic maps are useful guides to Piedmont regolith thickness and zonation. In regional design studies, geologic maps and regolith characteristics can be useful in environmental decision-making.

Classification and characterization of Japanese consumers' beef preferences by external preference mapping.

PubMed

Sasaki, Keisuke; Ooi, Motoki; Nagura, Naoto; Motoyama, Michiyo; Narita, Takumi; Oe, Mika; Nakajima, Ikuyo; Hagi, Tatsuro; Ojima, Koichi; Kobayashi, Miho; Nomura, Masaru; Muroya, Susumu; Hayashi, Takeshi; Akama, Kyoko; Fujikawa, Akira; Hokiyama, Hironao; Kobayashi, Kuniyuki; Nishimura, Takanori

2017-08-01

Over the past few decades, beef producers in Japan have improved marbling in their beef products. It was recently reported that marbling is not well correlated with palatability as rated by Japanese consumers. This study sought to identify the consumer segments in Japan that prefer sensory characteristics of beef other than high marbling. Three Wagyu beef, one Holstein beef and two lean imported beef longissimus samples were subjected to a descriptive sensory test, physicochemical analysis and a consumer (n = 307) preference test. According to consumer classification and external preference mapping, four consumer segments were identified as 'gradual high-fat likers', 'moderate-fat and distinctive taste likers', 'Wagyu likers' and 'distinctive texture likers'. Although the major trend of Japanese consumers' beef preference was 'marbling liking', 16.9% of the consumers preferred beef samples that had moderate marbling and distinctive taste. The consumers' attitudes expressed in a questionnaire survey were in good agreement with the preference for marbling among the 'moderate-fat and distinctive taste likers'. These results indicate that moderately marbled beef is a potent category in the Japanese beef market. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Distinct Motion of GFP-Tagged Histone Expressing Cells Under AC Electrokinetics in Electrode-Multilayered Microfluidic Device.

PubMed

Yao, Jiafeng; Sugawara, Michiko; Obara, Hiromichi; Mizutani, Takeomi; Takei, Masahiro

2017-12-01

The distinct motion of GFP-tagged histone expressing cells (Histone-GFP type cells) has been investigated under ac electrokinetics in an electrode-multilayered microfluidic device as compared with Wild type cells and GFP type cells in terms of different intracellular components. The Histone-GFP type cells were modified by the transfection of green fluorescent protein-fused histone from the human lung fibroblast cell line. The velocity of the Histone-GFP type cells obtained by particle tracking velocimetry technique is faster than Wild type cells by 24.9% and GFP type cells by 57.1%. This phenomenon is caused by the more amount of proteins in the intracellular of single Histone-GFP type cell than that of the Wild type and GFP type cells. The more amount of proteins in the Histone-GFP type cells corresponds to a lower electric permittivity ϵ c of the cells, which generates a lower dielectrophoretic force exerting on the cells. The velocity of Histone-GFP type cells is well agreed with Eulerian-Lagrangian two-phase flow simulation by 4.2% mean error, which proves that the fluid motion driven by thermal buoyancy and electrothermal force dominates the direction of cells motion, while the distinct motion of Histone-GFP type cells is caused by dielectrophoretic force. The fluid motion does not generate a distinct drag motion for Histone-GFP type cells because the Histone-GFP type cells have the same size to the Wild type and GFP type cells. These results clarified the mechanism of cells motion in terms of intracellular components, which helps to improve the cell manipulation efficiency with electrokinetics.

Variability in soil CO2 efflux across distinct urban land cover types

NASA Astrophysics Data System (ADS)

Weissert, Lena F.; Salmond, Jennifer A.; Schwendenmann, Luitgard

2015-04-01

As a main source of greenhouse gases urban areas play an important role in the global carbon cycle. To assess the potential role of urban vegetation in mitigating carbon emissions we need information on the magnitude of biogenic CO2 emissions and its driving factors. We examined how urban land use types (urban forest, parklands, sportsfields) vary in their soil CO2 efflux. We measured soil CO2 efflux and its isotopic signature, soil temperature and soil moisture over a complete growing season in Auckland, New Zealand. Soil physical and chemical properties and vegetation characteristics were also measured. Mean soil CO2 efflux ranged from 4.15 to 12 μmol m-2 s-1. We did not find significant differences in soil CO2 efflux among land cover types due to high spatial variability in soil CO2 efflux among plots. Soil (soil carbon and nitrogen density, texture, soil carbon:nitrogen ratio) and vegetation characteristics (basal area, litter carbon density, grass biomass) were not significantly correlated with soil CO2 efflux. We found a distinct seasonal pattern with significantly higher soil CO2 efflux in autumn (Apr/May) and spring (Oct). In urban forests and sportsfields over 80% of the temporal variation was explained by soil temperature and soil water content. The δ13C signature of CO2 respired from parklands and sportsfields (-20 permil - -25 permil) were more positive compared to forest plots (-29 permil) indicating that parkland and sportsfields had a considerable proportion of C4 grasses. Despite the large intra-urban variability, our results compare to values reported from other, often climatically different cities, supporting the hypothesis of homogenization across urban areas as a result of human management practices.

Resolving anthropogenic aerosol pollution types - deconvolution and exploratory classification of pollution events

NASA Astrophysics Data System (ADS)

Äijälä, Mikko; Heikkinen, Liine; Fröhlich, Roman; Canonaco, Francesco; Prévôt, André S. H.; Junninen, Heikki; Petäjä, Tuukka; Kulmala, Markku; Worsnop, Douglas; Ehn, Mikael

2017-03-01

Mass spectrometric measurements commonly yield data on hundreds of variables over thousands of points in time. Refining and synthesizing this raw data into chemical information necessitates the use of advanced, statistics-based data analytical techniques. In the field of analytical aerosol chemistry, statistical, dimensionality reductive methods have become widespread in the last decade, yet comparable advanced chemometric techniques for data classification and identification remain marginal. Here we present an example of combining data dimensionality reduction (factorization) with exploratory classification (clustering), and show that the results cannot only reproduce and corroborate earlier findings, but also complement and broaden our current perspectives on aerosol chemical classification. We find that applying positive matrix factorization to extract spectral characteristics of the organic component of air pollution plumes, together with an unsupervised clustering algorithm, k-means+ + , for classification, reproduces classical organic aerosol speciation schemes. Applying appropriately chosen metrics for spectral dissimilarity along with optimized data weighting, the source-specific pollution characteristics can be statistically resolved even for spectrally very similar aerosol types, such as different combustion-related anthropogenic aerosol species and atmospheric aerosols with similar degree of oxidation. In addition to the typical oxidation level and source-driven aerosol classification, we were also able to classify and characterize outlier groups that would likely be disregarded in a more conventional analysis. Evaluating solution quality for the classification also provides means to assess the performance of mass spectral similarity metrics and optimize weighting for mass spectral variables. This facilitates algorithm-based evaluation of aerosol spectra, which may prove invaluable for future development of automatic methods for spectra identification and classification. Robust, statistics-based results and data visualizations also provide important clues to a human analyst on the existence and chemical interpretation of data structures. Applying these methods to a test set of data, aerosol mass spectrometric data of organic aerosol from a boreal forest site, yielded five to seven different recurring pollution types from various sources, including traffic, cooking, biomass burning and nearby sawmills. Additionally, three distinct, minor pollution types were discovered and identified as amine-dominated aerosols.

Distinct effects of Cr bulk doping and surface deposition on the chemical environment and electronic structure of the topological insulator Bi2Se3

NASA Astrophysics Data System (ADS)

Yilmaz, Turgut; Hines, William; Sun, Fu-Chang; Pletikosić, Ivo; Budnick, Joseph; Valla, Tonica; Sinkovic, Boris

2017-06-01

In this report, it is shown that Cr doped into the bulk and Cr deposited on the surface of Bi2Se3 films produced by molecular beam epitaxy (MBE) have strikingly different effects on both the electronic structure and chemical environment. Angle resolved photoemission spectroscopy (ARPES) shows that Cr doped into the bulk opens a surface state energy gap which can be seen at room temperature; much higher than the measured ferromagnetic transition temperature of ≈10 K. On the other hand, similar ARPES measurements show that the surface states remain gapless down to 15 K for films with Cr surface deposition. In addition, core-level photoemission spectroscopy of the Bi 5d, Se 3d, and Cr 3p core levels show distinct differences in the chemical environment for the two methods of Cr introduction. Surface deposition of Cr results in the formation of shoulders on the lower binding energy side for the Bi 5d peaks and two distinct Cr 3p peaks indicative of two Cr sites. These striking differences suggests an interesting possibility that better control of doping at only near surface region may offer a path to quantum anomalous Hall states at higher temperatures than reported in the literature.

Isolation and characterization of lipid rafts in Emiliania huxleyi: a role for membrane microdomains in host-virus interactions.

PubMed

Rose, Suzanne L; Fulton, James M; Brown, Christopher M; Natale, Frank; Van Mooy, Benjamin A S; Bidle, Kay D

2014-04-01

Coccolithoviruses employ a suite of glycosphingolipids (GSLs) to successfully infect the globally important coccolithophore Emiliania huxleyi. Lipid rafts, chemically distinct membrane lipid microdomains that are enriched in GSLs and are involved in sensing extracellular stimuli and activating signalling cascades through protein-protein interactions, likely play a fundamental role in host-virus interactions. Using combined lipidomics, proteomics and bioinformatics, we isolated and characterized the lipid and protein content of lipid rafts from control E. huxleyi cells and those infected with EhV86, the type strain for Coccolithovirus. Lipid raft-enriched fractions were isolated and purified as buoyant, detergent-resistant membranes (DRMs) in OptiPrep density gradients. Transmission electron microscopy of vesicle morphology, polymerase chain reaction amplification of the EhV major capsid protein gene and immunoreactivity to flotillin antisera served as respective physical, molecular and biochemical markers. Subsequent lipid characterization of DRMs via high performance liquid chromatography-triple quadrapole mass spectrometry revealed four distinct GSL classes. Parallel proteomic analysis confirmed flotillin as a major lipid raft protein, along with a variety of proteins affiliated with host defence, programmed cell death and innate immunity pathways. The detection of an EhV86-encoded C-type lectin-containing protein confirmed that infection occurs at the interface between lipid rafts and cellular stress/death pathways via specific GSLs and raft-associated proteins. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

Assessing the influence of side-chain and main-chain aromatic benzyltrimethyl ammonium on anion exchange membranes.

PubMed

Li, Xiuhua; Nie, Guanghui; Tao, Jinxiong; Wu, Wenjun; Wang, Liuchan; Liao, Shijun

2014-05-28

3,3'-Di(4″-methyl-phenyl)-4,4'-difluorodiphenyl sulfone (DMPDFPS), a new monomer with two pendent benzyl groups, was easily prepared by Suzuki coupling reaction in high yield. A series of side-chain type ionomers (PAES-Qs) containing pendant side-chain benzyltrimethylammonium groups, which linked to the backbone by alkaline resisting conjugated C-C bonds, were synthesized via polycondensation, bromination, followed by quaternization and alkalization. To assess the influence of side-chain and main-chain aromatic benzyltrimethylammonium on anion exchange membranes (AEMs), the main-chain type ionomers (MPAES-Qs) with the same backbone were synthesized following the similar procedure. GPC and (1)H NMR results indicate that the bromination shows no reaction selectivity of polymer configurations and ionizations of the side-chain type polymers display higher conversions than that of the main-chain type ones do. These two kinds of AEMs were evaluated in terms of ion exchange capacity (IEC), water uptake, swelling ratio, λ, volumetric ion exchange capacity (IECVwet), hydroxide conductivity, mechanical and thermal properties, and chemical stability, respectively. The side-chain type structure endows AEMs with lower water uptake, swelling ratio and λ, higher IECVwet, much higher hydroxide conductivity, more robust dimensional stability, mechanical and thermal properties, and higher stability in hot alkaline solution. The side-chain type cationic groups containing molecular configurations have the distinction of being practical AEMs and membrane electrode assemblies of AEMFCs.

Syngenetic Au on the Carlin trend: Implications for Carlin-type deposits

USGS Publications Warehouse

Emsbo, P.; Hutchinson, R.W.; Hofstra, A.H.; Volk, J.A.; Bettles, K.H.; Baschuk, G.J.; Johnson, C.A.

1999-01-01

A new type of gold occurrence recently discovered in the Carlin trend, north-central Nevada, is clearly distinct from classic Carlin-type gold ore. These occurrences are interpreted to be of sedimentary exhalative (sedex) origin because they are stratiform and predate compaction and lithification of their unaltered Devonian host rocks. They contain barite that exhibits ??34S and ??18O values identical to sulfate in Late Devonian seawater and sedex-type barite deposits. Abrupt facies changes in the host rocks strongly suggest synsedimentary faulting and foundering of the carbonate shelf during mineralization, as is characteristic of sedex deposits. Gold occurs both as native inclusions in synsedimentary base-metal sulfides and barite, and as chemical enrichments in sulfide minerals. The absence of alteration and lack of ??13C and ??18O isotopic shift of primary carbonates in these rocks is strong evidence that this gold was not introduced with classic Carlin-type mineralization. Collectively, these features show that the Devonian strata were significantly enriched in gold some 300 m.y. prior to generation of the mid-Tertiary Carlin-type deposits. These strata may have been an important, perhaps even vital, source of gold for the latter. Although gold is typically low in most Zn-Pb-rich sedex deposits, our evidence suggests that transport of gold in basinal fluids, and its subsequent deposition in the sedex environment, can be significant.

Thermal infrared near-field spectroscopy.

PubMed

Jones, Andrew C; Raschke, Markus B

2012-03-14

Despite the seminal contributions of Kirchhoff and Planck describing far-field thermal emission, fundamentally distinct spectral characteristics of the electromagnetic thermal near-field have been predicted. However, due to their evanescent nature their direct experimental characterization has remained elusive. Combining scattering scanning near-field optical microscopy with Fourier-transform spectroscopy using a heated atomic force microscope tip as both a local thermal source and scattering probe, we spectroscopically characterize the thermal near-field in the mid-infrared. We observe the spectrally distinct and orders of magnitude enhanced resonant spectral near-field energy density associated with vibrational, phonon, and phonon-polariton modes. We describe this behavior and the associated distinct on- and off-resonance nanoscale field localization with model calculations of the near-field electromagnetic local density of states. Our results provide a basis for intrinsic and extrinsic resonant manipulation of optical forces, control of nanoscale radiative heat transfer with optical antennas, and use of this new technique of thermal infrared near-field spectroscopy for broadband chemical nanospectroscopy. © 2012 American Chemical Society

Chemical Laws, Idealization and Approximation

NASA Astrophysics Data System (ADS)

Tobin, Emma

2013-07-01

This paper examines the notion of laws in chemistry. Vihalemm ( Found Chem 5(1):7-22, 2003) argues that the laws of chemistry are fundamentally the same as the laws of physics they are all ceteris paribus laws which are true "in ideal conditions". In contrast, Scerri (2000) contends that the laws of chemistry are fundamentally different to the laws of physics, because they involve approximations. Christie ( Stud Hist Philos Sci 25:613-629, 1994) and Christie and Christie ( Of minds and molecules. Oxford University Press, New York, pp. 34-50, 2000) agree that the laws of chemistry are operationally different to the laws of physics, but claim that the distinction between exact and approximate laws is too simplistic to taxonomise them. Approximations in chemistry involve diverse kinds of activity and often what counts as a scientific law in chemistry is dictated by the context of its use in scientific practice. This paper addresses the question of what makes chemical laws distinctive independently of the separate question as to how they are related to the laws of physics. From an analysis of some candidate ceteris paribus laws in chemistry, this paper argues that there are two distinct kinds of ceteris paribus laws in chemistry; idealized and approximate chemical laws. Thus, while Christie ( Stud Hist Philos Sci 25:613-629, 1994) and Christie and Christie ( Of minds and molecules. Oxford University Press, New York, pp. 34--50, 2000) are correct to point out that the candidate generalisations in chemistry are diverse and heterogeneous, a distinction between idealizations and approximations can nevertheless be used to successfully taxonomise them.

Characterization of heterocyclic rings through quantum chemical topology.

PubMed

Griffiths, Mark Z; Popelier, Paul L A

2013-07-22

Five-membered rings are found in a myriad of molecules important in a wide range of areas such as catalysis, nutrition, and drug and agrochemical design. Systematic insight into their largely unexplored chemical space benefits from first principle calculations presented here. This study comprehensively investigates a grand total of 764 different rings, all geometry optimized at the B3LYP/6-311+G(2d,p) level, from the perspective of Quantum Chemical Topology (QCT). For the first time, a 3D space of local topological properties was introduced, in order to characterize rings compactly. This space is called RCP space, after the so-called ring critical point. This space is analogous to BCP space, named after the bond critical point, which compactly and successfully characterizes a chemical bond. The relative positions of the rings in RCP space are determined by the nature of the ring scaffold, such as the heteroatoms within the ring or the number of π-bonds. The summed atomic QCT charges of the five ring atoms revealed five features (number and type of heteroatom, number of π-bonds, substituent and substitution site) that dictate a ring's net charge. Each feature independently contributes toward a ring's net charge. Each substituent has its own distinct and systematic effect on the ring's net charge, irrespective of the ring scaffold. Therefore, this work proves the possibility of designing a ring with specific properties by fine-tuning it through manipulation of these five features.

A decision support framework for characterizing and managing dermal exposures to chemicals during Emergency Management and Operations.

PubMed

Dotson, G Scott; Hudson, Naomi L; Maier, Andrew

2015-01-01

Emergency Management and Operations (EMO) personnel are in need of resources and tools to assist in understanding the health risks associated with dermal exposures during chemical incidents. This article reviews available resources and presents a conceptual framework for a decision support system (DSS) that assists in characterizing and managing risk during chemical emergencies involving dermal exposures. The framework merges principles of three decision-making techniques: 1) scenario planning, 2) risk analysis, and 3) multicriteria decision analysis (MCDA). This DSS facilitates dynamic decision making during each of the distinct life cycle phases of an emergency incident (ie, preparedness, response, or recovery) and identifies EMO needs. A checklist tool provides key questions intended to guide users through the complexities of conducting a dermal risk assessment. The questions define the scope of the framework for resource identification and application to support decision-making needs. The framework consists of three primary modules: 1) resource compilation, 2) prioritization, and 3) decision. The modules systematically identify, organize, and rank relevant information resources relating to the hazards of dermal exposures to chemicals and risk management strategies. Each module is subdivided into critical elements designed to further delineate the resources based on relevant incident phase and type of information. The DSS framework provides a much needed structure based on contemporary decision analysis principles for 1) documenting key questions for EMO problem formulation and 2) a method for systematically organizing, screening, and prioritizing information resources on dermal hazards, exposures, risk characterization, and management.

A decision support framework for characterizing and managing dermal exposures to chemicals during Emergency Management and Operations

PubMed Central

Dotson, G. Scott; Hudson, Naomi L.; Maier, Andrew

2016-01-01

Emergency Management and Operations (EMO) personnel are in need of resources and tools to assist in understanding the health risks associated with dermal exposures during chemical incidents. This article reviews available resources and presents a conceptual framework for a decision support system (DSS) that assists in characterizing and managing risk during chemical emergencies involving dermal exposures. The framework merges principles of three decision-making techniques: 1) scenario planning, 2) risk analysis, and 3) multicriteria decision analysis (MCDA). This DSS facilitates dynamic decision making during each of the distinct life cycle phases of an emergency incident (ie, preparedness, response, or recovery) and identifies EMO needs. A checklist tool provides key questions intended to guide users through the complexities of conducting a dermal risk assessment. The questions define the scope of the framework for resource identification and application to support decision-making needs. The framework consists of three primary modules: 1) resource compilation, 2) prioritization, and 3) decision. The modules systematically identify, organize, and rank relevant information resources relating to the hazards of dermal exposures to chemicals and risk management strategies. Each module is subdivided into critical elements designed to further delineate the resources based on relevant incident phase and type of information. The DSS framework provides a much needed structure based on contemporary decision analysis principles for 1) documenting key questions for EMO problem formulation and 2) a method for systematically organizing, screening, and prioritizing information resources on dermal hazards, exposures, risk characterization, and management. PMID:26312660

New types of submarine groundwater discharge from a saliferous clay formation - the case of the Dead Sea

NASA Astrophysics Data System (ADS)

Siebert, Christian; Broder, Merkel; Thomas, Pohl; Yossi, Yechieli; Eldat, Hazan; Danny, Ionescu; Ulf, Mallast

2017-04-01

Along the coastline of the hyper-saline and dramatically dropping Dead Sea, fresh to highly saline groundwaters discharge abundantly from dry falling lakebed. During its history, the level and hence salinity of the lake strongly fluctuated, resulting in the deposition of an alternating sequence of clayey and chemical sediments (mainly halite, carbonates and sulfates), intercalated by thick beds of halite and of coarse clastics around wadi outlets, respectively. Due to the asymmetrical shape of the lake's basin, these strata are deposited unequally along the eastern and western flank, why only groundwaters coming from the west have to pass thick layers of these sediments on their way into the lake. On the base of trace elements (REE), element ratios, stable and radioisotopes and microbiological findings, the observed onshore and offshore springs revealed, freshwaters discharge from both Cretaceous limestone aquifers and efficiently dissolve the easily soluble halite and flush the interstitial brines from the saliferous clay formation, immediately after entering the sedimentary strata. Abundant microbial activity result in the widespread production of sulfuric acid, accelerating erosion of carbonates and sulfates. These processes result in a fast and striking karstification of the strata, enabling groundwaters to transcendent the fresh/saltwater interface trough open pipes. As results, submarine groundwater discharge (SGD) occurs randomly and in addition to terrestrial, submarine sinkholes develop very quickly too. Due to the variable maturity of the flow paths, salinity and chemical composition of SGD shows an extremely wide range, from potable water to TDS of >250 g/l. Submarine emerging groundwaters with salinities even higher then that of the Dead Sea and distinctly different chemical and isotopic composition form outlets, which are not known elsewhere and represent a novel and unique type of SGD, only observed in the Dead Sea yet.

The post-collisional late Variscan ferroan granites of southern Sardinia (Italy): Inferences for inhomogeneity of lower crust

NASA Astrophysics Data System (ADS)

Conte, Aida Maria; Cuccuru, Stefano; D'Antonio, Massimo; Naitza, Stefano; Oggiano, Giacomo; Secchi, Francesco; Casini, Leonardo; Cifelli, Francesca

2017-12-01

The post-collisional late Variscan magmatism of Sardinia-Corsica batholith attained a peak at about 290 Ma. In southern Sardinia, in the frontal part of the Variscan orogenic wedge, this magmatism is represented by three suites of granitoids, here defined as GS1, GS2 and GS3. GS1, GS2 and GS3 are slightly peraluminous and F-bearing granitoids; GS1 and GS3 granites show in addition a ferroan character, whereas GS2 rocks range from magnesian to ferroan, from granodiorites to leucogranites. From magnetic susceptibility data, GS1 and GS2 belong to the ilmenite series, whereas GS3 is a slightly oxidized rock-suite plotting on the ilmenite/magnetite series boundary. Each rock-suite shows distinctive characters, in terms of petrography, petrochemistry, rock associations, as well as metallogenic signature of the related fluids. The distinction among rock-suite types is made on the basis of both mafic and characteristic accessory minerals. Siderophyllitic dark mica as the only mafic phase, and accessory xenotime (Y) characterize the GS1 rocks; GS2 mineral associations include biotite ± hornblende + allanite + magnetite; GS3 rocks show an association of hastingsite + annite + allanite + magnetite. Chemical variations in the studied samples suggest different magmatic evolution of independent magmas. Pb, Sr and Nd isotopic data constrain the origin of magmas to lower crustal sources. Chemical composition of rocks and dark micas meet those of liquids experimentally obtained by low degrees of partial melting of different meta-igneous deep crustal sources, felsic for GS1 rock-types and more mafic for GS3 rock-types. GS1 intrusions show granophile-type (Sn-W-Mo) metallogenic signatures, very low magnetic susceptibility, and Nd model ages (referred to the Depleted Mantle - TDM) of 2.3 Ga, coherent with a possible derivation from an old (early Proterozoic-Neoarchean), reduced and weathered basement, tectonically buried under Variscan covers. A definite deep crustal inhomogeneity is mirrored by GS3 granites, whose compositional and isotopic features indicate a younger (Nd model age: 1.6 Ga) tonalitic amphibolite source. Overall, the peculiarities of the studied granitoids suggest further compositional differences in the deep crust between southern and northern portion of the Sardinia-Corsica Variscan transect. Late Variscan lithospheric delamination appears as the most reliable mechanism that may have determined the high thermal regime that triggered partial melting of the crust. The close field association, at 290 Ma, of tholeiitic dike swarms and ferroan granitoids, supports this inference.

Emergence of a few distinct structures from a single formal structure type during high-throughput screening for stable compounds: The case of RbCuS and RbCuSe

NASA Astrophysics Data System (ADS)

Trimarchi, Giancarlo; Zhang, Xiuwen; DeVries Vermeer, Michael J.; Cantwell, Jacqueline; Poeppelmeier, Kenneth R.; Zunger, Alex

2015-10-01

Theoretical sorting of stable and synthesizable "missing compounds" from those that are unstable is a crucial step in the discovery of previously unknown functional materials. This active research area often involves high-throughput (HT) examination of the total energy of a given compound in a list of candidate formal structure types (FSTs), searching for those with the lowest energy within that list. While it is well appreciated that local relaxation methods based on a fixed list of structure types can lead to inaccurate geometries, this approach is widely used in HT studies because it produces answers faster than global optimization methods (that vary lattice vectors and atomic positions without local restrictions). We find, however, a different failure mode of the HT protocol: specific crystallographic classes of formal structure types each correspond to a series of chemically distinct "daughter structure types" (DSTs) that have the same space group but possess totally different local bonding configurations, including coordination types. Failure to include such DSTs in the fixed list of examined candidate structures used in contemporary high-throughput approaches can lead to qualitative misidentification of the stable bonding pattern, not just quantitative inaccuracies. In this work, we (i) clarify the understanding of the general DST-FST relationship, thus improving current discovery HT approaches, (ii) illustrate this failure mode for RbCuS and RbCuSe (the latter being a yet unreported compound and is predicted here) by developing a synthesis method and accelerated crystal-structure determination, and (iii) apply the genetic-algorithm-based global space-group optimization (GSGO) approach which is not vulnerable to the failure mode of HT searches of fixed lists, demonstrating a correct identification of the stable DST. The broad impact of items (i)-(iii) lies in the demonstrated predictive ability of a more comprehensive search strategy than what is currently used—use HT calculations as the preliminary broad screening followed by unbiased GSGO of the final candidates.

Fast intraslab fluid-flow events linked to pulses of high pore fluid pressure at the subducted plate interface

NASA Astrophysics Data System (ADS)

Taetz, Stephan; John, Timm; Bröcker, Michael; Spandler, Carl; Stracke, Andreas

2018-01-01

A better understanding of the subduction zone fluid cycle and its chemical-mechanical feedback requires in-depth knowledge about how fluids flow within and out of descending slabs. Relicts of fluid-flow systems in exhumed rocks of fossil subduction zones allow for identification of the general relationships between dehydration reactions, fluid pathway formation, the dimensions and timescales of distinct fluid flow events; all of which are required for quantitative models for fluid-induced subduction zone processes. Two types of garnet-quartz-phengite veins can be distinguished in an eclogite-facies mélange block from the Pouébo Eclogite Mélange, New Caledonia. These veins record synmetamorphic internal fluid release by mineral breakdown reactions (type I veins), and infiltration of an external fluid (type II veins) with the associated formation of a reaction selvage. The dehydration and fluid migration documented by the type I veins likely occurred on a timescale of 105-106 years, based on average subduction rates and metamorphic conditions required for mineral dehydration and fluid flow. The timeframe of fluid-rock interaction between the external fluid and the wall-rock of the type II veins is quantified using a continuous bulk-rock Li-diffusion profile perpendicular to a vein and its metasomatic selvage. Differences in Li concentration between the internal and external fluid reservoirs resulted in a distinct diffusion profile (decreasing Li concentration and increasing δ7 Li) as the reaction front propagated into the host rock. Li-chronometric constraints indicate that the timescales of fluid-rock interaction associated with type II vein formation are on the order of 1 to 4 months (0.150-0.08+0.14 years). The short-lived, pulse-like character of this process is consistent with the notion that fluid flow caused by oceanic crust dehydration at the blueschist-to-eclogite transition contributes to or even dominates episodic pore fluid pressure increases at the plate interface, which in turn, may trigger slip events reported from many subduction zones.

Possible Sulfates in the Northeast Syrtis Major Region

NASA Image and Video Library

2015-09-16

A variety of diverse morphological features are present in this image (21 by 5.5 kilometers) located in the southeastern area of the Nili Fossae region and just northeast of Syrtis Major. This particular region has been studied intensely due to the presence of volcanics from Syrtis Major and impact ejecta from the Isidis Basin. The region is rich in unaltered mafic deposits, in contact with diverse altered deposits rich in clays, carbonates, and sulfates. These deposits make the Nili Fossae region one of the most colorful regions on Mars, which is most distinctive in infrared color composites (IRB). HiRISE IRB color aids in chemical and mineral-type mapping, especially when correlated with other MRO instruments such as CRISM. http://photojournal.jpl.nasa.gov/catalog/PIA19940

Anticancer Pyrroloquinazoline LBL1 Targets Nuclear Lamins.

PubMed

Li, Bingbing X; Chen, Jingjin; Chao, Bo; David, Larry L; Xiao, Xiangshu

2018-05-18

Target identification of bioactive compounds is critical for understanding their mechanism of action. We previously discovered a novel pyrroloquinazoline compound LBL1 with significant anticancer activity. However, its molecular targets remain to be established. Herein, we developed a clickable photoaffinity probe based on LBL1. Using extensive chemical, biochemical, and cellular studies with this probe and LBL1, we found that LBL1 targets nuclear lamins, which are type V intermediate filament (IF) proteins. Further studies showed that LBL1 binds to the coiled-coil domain of lamin A. These results revealed that IF proteins can also be targeted with appropriate small molecules besides two other cytoskeletal proteins actin filaments and microtubules, providing a novel avenue to investigate lamin biology and a novel strategy to develop distinct anticancer therapies.

Electrokinetic Supercapacitor for Simultaneous Harvesting and Storage of Mechanical Energy.

PubMed

Yang, Peihua; Qu, Xiaopeng; Liu, Kang; Duan, Jiangjiang; Li, Jia; Chen, Qian; Xue, Guobin; Xie, Wenke; Xu, Zhimou; Zhou, Jun

2018-03-07

Energy harvesting and storage are two distinct processes that are generally achieved using two separated parts based on different physical and chemical principles. Here we report a self-charging electrokinetic supercapacitor that directly couples the energy harvesting and storage processes into one device. The device consists of two identical carbon nanotube/titanium electrodes, separated by a piece of anodic aluminum oxide nanochannels membrane. Pressure-driven electrolyte flow through the nanochannels generates streaming potential, which can be used to charge the capacitive electrodes, accomplishing simultaneous energy generation and storage. The device stores electric charge density of 0.4 mC cm -2 after fully charging under pressure of 2.5 bar. This work may offer a train of thought for the development of a new type of energy unit for self-powered systems.

Ionotropic GABA receptor antagonism-induced adverse outcome pathways for potential neurotoxicity biomarkers.

PubMed

Gong, Ping; Hong, Huixiao; Perkins, Edward J

2015-01-01

Antagonism of ionotropic GABA receptors (iGABARs) can occur at three distinct types of receptor binding sites causing chemically induced epileptic seizures. Here we review three adverse outcome pathways, each characterized by a specific molecular initiating event where an antagonist competitively binds to active sites, negatively modulates allosteric sites or noncompetitively blocks ion channel on the iGABAR. This leads to decreased chloride conductance, followed by depolarization of affected neurons, epilepsy-related death and ultimately decreased population. Supporting evidence for causal linkages from the molecular to population levels is presented and differential sensitivity to iGABAR antagonists in different GABA receptors and organisms discussed. Adverse outcome pathways are poised to become important tools for linking mechanism-based biomarkers to regulated outcomes in next-generation risk assessment.

Spatial Molecular Architecture of the Microbial Community of a Peltigera Lichen.

PubMed

Garg, Neha; Zeng, Yi; Edlund, Anna; Melnik, Alexey V; Sanchez, Laura M; Mohimani, Hosein; Gurevich, Alexey; Miao, Vivian; Schiffler, Stefan; Lim, Yan Wei; Luzzatto-Knaan, Tal; Cai, Shengxin; Rohwer, Forest; Pevzner, Pavel A; Cichewicz, Robert H; Alexandrov, Theodore; Dorrestein, Pieter C

2016-01-01

Microbes are commonly studied as individual species, but they exist as mixed assemblages in nature. At present, we know very little about the spatial organization of the molecules, including natural products that are produced within these microbial networks. Lichens represent a particularly specialized type of symbiotic microbial assemblage in which the component microorganisms exist together. These composite microbial assemblages are typically comprised of several types of microorganisms representing phylogenetically diverse life forms, including fungi, photosymbionts, bacteria, and other microbes. Here, we employed matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) imaging mass spectrometry to characterize the distributions of small molecules within a Peltigera lichen. In order to probe how small molecules are organized and localized within the microbial consortium, analytes were annotated and assigned to their respective producer microorganisms using mass spectrometry-based molecular networking and metagenome sequencing. The spatial analysis of the molecules not only reveals an ordered layering of molecules within the lichen but also supports the compartmentalization of unique functions attributed to various layers. These functions include chemical defense (e.g., antibiotics), light-harvesting functions associated with the cyanobacterial outer layer (e.g., chlorophyll), energy transfer (e.g., sugars) surrounding the sun-exposed cyanobacterial layer, and carbohydrates that may serve a structural or storage function and are observed with higher intensities in the non-sun-exposed areas (e.g., complex carbohydrates). IMPORTANCE Microbial communities have evolved over centuries to live symbiotically. The direct visualization of such communities at the chemical and functional level presents a challenge. Overcoming this challenge may allow one to visualize the spatial distributions of specific molecules involved in symbiosis and to define their functional roles in shaping the community structure. In this study, we examined the diversity of microbial genes and taxa and the presence of biosynthetic gene clusters by metagenomic sequencing and the compartmentalization of organic chemical components within a lichen using mass spectrometry. This approach allowed the identification of chemically distinct sections within this composite organism. Using our multipronged approach, various fungal natural products, not previously reported from lichens, were identified and two different fungal layers were visualized at the chemical level.

Spatial Molecular Architecture of the Microbial Community of a Peltigera Lichen

PubMed Central

Garg, Neha; Zeng, Yi; Edlund, Anna; Melnik, Alexey V.; Mohimani, Hosein; Gurevich, Alexey; Miao, Vivian; Schiffler, Stefan; Lim, Yan Wei; Luzzatto-Knaan, Tal; Cai, Shengxin; Rohwer, Forest; Pevzner, Pavel A.; Cichewicz, Robert H.; Alexandrov, Theodore

2016-01-01

ABSTRACT Microbes are commonly studied as individual species, but they exist as mixed assemblages in nature. At present, we know very little about the spatial organization of the molecules, including natural products that are produced within these microbial networks. Lichens represent a particularly specialized type of symbiotic microbial assemblage in which the component microorganisms exist together. These composite microbial assemblages are typically comprised of several types of microorganisms representing phylogenetically diverse life forms, including fungi, photosymbionts, bacteria, and other microbes. Here, we employed matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) imaging mass spectrometry to characterize the distributions of small molecules within a Peltigera lichen. In order to probe how small molecules are organized and localized within the microbial consortium, analytes were annotated and assigned to their respective producer microorganisms using mass spectrometry-based molecular networking and metagenome sequencing. The spatial analysis of the molecules not only reveals an ordered layering of molecules within the lichen but also supports the compartmentalization of unique functions attributed to various layers. These functions include chemical defense (e.g., antibiotics), light-harvesting functions associated with the cyanobacterial outer layer (e.g., chlorophyll), energy transfer (e.g., sugars) surrounding the sun-exposed cyanobacterial layer, and carbohydrates that may serve a structural or storage function and are observed with higher intensities in the non-sun-exposed areas (e.g., complex carbohydrates). IMPORTANCE Microbial communities have evolved over centuries to live symbiotically. The direct visualization of such communities at the chemical and functional level presents a challenge. Overcoming this challenge may allow one to visualize the spatial distributions of specific molecules involved in symbiosis and to define their functional roles in shaping the community structure. In this study, we examined the diversity of microbial genes and taxa and the presence of biosynthetic gene clusters by metagenomic sequencing and the compartmentalization of organic chemical components within a lichen using mass spectrometry. This approach allowed the identification of chemically distinct sections within this composite organism. Using our multipronged approach, various fungal natural products, not previously reported from lichens, were identified and two different fungal layers were visualized at the chemical level. PMID:28028548

An Informatics Approach to Evaluating Combined Chemical Exposures from Consumer Products: A Case Study of Asthma-Associated Chemicals and Potential Endocrine Disruptors

PubMed Central

Gabb, Henry A.; Blake, Catherine

2016-01-01

Background: Simultaneous or sequential exposure to multiple environmental stressors can affect chemical toxicity. Cumulative risk assessments consider multiple stressors but it is impractical to test every chemical combination to which people are exposed. New methods are needed to prioritize chemical combinations based on their prevalence and possible health impacts. Objectives: We introduce an informatics approach that uses publicly available data to identify chemicals that co-occur in consumer products, which account for a significant proportion of overall chemical load. Methods: Fifty-five asthma-associated and endocrine disrupting chemicals (target chemicals) were selected. A database of 38,975 distinct consumer products and 32,231 distinct ingredient names was created from online sources, and PubChem and the Unified Medical Language System were used to resolve synonymous ingredient names. Synonymous ingredient names are different names for the same chemical (e.g., vitamin E and tocopherol). Results: Nearly one-third of the products (11,688 products, 30%) contained ≥ 1 target chemical and 5,229 products (13%) contained > 1. Of the 55 target chemicals, 31 (56%) appear in ≥ 1 product and 19 (35%) appear under more than one name. The most frequent three-way chemical combination (2-phenoxyethanol, methyl paraben, and ethyl paraben) appears in 1,059 products. Further work is needed to assess combined chemical exposures related to the use of multiple products. Conclusions: The informatics approach increased the number of products considered in a traditional analysis by two orders of magnitude, but missing/incomplete product labels can limit the effectiveness of this approach. Such an approach must resolve synonymy to ensure that chemicals of interest are not missed. Commonly occurring chemical combinations can be used to prioritize cumulative toxicology risk assessments. Citation: Gabb HA, Blake C. 2016. An informatics approach to evaluating combined chemical exposures from consumer products: a case study of asthma-associated chemicals and potential endocrine disruptors. Environ Health Perspect 124:1155–1165; http://dx.doi.org/10.1289/ehp.1510529 PMID:26955064

Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining.

PubMed

Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

2011-09-26

A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Pólya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).

9 CFR 75.4 - Interstate movement of equine infectious anemia reactors and approval of laboratories, diagnostic...

Code of Federal Regulations, 2014 CFR

2014-01-01

...: (1) The description, including age, breed, color, sex, and distinctive markings when present (such as... representative, State representative or accredited veterinarian who shall use for the purpose a hot iron or chemical brand, freezemarking or a lip tattoo. If hot iron or chemical branding or freezemarking is used...

9 CFR 75.4 - Interstate movement of equine infectious anemia reactors and approval of laboratories, diagnostic...

Code of Federal Regulations, 2012 CFR

2012-01-01

...: (1) The description, including age, breed, color, sex, and distinctive markings when present (such as... representative, State representative or accredited veterinarian who shall use for the purpose a hot iron or chemical brand, freezemarking or a lip tattoo. If hot iron or chemical branding or freezemarking is used...

9 CFR 75.4 - Interstate movement of equine infectious anemia reactors and approval of laboratories, diagnostic...

Code of Federal Regulations, 2013 CFR

2013-01-01

...: (1) The description, including age, breed, color, sex, and distinctive markings when present (such as... representative, State representative or accredited veterinarian who shall use for the purpose a hot iron or chemical brand, freezemarking or a lip tattoo. If hot iron or chemical branding or freezemarking is used...

Cellulose synthase complexes act in a concerted fashion to synthesize highly aggregated cellulose in secondary cell walls of plants

PubMed Central

Li, Shundai; Bashline, Logan; Zheng, Yunzhen; Xin, Xiaoran; Huang, Shixin; Kong, Zhaosheng; Kim, Seong H.; Cosgrove, Daniel J.; Gu, Ying

2016-01-01

Cellulose, often touted as the most abundant biopolymer on Earth, is a critical component of the plant cell wall and is synthesized by plasma membrane-spanning cellulose synthase (CESA) enzymes, which in plants are organized into rosette-like CESA complexes (CSCs). Plants construct two types of cell walls, primary cell walls (PCWs) and secondary cell walls (SCWs), which differ in composition, structure, and purpose. Cellulose in PCWs and SCWs is chemically identical but has different physical characteristics. During PCW synthesis, multiple dispersed CSCs move along a shared linear track in opposing directions while synthesizing cellulose microfibrils with low aggregation. In contrast, during SCW synthesis, we observed swaths of densely arranged CSCs that moved in the same direction along tracks while synthesizing cellulose microfibrils that became highly aggregated. Our data support a model in which distinct spatiotemporal features of active CSCs during PCW and SCW synthesis contribute to the formation of cellulose with distinct structure and organization in PCWs and SCWs of Arabidopsis thaliana. This study provides a foundation for understanding differences in the formation, structure, and organization of cellulose in PCWs and SCWs. PMID:27647923

Cellulose synthase complexes act in a concerted fashion to synthesize highly aggregated cellulose in secondary cell walls of plants.

PubMed

Li, Shundai; Bashline, Logan; Zheng, Yunzhen; Xin, Xiaoran; Huang, Shixin; Kong, Zhaosheng; Kim, Seong H; Cosgrove, Daniel J; Gu, Ying

2016-10-04

Cellulose, often touted as the most abundant biopolymer on Earth, is a critical component of the plant cell wall and is synthesized by plasma membrane-spanning cellulose synthase (CESA) enzymes, which in plants are organized into rosette-like CESA complexes (CSCs). Plants construct two types of cell walls, primary cell walls (PCWs) and secondary cell walls (SCWs), which differ in composition, structure, and purpose. Cellulose in PCWs and SCWs is chemically identical but has different physical characteristics. During PCW synthesis, multiple dispersed CSCs move along a shared linear track in opposing directions while synthesizing cellulose microfibrils with low aggregation. In contrast, during SCW synthesis, we observed swaths of densely arranged CSCs that moved in the same direction along tracks while synthesizing cellulose microfibrils that became highly aggregated. Our data support a model in which distinct spatiotemporal features of active CSCs during PCW and SCW synthesis contribute to the formation of cellulose with distinct structure and organization in PCWs and SCWs of Arabidopsis thaliana This study provides a foundation for understanding differences in the formation, structure, and organization of cellulose in PCWs and SCWs.

The mammalian respiratory system and critical windows of exposure for children's health.

PubMed Central

Pinkerton, K E; Joad, J P

2000-01-01

The respiratory system is a complex organ system composed of multiple cell types involved in a variety of functions. The development of the respiratory system occurs from embryogenesis to adult life, passing through several distinct stages of maturation and growth. We review embryonic, fetal, and postnatal phases of lung development. We also discuss branching morphogenesis and cellular differentiation of the respiratory system, as well as the postnatal development of xenobiotic metabolizing systems within the lungs. Exposure of the respiratory system to a wide range of chemicals and environmental toxicants during perinatal life has the potential to significantly affect the maturation, growth, and function of this organ system. Although the potential targets for exposure to toxic factors are currently not known, they are likely to affect critical molecular signals expressed during distinct stages of lung development. The effects of exposure to environmental tobacco smoke during critical windows of perinatal growth are provided as an example leading to altered cellular and physiological function of the lungs. An understanding of critical windows of exposure of the respiratory system on children's health requires consideration that lung development is a multistep process and cannot be based on studies in adults. Images Figure 1 Figure 4 PMID:10852845

Legacy effects of no-analogue disturbances alter plant community diversity and composition in semi-arid sagebrush steppe

USGS Publications Warehouse

Ripplinger, Julie; Franklin, Janet; Edwards, Thomas C.

2015-01-01

Questions(i) What role does the type of managed disturbance play in structuring sagebrush steppe plant communities? (ii) How does the composition of post-disturbance plant communities change with time since disturbance? (iii) Does plant community diversity change over time following managed disturbance?LocationField study within the sagebrush steppe ecosystem. Rich County, Utah, USA.MethodsWe developed a chronosequence spanning up to 50 yrs post-treatment to study sagebrush steppe vegetation dynamics. Direct ordination was used to examine plant community composition by managed disturbance type and time since disturbance, and factorial analysis of covariance was used to examine diversity dynamics following disturbance. Indicator species values were calculated in order to identify characteristic species for each disturbance type.ResultsPlant communities experienced a shift toward distinct community composition for each of the three managed disturbance types, and gave no indication of returning to untreated community composition or diversity. Small post-disturbance increases in the number of non-native grass species were observed in the treatments relative to reference, with native forb species making the largest contribution to altered composition. On fire- and chemically-treated sites the proportional native forb species richness increased over time since disturbance, while the proportional contribution of non-native forbs to total species richness decreased. For all three treatment types, native grasses contributed less on average to total richness than on reference sites, while non-native grasses made up a higher proportion of total richness.ConclusionsCommon shrubland management techniques have legacy effects on the composition and diversity of sagebrush steppe plant communities, and no-analogue disturbances, such as chemical or mechanical treatments, have more pronounced legacy effects than treatments similar to natural disturbance regimes (fire). This study informs a broader understanding of how management actions affect natural systems by highlighting the importance of long-term management legacies as drivers of plant community structure and function.

Chemically and geographically distinct solid-phase iron pools in the Southern Ocean.

PubMed

von der Heyden, B P; Roychoudhury, A N; Mtshali, T N; Tyliszczak, T; Myneni, S C B

2012-11-30

Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation and mineralogy are challenging to characterize on a regional scale. We describe a diverse array of iron particles, ranging from 20 to 700 nanometers in diameter, in the waters of the Southern Ocean euphotic zone. Distinct variations in the oxidation state and composition of these iron particles exist between the coasts of South Africa and Antarctica, with different iron pools occurring in different frontal zones. These speciation variations can result in solubility differences that may affect the production of bioavailable dissolved iron.

Silicene catalyzed reduction of nitrobenzene to aniline: A mechanistic study

NASA Astrophysics Data System (ADS)

Morrissey, Christopher; He, Haiying

2018-03-01

The reduction of nitrobenzene to aniline has broad applications in chemical and pharmaceutical industries. The high reaction temperatures and pressures and unavoidable hazardous chemicals of current metal catalysts call for more environmentally friendly non-metal catalysts. In this study, the plausibility of silicene as a potential catalyst for nitrobenzene reduction is investigated with a focus on the distinct reaction mechanism based on the density functional theory. The direct reaction pathway was shown to be distinctly different from the Haber mechanism following PhNO2∗ → PhNO∗ → PhNHO∗ → PhNH2O∗ → PhNH2∗. The hydroxyl groups remain bound to silicene after aniline is formed and acquire a high activation barrier to remove.

Deep-sea seabed habitats: Do they support distinct mega-epifaunal communities that have different vulnerabilities to anthropogenic disturbance?

NASA Astrophysics Data System (ADS)

Bowden, David A.; Rowden, Ashley A.; Leduc, Daniel; Beaumont, Jennifer; Clark, Malcolm R.

2016-01-01

Growing economic interest in seabed resources in the deep-sea highlights the need for information about the spatial distribution and vulnerability to disturbance of benthic habitats and fauna. Categorisation of seabed habitats for management is often based on topographic features such as canyons and seamounts that can be distinguished using regional bathymetry ('mega-habitats'). This is practical but because such habitats are contiguous with others, there is potential for overlap in the communities associated with them. Because concepts of habitat and community vulnerability are based on the traits of individual taxa, the nature and extent of differences between communities have implications for strategies to manage the environmental effects of resource use. Using towed video camera transects, we surveyed mega-epifaunal communities of three topographically-defined habitats (canyon, seamount or knoll, and continental slope) and two physico-chemically defined meso-scale habitats (cold seep and hydrothermal vent) in two regions off New Zealand to assess whether each supports a distinct type of community. Cold seep and hydrothermal vent communities were strongly distinct from those in other habitats. Across the other habitats, however, distinctions between communities were often weak and were not consistent between regions. Dissimilarities among communities across all habitats were stronger and the density of filter-feeding taxa was higher in the Bay of Plenty than on the Hikurangi Margin, whereas densities of predatory and scavenging taxa were higher on the Hikurangi Margin. Substratum diversity at small spatial scales (<1 km) and trawl history were significantly correlated with community composition in both regions. We conclude that, (1) a lack of consistent distinction between communities raises questions about the general utility of topographically-defined mega-habitats in environmental management, (2) fine-scale survey of individual features is necessary to identify the locations, characteristics, and extents of ecologically important or vulnerable seabed communities, and (3) evaluation of habitat vulnerability to future events should be in the context of previous and current disturbances.

Correlated silicon and titanium isotopic compositions of presolar SiC grains from the Murchison CM2 chondrite

NASA Astrophysics Data System (ADS)

Gyngard, Frank; Amari, Sachiko; Zinner, Ernst; Marhas, Kuljeet Kaur

2018-01-01

We report correlated Si, and Ti isotopic compositions and elemental concentrations of 238 presolar SiC grains from the Murchison CM2 meteorite. Combined with measurements of the C and N isotopic compositions of these 238 grains, 220 were determined to be of type mainstream, 10 type AB, 4 type Y and 4 type Z. SiC grains of diameter ≳2.5 μm, to ensure enough material to attempt Ti measurements, were randomly chosen without any other prejudice. The Ti isotopic compositions of the majority of the grains are characterized by enrichments in 46Ti, 47Ti, 49Ti, and 50Ti relative to 48Ti, and show linear isotopic correlations indicative of galactic chemical evolution and neutron capture of the grains parent stars. The variability in the observed Ti signal as a function of depth in most of the grains indicates the presence of distinct subgrains, likely TiC that have been previously observed in TEM studies. Vandium-51 concentrations correlate with those of Ti, indicating V substitutes for Ti in the TiC matrix in many of the grains. No isotopic anomalies in 52Cr/53Cr ratios were observed, and Cr concentrations did not correlate with those of either Ti or V.

Influence of colour type and previous cultivation on secondary metabolites in hypocotyls and leaves of maca (Lepidium meyenii Walpers).

PubMed

Clément, Céline; Diaz Grados, Diego A; Avula, Bharathi; Khan, Ihklas A; Mayer, Andrea C; Ponce Aguirre, Dante D; Manrique, Ivan; Kreuzer, Michael

2010-04-15

Maca is an Andean crop of the Brassicaceae family which is mainly known for its fertility-enhancing properties following consumption. The hypocotyls display various colours ranging from white to black. Each colour has different biological effects. The aim of this study was to analyse the concentrations of major secondary metabolites in hypocotyls and leaves of maca in a controlled planting experiment in the Peruvian Andes at 4130 m above sea level. The effects of colour type and of previous cultivation of the field were examined. In the hypocotyls, the colour type effect was significant for most secondary metabolites; exceptions were beta-sitosterol and campesterol. The lead-coloured, yellow and violet maca hypocotyls were rich in glucosinolates, macaene and macamides, respectively. Previous cultivation affected macaene, campesterol and indole glucosinolate concentrations. Effects on metabolite concentrations in the leaves were minor. Hypocotyls were richer in macaene, macamides and glucosinolates than were leaves, and were poorer in beta-sitosterol and total phenols. Colour type has to be considered in maca production, as colour associates with variations in concentrations of distinct bioactive metabolites. Leaves may be interesting for animal nutrition purposes as they contain essentially the same secondary metabolites as the hypocotyls but in clearly lower concentrations. (c) 2010 Society of Chemical Industry.

Draconibacterium orientale gen. nov., sp. nov., isolated from two distinct marine environments, and proposal of Draconibacteriaceae fam. nov.

PubMed

Du, Zong-Jun; Wang, Ying; Dunlap, Christopher; Rooney, Alejandro P; Chen, Guan-Jun

2014-05-01

The taxonomic characteristics of two bacterial strains, FH5T and SS4, isolated from enrichment cultures obtained from two distinct marine environments, were determined. These bacteria were Gram-stain-negative, facultatively anaerobic rods. Growth occurred at 20-40 °C (optimum, 28-32 °C), pH 5.5-9.0 (optimum, pH 7.0-7.5) and in the presence of 1-7% NaCl (optimum, 2-4%). The major cellular fatty acids were anteiso-C15:0 and iso-C15:0. Menaquinone 7 (MK-7) was the sole respiratory quinone. The major polar lipids were phosphatidylethanolamine, an unkown phospholipid and an unknown lipid. The DNA G+C contents of strains FH5T and SS4 were both determined to be 42.0 mol%. The results of DNA-DNA hybridization studies indicated that the FH5T and SS4 genomes share greater than 95% relatedness. The strains formed a distinct phyletic line within the class Bacteroidia, with less than 89.4% sequence similarity to their closest relatives with validly published names. On the basis of physiological and biochemical characteristics, 16S rRNA gene sequences and chemical properties, a novel genus and species, Draconibacterium orientale gen. nov., sp. nov., within the class Bacteroidia, are proposed, with strain FH5T (=DSM 25947T=CICC 10585T) as the type strain. In addition, a new family, Draconibacteriaceae fam. nov., is proposed to accommodate Draconibacterium gen. nov.

The occurrence of blue luminescing enstatite in E3 and E4 chondrites

NASA Technical Reports Server (NTRS)

Dehart, John M.; Lofgren, Gary E.

1994-01-01

Two compositional types of enstatite that emit cathodoluminescence (CL) are known to exist in E3 and E4 chondrites. The first type consists of the most common enstatites that are relatively FeO-poor and emit a red CL. Their CL is apparently activated by the presence of MnO and Cr2O3 in concentrations of 0.2 and 0.6 weight percent. The second type of enstatite is nearly FeO-free, contains no MnO or Cr2O3 and emits a blue CL. The origin of these two types of enstatite and their accompanying chemical and CL differences has long been a subject of discussion. Leitch and Smith first observed to two types and felt the compositional differences were too great to have formed under the same conditions. They postulated the two types of enstatite formed on separate parent bodies and were mixed when these bodies collided. McKinley et al. observed a continuous range of compositions between blue luminescing and red luminescing enstatites and concluded the two types of enstatite formed evidence that blue luminescing pyroxenes were relics that did not completely melt during the heating event which melted other precursor grains, and are distinct from the red CL pyroxene in the chondrules in E chondrites. In order to further clarify the nature and origin of the pyroxene that emits blue CL, the sections listed in another work were examined for the occurrence of blue luminescing enstatite.

Cell differentiation defines acute and chronic infection cell types in Staphylococcus aureus.

PubMed

García-Betancur, Juan-Carlos; Goñi-Moreno, Angel; Horger, Thomas; Schott, Melanie; Sharan, Malvika; Eikmeier, Julian; Wohlmuth, Barbara; Zernecke, Alma; Ohlsen, Knut; Kuttler, Christina; Lopez, Daniel

2017-09-12

A central question to biology is how pathogenic bacteria initiate acute or chronic infections. Here we describe a genetic program for cell-fate decision in the opportunistic human pathogen Staphylococcus aureus , which generates the phenotypic bifurcation of the cells into two genetically identical but different cell types during the course of an infection. Whereas one cell type promotes the formation of biofilms that contribute to chronic infections, the second type is planktonic and produces the toxins that contribute to acute bacteremia. We identified a bimodal switch in the agr quorum sensing system that antagonistically regulates the differentiation of these two physiologically distinct cell types. We found that extracellular signals affect the behavior of the agr bimodal switch and modify the size of the specialized subpopulations in specific colonization niches. For instance, magnesium-enriched colonization niches causes magnesium binding to S. aureus teichoic acids and increases bacterial cell wall rigidity. This signal triggers a genetic program that ultimately downregulates the agr bimodal switch. Colonization niches with different magnesium concentrations influence the bimodal system activity, which defines a distinct ratio between these subpopulations; this in turn leads to distinct infection outcomes in vitro and in an in vivo murine infection model. Cell differentiation generates physiological heterogeneity in clonal bacterial infections and helps to determine the distinct infection types.

Cell differentiation defines acute and chronic infection cell types in Staphylococcus aureus

PubMed Central

García-Betancur, Juan-Carlos; Goñi-Moreno, Angel; Horger, Thomas; Schott, Melanie; Sharan, Malvika; Eikmeier, Julian; Wohlmuth, Barbara; Zernecke, Alma; Ohlsen, Knut; Kuttler, Christina

2017-01-01

A central question to biology is how pathogenic bacteria initiate acute or chronic infections. Here we describe a genetic program for cell-fate decision in the opportunistic human pathogen Staphylococcus aureus, which generates the phenotypic bifurcation of the cells into two genetically identical but different cell types during the course of an infection. Whereas one cell type promotes the formation of biofilms that contribute to chronic infections, the second type is planktonic and produces the toxins that contribute to acute bacteremia. We identified a bimodal switch in the agr quorum sensing system that antagonistically regulates the differentiation of these two physiologically distinct cell types. We found that extracellular signals affect the behavior of the agr bimodal switch and modify the size of the specialized subpopulations in specific colonization niches. For instance, magnesium-enriched colonization niches causes magnesium binding to S. aureusteichoic acids and increases bacterial cell wall rigidity. This signal triggers a genetic program that ultimately downregulates the agr bimodal switch. Colonization niches with different magnesium concentrations influence the bimodal system activity, which defines a distinct ratio between these subpopulations; this in turn leads to distinct infection outcomes in vitro and in an in vivo murine infection model. Cell differentiation generates physiological heterogeneity in clonal bacterial infections and helps to determine the distinct infection types. PMID:28893374

Detection of chemical contraband using spectroscopic microwave imaging

NASA Astrophysics Data System (ADS)

Falconer, David G.; Watters, David G.

1994-02-01

We have developed and demonstrated a microwave technique for detecting high explosives, illegal drugs, and other chemical contraband in checked airline baggage. Our technique isolates suspicious materials using microwave tomography and identifies chemical contraband using microwave spectroscopy. Measurements in the frequency range 2 - 18 GHz indicate that microwave energy will penetrate nonmetallic suitcases and that contraband materials feature distinct dielectric spectra at these wavelengths. We have also formed microwave images of a soft-sided suitcase and its contents. After manually segmenting the microwave imagery, we successfully identified chemical simulants for both high explosives and illegal drugs.

Sea-dumped chemical weapons: environmental risk, occupational hazard.

PubMed

Greenberg, M I; Sexton, K J; Vearrier, D

2016-01-01

Chemical weapons dumped into the ocean for disposal in the twentieth century pose a continuing environmental and human health risk. In this review we discuss locations, quantity, and types of sea-dumped chemical weapons, related environmental concerns, and human encounters with sea-dumped chemical weapons. We utilized the Ovid (http://ovidsp.tx.ovid.com) and PubMed (http://www.pubmed.org) search engines to perform MEDLINE searches for the terms 'sea-dumped chemical weapons', 'chemical warfare agents', and 'chemical munitions'. The searches returned 5863 articles. Irrelevant and non-English articles were excluded. A review of the references for these articles yielded additional relevant sources, with a total of 64 peer-reviewed articles cited in this paper. History and geography of chemical weapons dumping at sea: Hundreds of thousands of tons of chemical munitions were disposed off at sea following World War II. European, Russian, Japanese, and United States coasts are the areas most affected worldwide. Several areas in the Baltic and North Seas suffered concentrated large levels of dumping, and these appear to be the world's most studied chemical warfare agent marine dumping areas. Chemical warfare agents: Sulfur mustard, Lewisite, and the nerve agents appear to be the chemical warfare agents most frequently disposed off at sea. Multiple other type of agents including organoarsenicals, blood agents, choking agents, and lacrimators were dumped at sea, although in lesser volumes. Environmental concerns: Numerous geohydrologic variables contribute to the rate of release of chemical agents from their original casings, leading to difficult and inexact modeling of risk of release into seawater. Sulfur mustard and the organoarsenicals are the most environmentally persistent dumped chemical agents. Sulfur mustard in particular has a propensity to form a solid or semi-solid lump with a polymer coating of breakdown products, and can persist in this state on the ocean floor for decades. Rates of solubility and hydrolysis and levels of innate toxicity of a chemical agent are used to predict the risk to the marine environments. The organoarsenicals eventually breakdown into arsenic, and thus present an indefinite timeline for contamination. Generally, studies assaying sediment and water levels of parent chemical agents and breakdown products at dumpsites have found minimal amounts of relevant chemicals, although arsenic levels are typically higher in dumpsites than reference areas. Studies of marine organisms have not shown concerning amounts of chemical agents or breakdown products in tissue, but have shown evidence of chronic toxicity. There is believed to be minimal risk posed by seafood consumption. Microbiota assays of dumpsites are significantly altered in species composition compared to reference sites, which may imply unseen but significant changes to ecosystems of dumpsites. Human health concerns: The major human health risk at this time appears to arise from acute exposure to an agent by either accidental recovery of a chemical weapon on a fishing vessel, or by munitions washed ashore onto beaches. Improving technology continues to make the deep sea more accessible, thus increasing the risk of disturbing munitions lying on or buried in the seabed. Pipe laying, cable burying, drilling, scuba diving, trawling, and undersea scientific research are the activities posing the most risk. The long-term threat to the benthic habitat via increased arsenic concentrations, shifts in microbiota speciation, and chronic toxicity to vertebrates and invertebrates is not currently understood. The risk to the environment of massive release via disturbance remains a distinct possibility. Terrorist recovery and re-weaponization of chemical agents is a remote possibility.

Adrenocortical Expression Profiling of Cattle with Distinct Juvenile Temperament Types.

PubMed

Friedrich, Juliane; Brand, Bodo; Graunke, Katharina Luise; Langbein, Jan; Schwerin, Manfred; Ponsuksili, Siriluck

2017-01-01

Temperament affects ease of handling, animal welfare, and economically important production traits in cattle. The use of gene expression profiles as molecular traits provides a novel means of gaining insight into behavioural genetics. In this study, differences in adrenocortical expression profiles between 60 F 2 cows (Charolais × German Holstein) of distinct temperament types were analysed. The cows were assessed in a novel-human test at an age of 90 days. Most of the adrenal cortex transcripts which were differentially expressed (FDR <0.05) were found between temperament types of 'fearful/neophobic-alert' and all other temperament types. These transcripts belong to several biological functions like NRF2-mediated oxidative stress response, Glucocorticoid Receptor Signalling and Complement System. Overall, the present study provides new insight into transcriptional differences in the adrenal cortex between cows of distinct temperament types. Genetic regulations of such molecular traits facilitate uncovering positional and functional gene candidates for temperament type in cattle.

Recommended nomenclature for zeolite minerals: Report of the Subcommittee on Zeolites of the International Mineralogical Association, Commission on New Minerals and Mineral Names

USGS Publications Warehouse

Coombs, D.S.; Alberti, A.; Armbruster, T.; Artioli, G.; Colella, C.; Galli, E.; Grice, Joel D.; Liebau, F.; Mandarino, J.A.; Minato, H.; Nickel, E.H.; Passaglia, E.; Peacor, D.R.; Quartieri, S.; Rinaldi, R.; Ross, M.; Sheppard, R.A.; Tillmanns, E.; Vezzalini, G.

1998-01-01

This report embodies recommendations on zeolite nomenclature approved by the International Mineralogical Association Commission on New Minerals and Mineral Names. In a working definition of a zeolite mineral used for this review, structures containing an interrupted containing an interrupted framework of tetrahedra are accepted where other zeolitic properties prevail, and complete substitution by elements other than Si and Al is alloowed. Separate species are recognized in topologically distinctive compositional series in which different extra-framework cations are the most abundant in atomic proportions. To name these, the appropriate chemical symbol is attached by a hyphen to the series name as a suffix, except for the names harmotome, pollucite and wairakite in the phillipsite and analcime series. Differences in space-group symmetry and in order-disorder relationships in zeolites having the same topologically distinctive framework do not in general provide adequate grounds for recognition of separate species. Zeolite species are not to be distinguished solely in Si:Al ratio except for heulandite (Si:Al < 4.0) and clinoptilolite (Si:Al ??? 4.0). Dehydration, partial hydration and over-hydration are not sufficient grounds for the recognition of separate species of zeolites. Use of the term 'ideal formula' should be avoided in referring to a simplified or averaged formula of zeolite. Newly recognized species in compositional series are as follows: brewsterite-Sr, -Ba; chabazite-Ca, -Na, -K; clinoptilolite-K, -Na, -Ca; dechiardite-Ca, -Na; erionite-Na, -K, -Ca,; faujasite-Na, -Ca, -Mg; ferrierite-Mg, -K, -Na; gmelinite-Na, -Ca, -K; heulandite-Ca, -Na, -K, -Sr; levyne-Ca, -Na; paulingite-K, -Ca; phillipsite-Na, -Ca, -K stilbite-Ca, -Na. Key references, type locality, origin of name, chemical data, IZA structure-type symbols, space-group symmetry, unit-cell dimensions, and comments on structure are listed for 13 compositional series, 82 accepted zeolite mineral species, and three of doubtful status. Herschelite, leonhardite, svetlozarite and wellsite are discredited as mineral species names. Obsolete and discredited names are listed.

Growth of fluorescence gold clusters using photo-chemically activated ligands

NASA Astrophysics Data System (ADS)

Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

2016-03-01

Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

Chemical sensors based on N-substituted polyaniline derivatives: reactivity and adsorption studies via electronic structure calculations.

PubMed

Mandú, Larissa O; Batagin-Neto, Augusto

2018-06-09

Conjugated organic polymers represent an important class of materials for varied technological applications including in active layers of chemical sensors. In this context, polyaniline (PANI) derivatives are promising candidates, mainly due to their high chemical stability, good processability, versatility of synthesis, polymerization, and doping, as well as relative low cost. In this study, electronic structure calculations were carried out for varied N-substituted PANI derivatives in order to investigate the potential sensory properties of these materials. The opto-electronic properties of nine distinct compounds were evaluated and discussed in terms of the employed substituents. Preliminary reactivity studies were performed in order to identify adsorption centers on the oligomer structures via condensed-to-atoms Fukui indexes (CAFI). Finally, adsorption studies were carried out for selected derivatives considering five distinct gaseous analytes. The influence of the analytes on the oligomer properties were investigated via the evaluation of average binding energies and changes on the structural features, optical absorption spectra, frontier orbitals distribution, and total density of states in relation to the isolated oligomers. The obtained results indicate the derivatives PANI-NO 2 and PANI-C 6 H 5 as promising materials for the development of improved chemical sensors.

Developmental toxicity in flounder embryos exposed to crude oils derived from different geographical regions.

PubMed

Jung, Jee-Hyun; Lee, Eun-Hee; Choi, Kwang-Min; Yim, Un Hyuk; Ha, Sung Yong; An, Joon Geon; Kim, Moonkoo

2017-06-01

Crude oils from distinct geographical regions have distinct chemical compositions, and, as a result, their toxicity may be different. However, developmental toxicity of crude oils derived from different geographical regions has not been extensively characterized. In this study, flounder embryos were separately exposed to effluents contaminated by three crude oils including: Basrah Light (BLO), Pyrenees (PCO), and Sakhalin Vityaz (SVO), in addition to a processed fuel oil (MFO-380), to measure developmental toxicity and for gene expressions. Each oil possessed a distinct chemical composition. Edema defect was highest in embryos exposed to PCO and MFO-380 that both have a greater fraction of three-ring PAHs (33% and 22%, respectively) compared to BLO and SVO. Observed caudal fin defects were higher in embryos exposed to SVO and MFO-380, which are both dominated by naphthalenes (81% and 52%, respectively). CYP1A gene expressions were also highest in embryos exposed to SVO and MFO-380. Higher incidence of cardiotoxicity and lower nkx 2.5 expression were detected in embryos exposed to PCO. Unique gene expression profiles were observed in embryos exposed to crude oils with distinct compositions. This study demonstrates that crude oils of different geographical origins with different compositional characteristics induce developmental toxicity to different degrees. Copyright © 2017 Elsevier Inc. All rights reserved.

Effects of Cluster Environment on Chemical Abundances in Virgo Cluster Spirals

NASA Astrophysics Data System (ADS)

Kennicutt, R. C.; Skillman, E. D.; Shields, G. A.; Zaritsky, D.

1995-12-01

We have obtained new chemical abundance measurements of HII regions in Virgo cluster spiral galaxies, in order to test whether the cluster environment has significantly influenced the gas-phase abundances and chemical evolution of spiral disks. The sample of 9 Virgo spirals covers a narrow range of morphological type (Sbc - Sc) but shows broad ranges in HI deficiencies and radii in the cluster. This allows us to compare the Virgo sample as a whole to field spirals, using a large sample from Zaritsky, Kennicutt, & Huchra, and to test for systematic trends with HI content and location within the cluster. The Virgo spirals show a wide dispersion in mean disk abundances and abundance gradients. Strongly HI deficient spirals closest to the cluster core show anomalously high oxygen abundances (by 0.3 to 0.5 dex), while outlying spirals with normal HI content show abundances similar to those of field spirals. The most HI depleted spirals also show weaker abundance gradients on average, but the formal significance of this trend is marginal. We find a strong correlation between mean abundance and HI/optical diameter ratio that is quite distinct from the behavior seen in field galaxies. This suggests that dynamical processes associated with the cluster environment are more important than cluster membership in determining the evolution of chemical abundances and stellar populations in spiral galaxies. Simple chemical evolution models are calculated to predict the magnitude of the abundance enhancement expected if ram-pressure stripping or curtailment of infall is responsible for the gas deficiencies. The increased abundances of the spirals in the cluster core may have significant effects on their use as cosmological standard candles.

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

PubMed

Schwartz, Thomas J; Shanks, Brent H; Dumesic, James A

2016-04-01

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Distinct effects of Cr bulk doping and surface deposition on the chemical environment and electronic structure of the topological insulator Bi 2 Se 3

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

Yilmaz, Turgut; Hines, William; Sun, Fu-Chang

In this report, it is shown that Cr doped into the bulk and Cr deposited on the surface of Bi2Se3 films produced by molecular beam epitaxy (MBE) have strikingly different effects on both the electronic structure and chemical environment. Angle resolved photoemission spectroscopy (ARPES) shows that Cr doped into the bulk opens a surface state energy gap which can be seen at room temperature; much higher than the measured ferromagnetic transition temperature of ≈ 10 K. On the other hand, similar ARPES measurements show that the surface states remain gapless down to 15 K for films with Cr surface deposition.more » In addition, core-level photoemission spectroscopy of the Bi 5d, Se 3d, and Cr 3p core levels show distinct differences in the chemical environment for the two methods of Cr introduction. Surface deposition of Cr results in the formation of shoulders on the lower binding energy side for the Bi 5d peaks and two distinct Cr 3p peaks indicative of two Cr sites. These striking differences suggests an interesting possibility that better control of doping at only near surface region may offer a path to quantum anomalous Hall states at higher temperatures than reported in the literature.« less

Distinct effects of Cr bulk doping and surface deposition on the chemical environment and electronic structure of the topological insulator Bi 2 Se 3

DOE PAGES

Yilmaz, Turgut; Hines, William; Sun, Fu-Chang; ...

2017-02-21

In this report, it is shown that Cr doped into the bulk and Cr deposited on the surface of Bi2Se3 films produced by molecular beam epitaxy (MBE) have strikingly different effects on both the electronic structure and chemical environment. Angle resolved photoemission spectroscopy (ARPES) shows that Cr doped into the bulk opens a surface state energy gap which can be seen at room temperature; much higher than the measured ferromagnetic transition temperature of ≈ 10 K. On the other hand, similar ARPES measurements show that the surface states remain gapless down to 15 K for films with Cr surface deposition.more » In addition, core-level photoemission spectroscopy of the Bi 5d, Se 3d, and Cr 3p core levels show distinct differences in the chemical environment for the two methods of Cr introduction. Surface deposition of Cr results in the formation of shoulders on the lower binding energy side for the Bi 5d peaks and two distinct Cr 3p peaks indicative of two Cr sites. These striking differences suggests an interesting possibility that better control of doping at only near surface region may offer a path to quantum anomalous Hall states at higher temperatures than reported in the literature.« less

Rapid Analysis of Corni fructus Using Paper Spray-Mass Spectrometry.

PubMed

Guo, Yuan; Gu, Zhixin; Liu, Xuemei; Liu, Jingjing; Ma, Ming; Chen, Bo; Wang, Liping

2017-07-01

Paper spray-mass spectrometry (PS-MS) is a kind of ambient MS technique for the rapid analysis of samples. Corni fructus has been widely used in traditional Chinese compound preparations and healthy food. However, a number of counterfeits of Corni fructus, such as Crataegi fructus, Lycii fructus, and grape skin are illegally sold in crude herb markets. Therefore, the development of a rapid and high-throughput quality evaluation method is important for ensuring the effectiveness and safety of the crude materials of Corni fructus. To develop PS-MS chemical profiles and a semi-quantitative method of Corni fructus for quality assessment and control, and species distinction of Corni fructus. Both positive and negative ion PS-MS chemical profiles were constructed for species distinction. The statistical analysis of the chemical profiles was accomplished by principal component analysis (PCA). Rapid semi-quantitative analysis of loganin and morroniside in the extracts of Corni fructus were accomplished by PS-MS. The profiles of the Corni fructus and Crataegi fructus samples were clearly clustered into two categories. The limit of quantification (LOQ) in the semi-quantitative analysis was 6 μg/mL and 5.6 μg/mL for loganin and morroniside, respectively. PS-MS is a simple, rapid, and high-throughput method for the quality control and species distinction of Corni fructus. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

The origin of soil organic matter controls its composition and bioreactivity across a mesic boreal forest latitudinal gradient

NASA Astrophysics Data System (ADS)

Kohl, L.; Philben, M. J.; Edwards, K. A.; Podrebarac, F. A.; Jamie, W.; Ziegler, S. E.

2017-12-01

Warmer climates have been associated with reduced soil organic matter (SOM) bioreactivity, lower respiration rates at a given temperature, which is typically attributed to the presence of more decomposed SOM. Cross site studies, however, indicate that ecosystem regime shifts associated with long-term climate warming can affect SOM properties through changes in vegetation and plant litter inputs to soils. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming remains poorly understood. To address this, we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. Climate effects on vascular plant litter chemistry explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer forests. These results indicate that a climate induced decrease in the proportion of moss inputs will not only impact SOM chemistry but also increase the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils.

[Management of agitated, violent or psychotic patients in the emergency department: an overdue protocol for an increasing problem].

PubMed

Jiménez Busselo, M T; Aragó Domingo, J; Nuño Ballesteros, A; Loño Capote, J; Ochando Perales, G

2005-12-01

Patients with extreme agitation, delirium, violent behavior or acute psychosis are frequently evaluated in the emergency departments of general hospitals. However, the traditional infrequency of this type of situation in pediatric emergency services can lead to a certain lack of foresight and efficiency in the initial management of these patients. Because of the current known increase of psychosocial disorders in pediatric emergencies, new pharmacological treatments for juvenile psychotic processes, and particularly the lack of compliance with these treatments, as well as the earlier consumption of ever more varied illicit drugs among young people, the frequency and diversity of this kind of disorder is on the increase. The treatment of agitation, aggression and violence begins with successful management of the acute episode, followed by strategies designed to reduce the intensity and frequency of subsequent episodes. The key to safety is early intervention to prevent progression from agitation to aggression and violence. Consequently, urgent measures designed to inhibit agitation should be adopted without delay by the staff initially dealing with the patient, usually in the emergency unit. Patients with psychomotor agitation disorder (PMAD) may require emergency physical and/or chemical restraints for their own safety and that of the healthcare provider in order to prevent harmful clinical sequelae and to expedite medical evaluation to determine the cause. However, the risks of restraint measures must be weighed against the benefits in each case. This review aims to present the emergency measures to be taken in children with PMAD. The distinct etiological situations and criteria for the choice of drugs for chemical restraint in each situation, as well as the complications associated with certain drugs, are discussed. It is advisable, therefore, that health professionals become familiar with the distinct pharmacological options.

Evaluation of land use and water quality in an agricultural watershed in the USA indicates multiple sources of bacterial impairment.

PubMed

Wittman, Jacob; Weckwerth, Andrew; Weiss, Chelsea; Heyer, Sharon; Seibert, Jacob; Kuennen, Ben; Ingels, Chad; Seigley, Lynette; Larsen, Kirk; Enos-Berlage, Jodi

2013-12-01

Pathogens are the number one cause of impairments of assessed rivers and streams in the USA and pose a significant human health hazard. The Dry Run Creek Watershed in Northeast Iowa has been designated as impaired by the State of Iowa because of high levels of Escherichia coli bacteria. To investigate the nature of this impairment, land use and stream bank assessments were coupled with comprehensive water quality monitoring. Physical, chemical, and biological parameters were measured at 13 different sites in the watershed, including pH, temperature, conductivity, dissolved oxygen, turbidity, total Kjeldahl nitrogen, ammonia-N, nitrate + nitrite-N, total phosphorus, and E. coli. In addition, benthic macroinvertebrate communities were analyzed at seven sites, and optical brightener tests were performed late in the season. Results identified segments of the watershed that were more prominent contributors of E. coli, and correlations were observed between levels of E. coli and several chemical parameters, including ammonia-N, total Kjeldahl nitrogen, and total phosphorus. Interestingly, distinct sites emerged as more prominent contributors of these elements during rain vs. non-rain events, suggesting different types of sources. Both the amount of rainfall and the time elapsed between the rain event and the sampling influenced E. coli levels during wet weather conditions. Nitrate + nitrite-N displayed a unique response to rain events compared with the other parameters, suggesting a different delivery route. Analyses of benthic macroinvertebrate communities were consistent with pollution trends. Collectively, these data suggest distinct agriculturally related E. coli contributions, as well as specific areas and practices for water quality improvement strategies. This study can serve as a resource for evaluating agricultural watersheds that are impaired for bacteria.

A diversity-oriented synthesis strategy enabling the combinatorial-type variation of macrocyclic peptidomimetic scaffolds† †Electronic supplementary information (ESI) available: Experimental procedures, characterization data and details of the computational analyses. See DOI: 10.1039/c5ob00371g Click here for additional data file.

PubMed Central

Isidro-Llobet, Albert; Hadje Georgiou, Kathy; Galloway, Warren R. J. D.; Giacomini, Elisa; Hansen, Mette R.; Méndez-Abt, Gabriela; Tan, Yaw Sing; Carro, Laura; Sore, Hannah F.

2015-01-01

Macrocyclic peptidomimetics are associated with a broad range of biological activities. However, despite such potentially valuable properties, the macrocyclic peptidomimetic structural class is generally considered as being poorly explored within drug discovery. This has been attributed to the lack of general methods for producing collections of macrocyclic peptidomimetics with high levels of structural, and thus shape, diversity. In particular, there is a lack of scaffold diversity in current macrocyclic peptidomimetic libraries; indeed, the efficient construction of diverse molecular scaffolds presents a formidable general challenge to the synthetic chemist. Herein we describe a new, advanced strategy for the diversity-oriented synthesis (DOS) of macrocyclic peptidomimetics that enables the combinatorial variation of molecular scaffolds (core macrocyclic ring architectures). The generality and robustness of this DOS strategy is demonstrated by the step-efficient synthesis of a structurally diverse library of over 200 macrocyclic peptidomimetic compounds, each based around a distinct molecular scaffold and isolated in milligram quantities, from readily available building-blocks. To the best of our knowledge this represents an unprecedented level of scaffold diversity in a synthetically derived library of macrocyclic peptidomimetics. Cheminformatic analysis indicated that the library compounds access regions of chemical space that are distinct from those addressed by top-selling brand-name drugs and macrocyclic natural products, illustrating the value of our DOS approach to sample regions of chemical space underexploited in current drug discovery efforts. An analysis of three-dimensional molecular shapes illustrated that the DOS library has a relatively high level of shape diversity. PMID:25778821

Geochemistry of mineral waters and associated gases of the Sakhalin Island (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chelnokov, George A.; Bragin, Ivan V.; Kharitonova, Natalia A.

2018-04-01

Isotopic and chemical data on the mineral water, mud volcanoes fluid and associated gases from the biggest Russian island Sakhalin, together with previous stable isotope data (d18O, dD, 13C), allow elucidation of their origin and general evolution. The water fluid circulation is mainly related to marine environment inducing three distinct types: Na-HCO3-Cl alkali carbonate groundwaters, Na-Cl-HCO3 highly evolved saline and Na-Cl mature groundwaters, indicating different evolution. Chemical evolution of groundwater on Sakhalin Island demonstrated cation exchange and salinization as dominant evolutionary pathways. Isotopic composition of groundwaters varies from meteoric to metamorphic waters. These metamorphic waters consist of water hydration from the clay and seawater are traced in fluids of Yuzhno-Sakhalin mud volcano despite modification by mixing with meteoric waters and water-rock interaction processes. Fault systems that define the areas of highly mineralized water circulation appear to play a major role in the CO2 migration to the surface and CH4 generation. The δ13C(CO2) values have pointed that gas phase in high-pCO2 waters mostly consists of mantle-derived CO2. The carbon isotope signature of methane δ13C(CH4) and δD(CH4) indicates its distinct origin which is specified by tectonics. Methane manifestation in the south of the Sakhalin Island is mainly related to thermogenic reservoirs as they are more often dislocate by tectonics, and crossed by active and permeable faults. The sources of biogenous methane in the north of Sakhalin Island is related to younger and shallower reservoirs, and less affected by tectonic processes. The determinations of 222Rn have allowed observing that maximal radon flux is associated with high pCO2 waters.

Micromotors for "Chemistry-on-the-Fly".

PubMed

Karshalev, Emil; Esteban-Fernández de Ávila, Berta; Wang, Joseph

2018-03-21

This perspective reviews mobile micro/nanomotor scaffolds for performing "chemistry-on-the-fly". Synthetic nano/micromotors offer great versatility and distinct advantages in diverse chemical applications owing to their efficient propulsion and facile surface functionalization that allow these mobile platforms to move and disperse reactive materials across the solution. Such dynamic microreactors have led to accelerated chemical processes, including organic pollutant degradation, metal chelation, biorecognition, redox chemistry, chemical "writing", and a variety of other chemical transformations. Representative examples of such micromotor-enhanced chemical reactions are discussed, focusing on the specific chemical role of these mobile microreactors. The advantages, gaps and limitations of using micromotors as mobile chemical platforms are discussed, concluding with the future prospects of this emerging field. We envision that artificial nano/micromotors will become attractive dynamic tools for speeding up and enhancing "on-the-fly" chemical reactions.

A Bacterial Pathogen uses Distinct Type III Secretion Systems to Alternate between Host Kingdom

USDA-ARS?s Scientific Manuscript database

Gram-negative bacterial pathogens of eukaryotes often secrete proteins directly into host cells via a needle-like protein channel called a ‘type III secretion system’ (T3SS). Bacteria that are adapted to either animal or plant hosts use phylogenetically distinct T3SSs for secreting proteins. Here, ...

Neuronal migration disorders in microcephalic osteodysplastic primordial dwarfism type I/III.

PubMed

Juric-Sekhar, Gordana; Kapur, Raj P; Glass, Ian A; Murray, Mitzi L; Parnell, Shawn E; Hevner, Robert F

2011-04-01

Microcephalic osteodysplastic primordial dwarfism (MOPD) is a rare microlissencephaly syndrome, with at least two distinct phenotypic and genetic types. MOPD type II is caused by pericentrin mutations, while types I and III appear to represent a distinct entity (MOPD I/III) with variably penetrant phenotypes and unknown genetic basis. The neuropathology of MOPD I/III is little understood, especially in comparison to other forms of lissencephaly. Here, we report postmortem brain findings in an 11-month-old female infant with MOPD I/III. The cerebral cortex was diffusely pachygyric, with a right parietal porencephalic lesion. Histologically, the cortex was abnormally thick and disorganized. Distinct malformations were observed in different cerebral lobes, as characterized using layer-specific neuronal markers. Frontal cortex was severely disorganized and coated with extensive leptomeningeal glioneuronal heterotopia. Temporal cortex had a relatively normal 6-layered pattern, despite cortical thickening. Occipital cortex was variably affected. The corpus callosum was extremely hypoplastic. Brainstem and cerebellar malformations were also present, as well as old necrotic foci. Findings in this case suggest that the cortical malformation in MOPD I/III is distinct from other forms of pachygyria-lissencephaly.

Mathematical model of macrophage-facilitated breast cancer cells invasion.

PubMed

Knútsdóttir, Hildur; Pálsson, Eirikur; Edelstein-Keshet, Leah

2014-09-21

Mortality from breast cancer stems from its tendency to invade into surrounding tissues and organs. Experiments have shown that this metastatic process is facilitated by macrophages in a short-ranged chemical signalling loop. Macrophages secrete epidermal growth factor, EGF, and respond to the colony stimulating factor 1, CSF-1. Tumor cells secrete CSF-1 and respond to EGF. In this way, the cells coordinate aggregation and cooperative migration. Here we investigate this process in a model for in vitro interactions using two distinct but related mathematical approaches. In the first, we analyze and simulate a set of partial differential equations to determine conditions for aggregation. In the second, we use a cell-based discrete 3D simulation to follow the fates and motion of individual cells during aggregation. Linear stability analysis of the PDE model reveals that decreasing the chemical secretion, chemotaxis coefficients or density of cells or increasing the chemical degradation in the model could eliminate the spontaneous aggregation of cells. Simulations with the discrete model show that the ratio between tumor cells and macrophages in aggregates increases when the EGF secretion parameter is increased. The results also show how CSF-1/CSF-1R autocrine signalling in tumor cells affects the ratio between the two cell types. Comparing the continuum results with simulations of a discrete cell-based model, we find good qualitative agreement. Copyright © 2014 Elsevier Ltd. All rights reserved.

Room Temperature Sensing Achieved by GaAs Nanowires and oCVD Polymer Coating.

PubMed

Wang, Xiaoxue; Ermez, Sema; Goktas, Hilal; Gradečak, Silvija; Gleason, Karen

2017-06-01

Novel structures comprised of GaAs nanowire arrays conformally coated with conducting polymers (poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3,4-ethylenedioxythiophene-co-3-thiophene acetic acid) display both sensitivity and selectivity to a variety of volatile organic chemicals. A key feature is room temperature operation, so that neither a heater nor the power it would consume, is required. It is a distinct difference from traditional metal oxide sensors, which typically require elevated operational temperature. The GaAs nanowires are prepared directly via self-seeded metal-organic chemical deposition, and conducting polymers are deposited on GaAs nanowires using oxidative chemical vapor deposition (oCVD). The range of thickness for the oCVD layer is between 100 and 200 nm, which is controlled by changing the deposition time. X-ray diffraction analysis indicates an edge-on alignment of the crystalline structure of the PEDOT coating layer on GaAs nanowires. In addition, the positive correlation between the improvement of sensitivity and the increasing nanowire density is demonstrated. Furthermore, the effect of different oCVD coating materials is studied. The sensing mechanism is also discussed with studies considering both nanowire density and polymer types. Overall, the novel structure exhibits good sensitivity and selectivity in gas sensing, and provides a promising platform for future sensor design. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neuronal apoptotic signaling pathways probed and intervened by synthetically and modularly modified (SMM) chemokines.

PubMed

Choi, Won-Tak; Kaul, Marcus; Kumar, Santosh; Wang, Jun; Kumar, I M Krishna; Dong, Chang-Zhi; An, Jing; Lipton, Stuart A; Huang, Ziwei

2007-03-09

As the main coreceptors for human immunodeficiency virus type 1 (HIV-1) entry, CXCR4 and CCR5 play important roles in HIV-associated dementia (HAD). HIV-1 glycoprotein gp120 contributes to HAD by causing neuronal damage and death, either directly by triggering apoptotic pathways or indirectly by stimulating glial cells to release neurotoxins. Here, to understand the mechanism of CXCR4 or CCR5 signaling in neuronal apoptosis associated with HAD, we have applied synthetically and modularly modified (SMM)-chemokine analogs derived from natural stromal cell-derived factor-1alpha or viral macrophage inflammatory protein-II as chemical probes of the mechanism(s) whereby these SMM-chemokines prevent or promote neuronal apoptosis. We show that inherently neurotoxic natural ligands of CXCR4, such as stromal cell-derived factor-1alpha or viral macrophage inflammatory protein-II, can be modified to protect neurons from apoptosis induced by CXCR4-preferring gp120(IIIB), and that the inhibition of CCR5 by antagonist SMM-chemokines, unlike neuroprotective CCR5 natural ligands, leads to neurotoxicity by activating a p38 mitogen-activated protein kinase (MAPK)-dependent pathway. Furthermore, we discover distinct signaling pathways activated by different chemokine ligands that are either natural agonists or synthetic antagonists, thus demonstrating a chemical biology strategy of using chemically engineered inhibitors of chemokine receptors to study the signaling mechanism of neuronal apoptosis and survival.

An NMR-Based Structural Rationale for Contrasting Stoichiometry and Ligand Binding Site(s) in Fatty Acid-binding Proteins†

PubMed Central

He, Yan; Estephan, Rima; Yang, Xiaomin; Vela, Adriana; Wang, Hsin; Bernard, Cédric; Stark, Ruth E.

2011-01-01

Liver fatty acid-binding protein (LFABP) is a 14-kDa cytosolic polypeptide, differing from other family members in number of ligand binding sites, diversity of bound ligands, and transfer of fatty acid(s) to membranes primarily via aqueous diffusion rather than direct collisional interactions. Distinct two-dimensional 1H-15N NMR signals indicative of slowly exchanging LFABP assemblies formed during stepwise ligand titration were exploited, without solving the protein-ligand complex structures, to yield the stoichiometries for the bound ligands, their locations within the protein binding cavity, the sequence of ligand occupation, and the corresponding protein structural accommodations. Chemical shifts were monitored for wild-type LFABP and a R122L/S124A mutant in which electrostatic interactions viewed as essential to fatty acid binding were removed. For wild-type LFABP the results compared favorably with previous tertiary structures of oleate-bound wild-type LFABP in crystals and in solution: there are two oleates, one U-shaped ligand that positions the long hydrophobic chain deep within the cavity and another extended structure with the hydrophobic chain facing the cavity and the carboxylate group lying close to the protein surface. The NMR titration validated a prior hypothesis that the first oleate to enter the cavity occupies the internal protein site. In contrast, 1H/15N chemical shift changes supported only one liganded oleate for R122L/S124A LFABP, at an intermediate location within the protein cavity. A rationale based on protein sequence and electrostatics was developed to explain the stoichiometry and binding site trends for LFABPs and to put these findings into context within the larger protein family. PMID:21226535

Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization

PubMed Central

2015-01-01

The oxygen exchange activity of mixed conducting oxide surfaces has been widely investigated, but a detailed understanding of the corresponding reaction mechanisms and the rate-limiting steps is largely still missing. Combined in situ investigation of electrochemically polarized model electrode surfaces under realistic temperature and pressure conditions by near-ambient pressure (NAP) XPS and impedance spectroscopy enables very surface-sensitive chemical analysis and may detect species that are involved in the rate-limiting step. In the present study, acceptor-doped perovskite-type La0.6Sr0.4CoO3-δ (LSC), La0.6Sr0.4FeO3-δ (LSF), and SrTi0.7Fe0.3O3-δ (STF) thin film model electrodes were investigated under well-defined electrochemical polarization as cathodes in oxidizing (O2) and as anodes in reducing (H2/H2O) atmospheres. In oxidizing atmosphere all materials exhibit additional surface species of strontium and oxygen. The polaron-type electronic conduction mechanism of LSF and STF and the metal-like mechanism of LSC are reflected by distinct differences in the valence band spectra. Switching between oxidizing and reducing atmosphere as well as electrochemical polarization cause reversible shifts in the measured binding energy. This can be correlated to a Fermi level shift due to variations in the chemical potential of oxygen. Changes of oxidation states were detected on Fe, which appears as FeIII in oxidizing atmosphere and as mixed FeII/III in H2/H2O. Cathodic polarization in reducing atmosphere leads to the reversible formation of a catalytically active Fe0 phase. PMID:26877827

Three types of ependymal cells with intracellular calcium oscillation are characterized by distinct cilia beating properties.

PubMed

Liu, Tongyu; Jin, Xingjian; Prasad, Rahul M; Sari, Youssef; Nauli, Surya M

2014-09-01

Ependymal cells are multiciliated epithelial cells that line the ventricles in the adult brain. Abnormal function or structure of ependymal cilia has been associated with various neurological deficits. For the first time, we report three distinct ependymal cell types, I, II, and III, based on their unique ciliary beating frequency and beating angle. These ependymal cells have specific localizations within the third ventricle of the mouse brain. Furthermore, neither ependymal cell types nor their localizations are altered by aging. Our high-speed fluorescence imaging analysis reveals that these ependymal cells have an intracellular pacing calcium oscillation property. Our study further shows that alcohol can significantly repress the amplitude of calcium oscillation and the frequency of ciliary beating, resulting in an overall decrease in volume replacement by the cilia. Furthermore, the pharmacological agent cilostazol could differentially increase cilia beating frequency in type II, but not in type I or type III, ependymal cells. In summary, we provide the first evidence of three distinct types of ependymal cells with calcium oscillation properties. © 2014 Wiley Periodicals, Inc.

Microfossils of Cyanobacteria in Carbonaceous Meteorites

NASA Technical Reports Server (NTRS)

Hoover, Richard B.

2007-01-01

During the past decade, Environmental and Field Emission Scanning Electron Microscopes have been used at the NASA/Marshall Space Flight Center to investigate freshly fractured interior surfaces of a large number of different types of meteorites. Large, complex, microfossils with clearly recognizable biological affinities have been found embedded in several carbonaceous meteorites. Similar forms were notably absent in all stony and nickel-iron meteorites investigated. The forms encountered are consistent in size and morphology with morphotypes of known genera of Cyanobacteria and microorganisms that are typically encountered in associated benthic prokaryotic mats. Even though many coccoidal and isodiametric filamentous cyanobacteria have a strong morphological convergence with some other spherical and filamentous bacteria and algae, many genera of heteropolar cyanobacteria have distinctive apical and basal regions and cellular differentiation that makes it possible to unambiguously recognize the forms based entirely upon cellular dimensions, filament size and distinctive morphological characteristics. For almost two centuries, these morphological characteristics have historically provided the basis for the systematics and taxonomy of cyanobacteria. This paper presents ESEM and FESEM images of embedded filaments and thick mats found in-situ in the Murchison CM2 and Orgueil cn carbonaceous meteorites. Comparative images are also provided for known genera and species of cyanobacteria and other microbial extremophiles. Energy Dispersive X-ray Spectroscopy (EDS) studies indicate that the meteorite filaments typically exhibit dramatic chemical differentiation with distinctive difference between the possible microfossil and the meteorite matrix in the immediate proximity. Chemical differentiation is also observed within these microstructures with many of the permineralized filaments enveloped within electron transparent carbonaceous sheaths. Elemental distributions of these embedded filaments are not consistent with recent cyanobacteria or other living or preserved microbial extremophiles that have been investigated during this research. The meteorite filaments often have nitrogen content below the sensitivity level of the EDS detector. Carbon, Sulphur, Iron or Silicon are often highly enriched and hence anomalous C/N and CIS ratios when compared with modem cyanobacteria. The meteorite forms that are unambiguously recognizable as biological filaments are interpreted as indigenous microfossils analogous to several known genera of modem cyanobacteria and associated trichomic filamentous prokaryotes.

Interaction between the Bacterium Pseudomonas fluorescens strain CHA0, its genetic derivatives and vermiculite: Effects on chemical, mineralogical and mechanical properties of vermiculite

NASA Astrophysics Data System (ADS)

Mueller, Barbara

2016-04-01

Using bacteria of the strain Pseudomonas fluorescens wild type CHA0 and its genetic derivative strains CHA77, CHA89, CHA400, CHA631 and CHA661 (which differ in one gene only) the changes in chemical, mineralogical and rheological properties of the clay mineral vermiculite affected by microbial activity were studied in order to test whether the individually different production of metabolites by the genetically engineered strains may alter the clay mineral vermiculite in distinct ways. With the novel strategy of working with living wild type bacteria, their genetic derivatives and clay, the following properties of the mineral altered by the various strains of Pseudomonas fluorescens were determined: grain size, X-Ray diffraction pattern, intercrystalline swelling with glycerol, layer charge, CEC, BET surface and uptake of trace elements. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to determine the changes in major, minor and trace elements of the clay vermiculite affected by microbial activity. Among all analyzed trace elements, Fe, Mn and Cu are the most interesting. Fe and Mn are taken up from the clay mineral by all bacterial strains whereas Cu is only removed from vermiculite by strains CHA0, CHA77, CHA400 and CHA661. The latter mentioned strains all produce the antibiotics 2,4-diacetylphloroglucinol and monoacetylphloroglucinol which can complex Cu efficiently. Therefore the alteration of only one gene of the bacteria is causing significant effects on the clay mineral.

A framework to spatially cluster air pollution monitoring sites in US based on the PM2.5 composition

PubMed Central

Austin, Elena; Coull, Brent A.; Zanobetti, Antonella; Koutrakis, Petros

2013-01-01

Background Heterogeneity in the response to PM2.5 is hypothesized to be related to differences in particle composition across monitoring sites which reflect differences in source types as well as climatic and topographic conditions impacting different geographic locations. Identifying spatial patterns in particle composition is a multivariate problem that requires novel methodologies. Objectives Use cluster analysis methods to identify spatial patterns in PM2.5 composition. Verify that the resulting clusters are distinct and informative. Methods 109 monitoring sites with 75% reported speciation data during the period 2003–2008 were selected. These sites were categorized based on their average PM2.5 composition over the study period using k-means cluster analysis. The obtained clusters were validated and characterized based on their physico-chemical characteristics, geographic locations, emissions profiles, population density and proximity to major emission sources. Results Overall 31 clusters were identified. These include 21 clusters with 2 or more sites which were further grouped into 4 main types using hierarchical clustering. The resulting groupings are chemically meaningful and represent broad differences in emissions. The remaining clusters, encompassing single sites, were characterized based on their particle composition and geographic location. Conclusions The framework presented here provides a novel tool which can be used to identify and further classify sites based on their PM2.5 composition. The solution presented is fairly robust and yielded groupings that were meaningful in the context of air-pollution research. PMID:23850585

Evidence for Cyclical Fractional Crystallization, Recharge, and Assimilation in Basalts of the Kimama Core, Central Snake River Plain, Idaho: A 5.5-million-year Highlight Reel of Petrogenetic processes in a Mid-Crustal Sill Complex

NASA Astrophysics Data System (ADS)

Potter, Katherine E.; Shervais, John W.; Christiansen, Eric H.; Vetter, Scott K.

2018-02-01

Basalts erupted in the Snake River Plain of central Idaho and sampled in the Kimama drill core link eruptive processes to the construction of mafic intrusions over 5.5 Ma. Cyclic variations in basalt composition reveal temporal chemical heterogeneity related to fractional crystallization and the assimilation of previously-intruded mafic sills. A range of compositional types are identified within 1912 m of continuous drill core: Snake River olivine tholeiite (SROT), low K SROT, high Fe-Ti, and evolved and high K-Fe lavas similar to those erupted at Craters of the Moon National Monument. Detailed lithologic and geophysical logs document 432 flow units comprising 183 distinct lava flows and 78 flow groups. Each lava flow represents a single eruptive episode, while flow groups document chemically and temporally related flows that formed over extended periods of time. Temporal chemical variation demonstrates the importance of source heterogeneity and magma processing in basalt petrogenesis. Low-K SROT and high Fe-Ti basalts are genetically related to SROT as, respectively, hydrothermally-altered and fractionated daughters. Cyclic variations in the chemical composition of Kimama flow groups are apparent as 21 upward fractionation cycles, six recharge cycles, eight recharge-fractionation cycles, and five fractionation-recharge cycles. We propose that most Kimama basalt flows represent typical fractionation and recharge patterns, consistent with the repeated influx of primitive SROT parental magmas and extensive fractional crystallization coupled with varying degrees of assimilation of gabbroic to ferrodioritic sills at shallow to intermediate depths over short durations. Trace element models show that parental SROT basalts were generated by 5-10% partial melting of enriched mantle at shallow depths above the garnet-spinel lherzolite transition. The distinctive evolved and high K-Fe lavas are rare. Found at four depths, 319 m, 1045 m, 1078 m, and 1189 m, evolved and high K-Fe flows are compositionally unrelated to SROT magmas and represent highly fractionated basalt, probably accompanied by crustal assimilation. These evolved lavas may be sourced from the Craters of the Moon/Great Rift system to the northeast. The Kimama drill core is the longest record of geochemical variation in the central Snake River Plain and reinforces the concept of magma processing in a layered complex.

Complete (1)H resonance assignment of beta-maltose from (1)H-(1)H DQ-SQ CRAMPS and (1)H (DQ-DUMBO)-(13)C SQ refocused INEPT 2D solid-state NMR spectra and first principles GIPAW calculations.

PubMed

Webber, Amy L; Elena, Bénédicte; Griffin, John M; Yates, Jonathan R; Pham, Tran N; Mauri, Francesco; Pickard, Chris J; Gil, Ana M; Stein, Robin; Lesage, Anne; Emsley, Lyndon; Brown, Steven P

2010-07-14

A disaccharide is a challenging case for high-resolution (1)H solid-state NMR because of the 24 distinct protons (14 aliphatic and 10 OH) having (1)H chemical shifts that all fall within a narrow range of approximately 3 to 7 ppm. High-resolution (1)H (500 MHz) double-quantum (DQ) combined rotation and multiple pulse sequence (CRAMPS) solid-state NMR spectra of beta-maltose monohydrate are presented. (1)H-(1)H DQ-SQ CRAMPS spectra are presented together with (1)H (DQ)-(13)C correlation spectra obtained with a new pulse sequence that correlates a high-resolution (1)H DQ dimension with a (13)C single quantum (SQ) dimension using the refocused INEPT pulse-sequence element to transfer magnetization via one-bond (13)C-(1)H J couplings. Compared to the observation of only a single broad peak in a (1)H DQ spectrum recorded at 30 kHz magic-angle spinning (MAS), the use of DUMBO (1)H homonuclear decoupling in the (1)H DQ CRAMPS experiment allows the resolution of distinct DQ correlation peaks which, in combination with first-principles chemical shift calculations based on the GIPAW (Gauge Including Projector Augmented Waves) plane-wave pseudopotential approach, enables the assignment of the (1)H resonances to the 24 distinct protons. We believe this to be the first experimental solid-state NMR determination of the hydroxyl OH (1)H chemical shifts for a simple sugar. Variable-temperature (1)H-(1)H DQ CRAMPS spectra reveal small increases in the (1)H chemical shifts of the OH resonances upon decreasing the temperature from 348 K to 248 K.

Distinct roles for RDE-1 and RDE-4 during RNA interference in Caenorhabditis elegans.

PubMed

Parrish, S; Fire, A

2001-10-01

RNA interference (RNAi) is a cellular defense mechanism that uses double-stranded RNA (dsRNA) as a sequence-specific trigger to guide the degradation of homologous single-stranded RNAs. RNAi is a multistep process involving several proteins and at least one type of RNA intermediate, a population of small 21-25 nt RNAs (called siRNAs) that are initially derived from cleavage of the dsRNA trigger. Genetic screens in Caenorhabditis elegans have identified numerous mutations that cause partial or complete loss of RNAi. In this work, we analyzed cleavage of injected dsRNA to produce the initial siRNA population in animals mutant for rde-1 and rde-4, two genes that are essential for RNAi but that are not required for organismal viability or fertility. Our results suggest distinct roles for RDE-1 and RDE-4 in the interference process. Although null mutants lacking rde-1 show no phenotypic response to dsRNA, the amount of siRNAs generated from an injected dsRNA trigger was comparable to that of wild-type. By contrast, mutations in rde-4 substantially reduced the population of siRNAs derived from an injected dsRNA trigger. Injection of chemically synthesized 24- or 25-nt siRNAs could circumvent RNAi resistance in rde-4 mutants, whereas no bypass was observed in rde-1 mutants. These results support a model in which RDE-4 is involved before or during production of siRNAs, whereas RDE-1 acts after the siRNAs have been formed.

Distinct roles for RDE-1 and RDE-4 during RNA interference in Caenorhabditis elegans.

PubMed Central

Parrish, S; Fire, A

2001-01-01

RNA interference (RNAi) is a cellular defense mechanism that uses double-stranded RNA (dsRNA) as a sequence-specific trigger to guide the degradation of homologous single-stranded RNAs. RNAi is a multistep process involving several proteins and at least one type of RNA intermediate, a population of small 21-25 nt RNAs (called siRNAs) that are initially derived from cleavage of the dsRNA trigger. Genetic screens in Caenorhabditis elegans have identified numerous mutations that cause partial or complete loss of RNAi. In this work, we analyzed cleavage of injected dsRNA to produce the initial siRNA population in animals mutant for rde-1 and rde-4, two genes that are essential for RNAi but that are not required for organismal viability or fertility. Our results suggest distinct roles for RDE-1 and RDE-4 in the interference process. Although null mutants lacking rde-1 show no phenotypic response to dsRNA, the amount of siRNAs generated from an injected dsRNA trigger was comparable to that of wild-type. By contrast, mutations in rde-4 substantially reduced the population of siRNAs derived from an injected dsRNA trigger. Injection of chemically synthesized 24- or 25-nt siRNAs could circumvent RNAi resistance in rde-4 mutants, whereas no bypass was observed in rde-1 mutants. These results support a model in which RDE-4 is involved before or during production of siRNAs, whereas RDE-1 acts after the siRNAs have been formed. PMID:11680844

Textural and mineral chemistry constraints on evolution of Merapi Volcano, Indonesia

NASA Astrophysics Data System (ADS)

Innocenti, Sabrina; del Marmol, Mary-Ann; Voight, Barry; Andreastuti, Supriyati; Furman, Tanya

2013-07-01

We analyze and compare the textures of Merapi lavas (basalts and basaltic andesites) ranging in age from Proto-Merapi through modern activity, with the goal of gaining insights on the temporal evolution of Merapi's magmatic system. Analysis of textural parameters, such as phenocryst and microphenocryst crystallinity, coupled with crystal size distribution theory, provides information about the storage and transport of magmas. We combine textural analyses with geochemical investigations for a comprehensive comparison of erupted lavas over time. The chemical analyses identify crystal growth processes in magma chambers and underline differences between sample groups. Our work suggests the occurrence of two distinct histories, presumably associated with (at least) two generally distinct types of rheological behaviors and storage/transport systems. These behaviors are associated with different plagioclase growth patterns, with both groups influenced by late-stage shallow decompression degassing-induced microlite crystallization. Both groups contain amphibole crystals that indicate an early period of mid-crustal to deep-crustal storage of water-rich magmas. Dome lavas from the 20th century eruptive activity indicate quasi-steady-state nucleation-and-growth evolution interspersed with episodes of reheating and textural coarsening, suggesting residence in magma storage at multiple depths, both > 10 km, and < 10 km, while samples from the older stratigraphic history of Merapi record both repeated attainment and loss of quasi-steady-state conditions. These observations, coupled with our companion study of Merapi tephra samples, suggest that the relatively benign type of activity observed in the 20th century will be interrupted from time to time in the future by more explosive eruptions, such as that of 2010.

The interaction between awareness of one's own speech disorder with linguistics variables: distinctive features and severity of phonological disorder.

PubMed

Dias, Roberta Freitas; Melo, Roberta Michelon; Mezzomo, Carolina Lisbôa; Mota, Helena Bolli

2013-01-01

To analyze the possible relationship among the awareness of one's own speech disorder and some aspects of the phonological system, as the number and the type of changed distinctive features, as well as the interaction among the severity of the disorder and the non-specification of distinctive features. The analyzed group has 23 children with diagnosis of speech disorder, aged 5:0 to 7:7. The speech data were analyzed through the Distinctive Features Analysis and classified by the Percentage of Correct Consonants. One also applied the Awareness of one's own speech disorder test. The children were separated in two groups: with awareness of their own speech disorder established (more than 50% of correct identification) and without awareness of their own speech disorder established (less than 50% of correct identification). Finally, the variables of this research were submitted to analysis using descriptive and inferential statistics. The type of changed distinctive features weren't different between the groups, as well as the total of changed features and the severity disorder. However, a correlation between the severity disorder and the non-specification of distinctive features was verified, because the more severe disorders have more changes in these linguistic variables. The awareness of one's own speech disorder doesn't seem to be directly influenced by the type and by the number of changed distinctive features, neither by the speech disorder severity. Moreover, one verifies that the greater phonological disorder severity, the greater the number of changed distinctive features.

CHEMICAL DIVERSITY IN THE ULTRA-FAINT DWARF GALAXY TUCANA II

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

Ji, Alexander P.; Frebel, Anna; Ezzeddine, Rana

We present the first detailed chemical abundance study of the ultra-faint dwarf galaxy Tucana II, based on high-resolution Magellan/MIKE spectra of four red giant stars. The metallicities of these stars range from [Fe/H] = −3.2 to −2.6, and all stars are low in neutron-capture abundances ([Sr/Fe] and [Ba/Fe] < −1). However, a number of anomalous chemical signatures are present. One star is relatively metal-rich ([Fe/H] = −2.6) and shows [Na, α , Sc/Fe] < 0, suggesting an extended star formation history with contributions from AGB stars and SNe Ia. Two stars with [Fe/H] < −3 are mildly carbon-enhanced ([C/Fe] ∼more » 0.7) and may be consistent with enrichment by faint supernovae, if such supernovae can produce neutron-capture elements. A fourth star with [Fe/H] = −3 is carbon-normal, and exhibits distinct light element abundance ratios from the carbon-enhanced stars. This carbon-normal star implies that at least two distinct nucleosynthesis sources, both possibly associated with Population III stars, contributed to the early chemical enrichment of this galaxy. Despite its very low luminosity, Tucana II shows a diversity of chemical signatures that preclude it from being a simple “one-shot” first galaxy yet still provide a window into star and galaxy formation in the early universe.« less

The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam Onboard Curiosity

USGS Publications Warehouse

Le Deit, Laetitia; Mangold, Nicolas; Forni, Olivier; Cousin, Agnes; Lasue, Jeremie; Schröder, Susanne; Wiens, Roger C.; Sumner, Dawn Y.; Fabre, Cecile; Stack, Katherine M.; Anderson, Ryan; Blaney, Diana L.; Clegg, Samuel M.; Dromart, Gilles; Fisk, Martin; Gasnault, Olivier; Grotzinger, John P.; Gupta, Sanjeev; Lanza, Nina; Le Mouélic, Stephane; Maurice, Sylvestre; McLennan, Scott M.; Meslin, Pierre-Yves; Nachon, Marion; Newsom, Horton E.; Payre, Valerie; Rapin, William; Rice, Melissa; Sautter, Violaine; Treiman, Alan H.

2016-01-01

The Mars Science Laboratory rover Curiosity encountered potassium-rich clastic sedimentary rocks at two sites in Gale Crater, the waypoints Cooperstown and Kimberley. These rocks include several distinct meters thick sedimentary outcrops ranging from fine sandstone to conglomerate, interpreted to record an ancient fluvial or fluvio-deltaic depositional system. From ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) chemical analyses, this suite of sedimentary rocks has an overall mean K2O abundance that is more than 5 times higher than that of the average Martian crust. The combined analysis of ChemCam data with stratigraphic and geographic locations reveals that the mean K2O abundance increases upward through the stratigraphic section. Chemical analyses across each unit can be represented as mixtures of several distinct chemical components, i.e., mineral phases, including K-bearing minerals, mafic silicates, Fe-oxides, and Fe-hydroxide/oxyhydroxides. Possible K-bearing minerals include alkali feldspar (including anorthoclase and sanidine) and K-bearing phyllosilicate such as illite. Mixtures of different source rocks, including a potassium-rich rock located on the rim and walls of Gale Crater, are the likely origin of observed chemical variations within each unit. Physical sorting may have also played a role in the enrichment in K in the Kimberley formation. The occurrence of these potassic sedimentary rocks provides additional evidence for the chemical diversity of the crust exposed at Gale Crater.

How native yeasts may influence the chemical profile of the Brazilian spirit, cachaça?

PubMed

Portugal, Cauré B; de Silva, Arthur Paron; Bortoletto, Aline M; Alcarde, André R

2017-01-01

Cachaça is the typical Brazilian spirit, obtained by distillation of fermented sugarcane must, whose production is closely related to regional heritage and geographical traits. In this work, we investigate the influence of different autochthonous yeast species, in comparison to other commercial strains, on the chemical profile of cachaça. Fermentations were performed with four different wild species, a mixed starter culture with native yeasts, and two commercial strains. Procedures were carried out simulating traditional practices, the distillates analyzed by gas chromatography, and data analyzed by multivariate statistics. Results show that the overgrowth of some non-Saccharomyces during fermentation can lead to higher concentration of contaminant compounds in the distillate. However, those microorganisms do not impress negative traits when working in cluster association, and may indeed contribute to the distinctive chemical quality and flavor of cachaça. Spontaneous fermentation are still the traditional method used for the production of cachaça, and our results indeed suggest that higher diversity, and evened fermentative environments, enable yeasts to act as a complex cluster and imprint a distinctive, quality chemical profile to the distillate. Finally, this study may help to understand the role of the native microbiota and its influence on cachaça's chemical and sensory profiles, besides demonstrating the importance of adopting insightful handling practices and strict control of technical guidelines. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of binary taste stimuli on the neural activity of the hamster chorda tympani

PubMed Central

1980-01-01

Binary mixtures of taste stimuli were applied to the tongue of the hamster and the reaction of the whole corda tympani was recorded. Some of the chemicals that were paired in mixtures (HCl, NH4Cl, NaCl, CaCl2, sucrose, and D-phenylalanine) have similar tastes to human and/or hamster, and/or common stimulatory effects on individual fibers of the hamster chorda tympani; other pairs of these chemicals have dissimilar tastes and/or distinct neural stimulatory effects. The molarity of each chemical with approximately the same effect on the activity of the nerve as 0.01 M NaCl was selected, and an established relation between stimulus concentration and response allowed estimation of the effect of a "mixture" of two concentrations of one chemical. Each mixture elicited a response that was smaller than the sum of the responses to its components. However, responses to some mixtures approached this sum, and responses to other mixtures closely approached the response to a "mixture" of two concentrations of one chemical. Responses of the former variety were generated by mixtures of an electrolyte and a nonelectrolyte and the latter by mixtures of two electrolytes or two nonelectrolytes. But, beyond the distinction between electrolytes and nonelectrolytes, the whole-nerve response to a mixture could not be predicted from the known neural or psychophysical effects of its components. PMID:7411114

The influence of botulinum toxin type A (BTX) on the immunohistochemical characteristics of noradrenergic and cholinergic nerve fibers supplying the porcine urinary bladder wall.

PubMed

Lepiarczyk, E; Bossowska, A; Kaleczyc, J; Majewski, M

2011-01-01

Botulinum toxin (BTX) belongs to a family of neurotoxins which strongly influence the function of autonomic neurons supplying the urinary bladder. Accordingly, BTX has been used as an effective drug in experimental therapies of a range of neurogenic bladder disorders. However, there is no detailed information dealing with the influence of BTX on the morphological and chemical properties of nerve fibres supplying the urinary bladder wall. Therefore, the present study investigated, using double-labeling immunohistochemistry, the distribution, relative frequency and chemical coding of cholinergic and noradrenergic nerve fibers supplying the wall of the urinary bladder in normal female pigs (n = 6) and in the pigs (n = 6) after intravesical BTX injections. In the pigs injected with BTX, the number of adrenergic (DbetaH-positive) nerve fibers distributed in the bladder wall (urothelium, submucosa and muscle coat) was distinctly higher while the number of cholinergic (VAChT-positive) nerve terminals was lower than that found in the control animals. Moreover, the injections of BTX resulted in some changes dealing with the chemical coding of the adrenergic nerve fibers. In contrast to the normal pigs, in BTX injected animals the number of DbetaH/NPY- or DbetaH/CGRP-positive axons was higher in the muscle coat, and some fibres distributed in the urothelium and submucosa expressed immunoreactivity to CGRP. The results obtained suggest that the therapeutic effects of BTX on the urinary bladder might be dependent on changes in the distribution and chemical coding of nerve fibers supplying this organ.

Structural, optical and electrical properties of copper antimony sulfide thin films grown by a citrate-assisted single chemical bath deposition

NASA Astrophysics Data System (ADS)

Loranca-Ramos, F. E.; Diliegros-Godines, C. J.; Silva González, R.; Pal, Mou

2018-01-01

Copper antimony sulfide (CAS) has been proposed as low toxicity and earth abundant absorber materials for thin film photovoltaics due to their suitable optical band gap, high absorption coefficient and p-type electrical conductivity. The present work reports the formation of copper antimony sulfide by chemical bath deposition using sodium citrate as a complexing agent. We show that by tuning the annealing condition, one can obtain either chalcostibite or tetrahedrite phase. However, the main challenge was co-deposition of copper and antimony as ternary sulfides from a single chemical bath due to the distinct chemical behavior of these metals. The as-deposited films were subjected to several trials of thermal treatment using different temperatures and time to find the optimized annealing condition. The films were characterized by different techniques including Raman spectroscopy, X-ray diffraction (XRD), profilometer, scanning electron microscopy (SEM), UV-vis spectrophotometer, and Hall Effect measurements. The results show that the formation of chalcostibite and tetrahedrite phases is highly sensitive to annealing conditions. The electrical properties obtained for the chalcostibite films varied as the annealing temperature increases from 280 to 350 °C: hole concentration (n) = 1017-1018 cm-3, resistivity (ρ) = 1.74-2.14 Ωcm and carrier mobility (μ) = 4.7-9.26 cm2/Vseg. While for the tetrahedrite films, the electrical properties were n = 5 × 1019 cm-3, μ = 18.24 cm2/Vseg, and ρ = 5.8 × 10-3 Ωcm. A possible mechanism for the formation of ternary copper antimony sulfide has also been proposed.

ARO - Terrestrial Research Program, Methodologies and Protocols for Characterization of Geomaterials

DTIC Science & Technology

2015-05-14

of ice involves melting, digestion, and analysis using inductively coupled plasma – mass spectrometry (ICPMS). ICP-MS analysis established elemental...4] have distinct chemical compositions. Knowledge of the chemical composition of the mineral assemblage present in a rock is critical to...activation analysis (INAA), to inductively-coupled plasma analysis and mass spectrometry (ICP & ICP-MS), mass spectrometry (MS), and laser-ablation

A Qualitative Report of the Ways High School Chemistry Students Attempt to Represent a Chemical Reaction at the Atomic/Molecular Level

ERIC Educational Resources Information Center

Kern, Anne L.; Wood, Nathan B.; Roehrig, Gillian H.; Nyachwaya, James

2010-01-01

We report the findings of a large-scale (n = 1,337) qualitative descriptive analysis of U.S. high schools students' particulate representations of a chemical reaction, specifically, the combustion of methane. Data were collected as part of an end of course exam. Student representations were coded into 17 distinct subcategories under one of five…

Extrasynaptic GABAA receptors in the crosshairs of hormones and ethanol

PubMed Central

Mody, Istvan

2008-01-01

Gamma-aminobutyric acid (GABA) is the main chemical inhibitory neurotransmitter in the brain. In the central nervous system (CNS) it acts on two distinct types of receptor: an ion channel, i.e., an “ionotropic” receptor permeable to Cl− and HCO3− (GABAA receptors) and a G-protein coupled “metabotropic” receptor that is linked to various effector mechanisms (GABAB receptors). This review will summarize novel developments in the physiology and pharmacology of GABAA receptors (GABAARs), specifically those found outside synapses. The focus will be on a particular combination of GABAAR subunits sensitive to ovarian and adrenal cortical steroid hormone metabolites that are synthesized in the brain (neurosteroids) and to sobriety impairing concentrations of ethanol. These receptors may be the final common pathway for interactions between ethanol and ovarian and stress-related neurosteroids. PMID:17714830

Intrinsic and chemically produced microheterogeneity of Staphylococcus aureus enterotoxin type C.

PubMed Central

Metzger, J F; Johnson, A D; Spero, L

1975-01-01

Staphylococcus aureus enterotoxins C1 (SEC1) and C2 (SEC2) produced from 50-liter quantities of crude culture supernatants were purified chromatographically in a neutral or acid milieu. Microheterogenity of SEC1 was markedly increased by treatment of the purified toxin with alkali, and new more acidic charged species appeared. SEC2 was more heterogenous than any of the other S. aureus enterotoxins and was affected only slightly by treatment with alkali. Prolonged incubation of the organism during production of the SEC2 produced changes in charged species that may be related to a bacterial deamidase, since similar changes were not seen with alkaline treatment of the purified toxin. Although SEC1 and SEC2 showed complete identity immunologically, they are separate, distinct toxins, and alkali treatment of SEC1 did not produce SEC2. Images PMID:237837

Identification and staining of distinct populations of secretory organelles in astrocytes.

PubMed

Bezzi, Paola; Volterra, Andrea

2014-05-01

Increasing evidence indicates that astrocytes, the most abundant glial cell type in the brain, respond to an elevation in cytoplasmic calcium concentration ([Ca(2+)]i) by releasing chemical transmitters (also called gliotransmitters) via regulated exocytosis of heterogeneous classes of organelles. By this process, astrocytes exert modulatory influences on neighboring cells and are thought to participate in the control of synaptic circuits and cerebral blood flow. Studying the properties of exocytosis in astrocytes is a challenge, because the cell biological basis of this process is incompletely defined. Astrocytic exocytosis involves multiple populations of secretory vesicles, including synaptic-like microvesicles (SLMVs), dense-core granules (DCGs), and lysosomes. Here we summarize the available information for identifying individual populations of secretory organelles in astrocytes, including DCGs, SLMVs, and lysosomes, and present experimental procedures for specifically staining such populations.

Differentiation of Wines Treated with Wood Chips Based on Their Phenolic Content, Volatile Composition, and Sensory Parameters.

PubMed

Kyraleou, Maria; Kallithraka, Stamatina; Chira, Kleopatra; Tzanakouli, Eleni; Ligas, Ioannis; Kotseridis, Yorgos

2015-12-01

The effects of both wood chips addition and contact time on phenolic content, volatile composition, color parameters, and organoleptic character of red wine made by a native Greek variety (Agiorgitiko) were evaluated. For this purpose, chips from American, French, Slavonia oak, and Acacia were added in the wine after fermentation. A mixture consisting of 50% French and 50% Americal oak chips was also evaluated. In an attempt to categorize wine samples, various chemical parameters of wines and sensory parameters were studied after 1, 2, and 3 mo of contact time with chips. The results showed that regardless of the type of wood chips added in the wines, it was possible to differentiate the samples according to the contact time based on their phenolic composition and color parameters. In addition, wood-extracted volatile compounds seem to be the critical parameter that could separate the samples according to the wood type. The wines that were in contact with Acacia and Slavonia chips could be separated from the rest mainly due to their distinct sensory characters. © 2015 Institute of Food Technologists®

Identifying elemental genomic track types and representing them uniformly

PubMed Central

2011-01-01

Background With the recent advances and availability of various high-throughput sequencing technologies, data on many molecular aspects, such as gene regulation, chromatin dynamics, and the three-dimensional organization of DNA, are rapidly being generated in an increasing number of laboratories. The variation in biological context, and the increasingly dispersed mode of data generation, imply a need for precise, interoperable and flexible representations of genomic features through formats that are easy to parse. A host of alternative formats are currently available and in use, complicating analysis and tool development. The issue of whether and how the multitude of formats reflects varying underlying characteristics of data has to our knowledge not previously been systematically treated. Results We here identify intrinsic distinctions between genomic features, and argue that the distinctions imply that a certain variation in the representation of features as genomic tracks is warranted. Four core informational properties of tracks are discussed: gaps, lengths, values and interconnections. From this we delineate fifteen generic track types. Based on the track type distinctions, we characterize major existing representational formats and find that the track types are not adequately supported by any single format. We also find, in contrast to the XML formats, that none of the existing tabular formats are conveniently extendable to support all track types. We thus propose two unified formats for track data, an improved XML format, BioXSD 1.1, and a new tabular format, GTrack 1.0. Conclusions The defined track types are shown to capture relevant distinctions between genomic annotation tracks, resulting in varying representational needs and analysis possibilities. The proposed formats, GTrack 1.0 and BioXSD 1.1, cater to the identified track distinctions and emphasize preciseness, flexibility and parsing convenience. PMID:22208806

Hygroscopic properties of internally mixed particles composed of NaCl and water-soluble organic acids.

PubMed

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei; Laskin, Alexander

2014-02-18

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water-soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy, atomic force microscopy, and X-ray elemental microanalysis. Hygroscopic properties of internally mixed NaCl and organic acid particles were distinctly different from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of sodium malonate and sodium glutarate salts resulted by HCl evaporation from dehydrating particles.

Hygroscopic Properties of Internally Mixed Particles Composed of NaCl and Water-Soluble Organic Acids

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

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei V.

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy and X-ray elemental microanalysis.Hygroscopic properties of inte rnally mixed NaCl and organic acid particles were distinctly differentmore » from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of Na-malonate and Na-glutarate salts resulted by HCl evaporation from dehydrating particles.« less

Fluorophore labeling of a cell-penetrating peptide induces differential effects on its cellular distribution and affects cell viability.

PubMed

Birch, Ditlev; Christensen, Malene Vinther; Staerk, Dan; Franzyk, Henrik; Nielsen, Hanne Mørck

2017-12-01

Cell-penetrating peptides constitute efficient delivery vectors, and studies of their uptake and mechanism of translocation typically involve fluorophore-labeled conjugates. In the present study, the influence of a number of specific fluorophores on the physico-chemical properties and uptake-related characteristics of penetratin were studied. An array of seven fluorophores belonging to distinct structural classes was examined, and the impact of fluorophore labeling on intracellular distribution and cytotoxicity was correlated to the physico-chemical properties of the conjugates. Exposure of several mammalian cell types to fluorophore-penetratin conjugates revealed a strong structure-dependent reduction in viability (1.5- to 20-fold lower IC 50 values as compared to those of non-labeled penetratin). Also, the degree of less severe effects on membrane integrity, as well as intracellular distribution patterns differed among the conjugates. Overall, neutral hydrophobic fluorophores or negatively charged fluorophores conferred less cytotoxicity as compared to the effect exerted by positively charged, hydrophobic fluorophores. The latter conjugates, however, exhibited less membrane association and more clearly defined intracellular distribution patterns. Thus, selection of the appropriate flurophore is critical. Copyright © 2017 Elsevier B.V. All rights reserved.

Vapor-Driven Propulsion of Catalytic Micromotors

NASA Astrophysics Data System (ADS)

Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

2015-08-01

Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

Vapor-Driven Propulsion of Catalytic Micromotors

PubMed Central

Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

2015-01-01

Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors. PMID:26285032

Diversity of exophillic acid derivatives in strains of an endophytic Exophiala sp.

PubMed

Cheikh-Ali, Zakaria; Glynou, Kyriaki; Ali, Tahir; Ploch, Sebastian; Kaiser, Marcel; Thines, Marco; Bode, Helge B; Maciá-Vicente, Jose G

2015-10-01

Members of the fungal genus Exophiala are common saprobes in soil and water environments, opportunistic pathogens of animals, or endophytes in plant roots. Their ecological versatility could imply a capacity to produce diverse secondary metabolites, but only a few studies have aimed at characterizing their chemical profiles. Here, we assessed the secondary metabolites produced by five Exophiala sp. strains of a particular phylotype, isolated from roots of Microthlaspi perfoliatum growing in different European localities. Exophillic acid and two previously undescribed compounds were isolated from these strains, and their structures were elucidated by spectroscopic methods using MS, 1D and 2D NMR. Bioassays revealed a weak activity of these compounds against disease-causing protozoa and mammalian cells. In addition, 18 related structures were identified by UPLC/MS based on comparisons with the isolated structures. Three Exophiala strains produced derivatives containing a β-d-glucopyranoside moiety, and their colony morphology was distinct from the other two strains, which produced derivatives lacking β-d-glucopyranoside. Whether the chemical/morphological strain types represent variants of the same genotype or independent genetic populations within Exophiala remains to be evaluated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modified nucleoside triphosphates exist in mammals† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc05472f

PubMed Central

Jiang, Han-Peng; Xiong, Jun; Liu, Fei-Long; Ma, Cheng-Jie; Tang, Xing-Lin; Feng, Yu-Qi

2018-01-01

DNA and RNA contain diverse chemical modifications that exert important influences in a variety of cellular processes. In addition to enzyme-mediated modifications of DNA and RNA, previous in vitro studies showed that pre-modified nucleoside triphosphates (NTPs) can be incorporated into DNA and RNA during replication and transcription. Herein, we established a chemical labeling method in combination with liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) analysis for the determination of endogenous NTPs in the mammalian cells and tissues. We synthesized 8-(diazomethyl)quinoline (8-DMQ) that could efficiently react with the phosphate group under mild condition to label NTPs. The developed method allowed sensitive detection of NTPs, with the detection limits improved by 56–137 folds. The results showed that 12 types of endogenous modified NTPs were distinctly determined in the mammalian cells and tissues. In addition, the majority of these modified NTPs exhibited significantly decreased contents in human hepatocellular carcinoma (HCC) tissues compared to tumor-adjacent normal tissues. Taken together, our study revealed the widespread existence of various modified NTPs in eukaryotes. PMID:29780546

Variations in some environmental characteristics including C and N stable isotopic composition of suspended organic matter in the Mandovi estuary.

PubMed

Maya, M V; Soares, Melena A; Agnihotri, Rajesh; Pratihary, A K; Karapurkar, Supriya; Naik, Hema; Naqvi, S W A

2011-04-01

Chemical and isotopic (δ13C and δ15N) investigation of the Mandovi estuary along the Indian west coast affected strongly by the seasonal monsoon cycle was carried out. The Mandovi estuary is a major waterway for Goa and extensively used for transportation of iron and manganese ore. In addition, with large population centers as well as agricultural fields located on its shores, the estuary is assumed to have been influenced by human activities. Measurements of chemical and isotopic parameters made in the lower part of the estuary during the southwest (SW) monsoon and post-monsoon seasons reveal distinct changes, and it is observed that despite considerable enrichment of macronutrients during the SW monsoon, productivity of the estuary (phytoplankton biomass), as inferred from the chlorophyll-a content, is not as high as expected. This is due to occurrences of high turbidity and cloud cover that limits photosynthetic productivity. The isotopic characterization (C and N isotopes) of suspended organic matter produced/transported during the monsoon and post-monsoon seasons of year 2007 provides a baseline dataset for future isotopic studies in such type of tropical estuaries.

A forward chemical screen in zebrafish identifies a retinoic acid derivative with receptor specificity.

PubMed

Das, Bhaskar C; McCartin, Kellie; Liu, Ting-Chun; Peterson, Randall T; Evans, Todd

2010-04-02

Retinoids regulate key developmental pathways throughout life, and have potential uses for differentiation therapy. It should be possible to identify novel retinoids by coupling new chemical reactions with screens using the zebrafish embryonic model. We synthesized novel retinoid analogues and derivatives by amide coupling, obtaining 80-92% yields. A small library of these compounds was screened for bioactivity in living zebrafish embryos. We found that several structurally related compounds significantly affect development. Distinct phenotypes are generated depending on time of exposure, and we characterize one compound (BT10) that produces specific cardiovascular defects when added 1 day post fertilization. When compared to retinoic acid (ATRA), BT10 shows similar but not identical changes in the expression pattern of embryonic genes that are known targets of the retinoid pathway. Reporter assays determined that BT10 interacts with all three RAR receptor sub-types, but has no activity for RXR receptors, at all concentrations tested. Our screen has identified a novel retinoid with specificity for retinoid receptors. This lead compound may be useful for manipulating components of retinoid signaling networks, and may be further derivatized for enhanced activity.

Chemical Kinetics Database

National Institute of Standards and Technology Data Gateway

SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

A Molecular Census of Arcuate Hypothalamus and Median Eminence Cell Types

PubMed Central

Campbell, John N.; Macosko, Evan Z.; Fenselau, Henning; Pers, Tune H.; Lyubetskaya, Anna; Tenen, Danielle; Goldman, Melissa; Verstegen, Anne M.J.; Resch, Jon M.; McCarroll, Steven A.; Rosen, Evan D.; Lowell, Bradford B.; Tsai, Linus

2017-01-01

The hypothalamic arcuate-median eminence complex (Arc-ME) controls energy balance, fertility, and growth through molecularly distinct cell types, many of which remain unknown. To catalog cell types in an unbiased way, we profiled gene expression in 20,921 individual cells in and around the adult mouse Arc-ME using Drop-seq. We identify 50 transcriptionally distinct Arc-ME cell populations, including a rare tanycyte population at the Arc-ME diffusion barrier, a novel leptin-sensing neuronal population, multiple AgRP and POMC subtypes, and an orexigenic somatostatin neuronal population. We extended Drop-seq to detect dynamic expression changes across relevant physiological perturbations, revealing cell type-specific responses to energy status, including distinctly responsive subtypes of AgRP and POMC neurons. Finally, integrating our data with human GWAS data implicates two previously unknown neuronal subtypes in the genetic control of obesity. This resource will accelerate biological discovery by providing insights into molecular and cell type diversity from which function can be inferred. PMID:28166221

Chemical Expertise: Chemistry in the Royal Prussian Porcelain Manufactory.

PubMed

Klein, Ursula

2014-01-01

Eighteenth-century chemists defined chemistry as both a "science and an art." By "chemical art" they meant not merely experimentation but also parts of certain arts and crafts. This raises the question of how to identify the "chemical parts" of the arts and crafts in eighteenth-century Europe. In this essay I tackle this question with respect to porcelain manufacture. My essay begins with a brief discussion of historiographical problems related to this question. It then analyzes practices involved in porcelain manufacture that can be reasonably identified as chemical practices or a chemical art. My analysis yields evidence for the argument that chemical experts and expertise fulfilled distinct technical functions in porcelain manufacture and, by extension, in eighteenth-century "big industry," along with its system of division of labor.

Emotion differentiation dissected: between-category, within-category, and integral emotion differentiation, and their relation to well-being.

PubMed

Erbas, Yasemin; Ceulemans, Eva; Blanke, Elisabeth S; Sels, Laura; Fischer, Agneta; Kuppens, Peter

2018-04-24

Emotion differentiation, the ability to describe and label our own emotions in a differentiated and specific manner, has been repeatedly associated with well-being. However, it is unclear exactly what type of differentiation is most strongly related to well-being: the ability to make fine-grained distinctions between emotions that are relatively closely related (e.g. anger and irritation), the ability to make larger distinctions between very distinct emotions (e.g. anger and sadness), or the combination of both. To determine which type of differentiation is most predictive of well-being, we performed a comprehensive meta-analysis across six datasets. We examined the correlations between these three types of differentiation and several indicators of well-being (depression, emotional clarity, and self-esteem). Results showed that individuals differentiated most between very distinct emotions and least between more related emotions, and that an index computed across emotions from both the same and different emotion categories was most strongly associated with well-being indicators.

Cerebral vascular amyloid seeds drive amyloid β-protein fibril assembly with a distinct anti-parallel structure

PubMed Central

Xu, Feng; Fu, Ziao; Dass, Sharmila; Kotarba, AnnMarie E.; Davis, Judianne; Smith, Steven O.; Van Nostrand, William E.

2016-01-01

Cerebrovascular accumulation of amyloid β-protein (Aβ), a condition known as cerebral amyloid angiopathy (CAA), is a common pathological feature of patients with Alzheimer's disease. Familial Aβ mutations, such as Dutch-E22Q and Iowa-D23N, can cause severe cerebrovascular accumulation of amyloid that serves as a potent driver of vascular cognitive impairment and dementia. The distinctive features of vascular amyloid that underlie its unique pathological properties remain unknown. Here, we use transgenic mouse models producing CAA mutants (Tg-SwDI) or overproducing human wild-type Aβ (Tg2576) to demonstrate that CAA-mutant vascular amyloid influences wild-type Aβ deposition in brain. We also show isolated microvascular amyloid seeds from Tg-SwDI mice drive assembly of human wild-type Aβ into distinct anti-parallel β-sheet fibrils. These findings indicate that cerebrovascular amyloid can serve as an effective scaffold to promote rapid assembly and strong deposition of Aβ into a unique structure that likely contributes to its distinctive pathology. PMID:27869115

Biocommodity Engineering.

PubMed

Lynd; Wyman; Gerngross

1999-10-01

The application of biotechnology to the production of commodity products (fuels, chemicals, and materials) offering benefits in terms of sustainable resource supply and environmental quality is an emergent area of intellectual endeavor and industrial practice with great promise. Such "biocommodity engineering" is distinct from biotechnology motivated by health care at multiple levels, including economic driving forces, the importance of feedstocks and cost-motivated process engineering, and the scale of application. Plant biomass represents both the dominant foreseeable source of feedstocks for biotechnological processes as well as the only foreseeable sustainable source of organic fuels, chemicals, and materials. A variety of forms of biomass, notably many cellulosic feedstocks, are potentially available at a large scale and are cost-competitive with low-cost petroleum whether considered on a mass or energy basis, and in terms of price defined on a purchase or net basis for both current and projected mature technology, and on a transfer basis for mature technology. Thus the central, and we believe surmountable, impediment to more widespread application of biocommodity engineering is the general absence of low-cost processing technology. Technological and research challenges associated with converting plant biomass into commodity products are considered relative to overcoming the recalcitrance of cellulosic biomass (converting cellulosic biomass into reactive intermediates) and product diversification (converting reactive intermediates into useful products). Advances are needed in pretreatment technology to make cellulosic materials accessible to enzymatic hydrolysis, with increased attention to the fundamental chemistry operative in pretreatment processes likely to accelerate progress. Important biotechnological challenges related to the utilization of cellulosic biomass include developing cellulase enzymes and microorganisms to produce them, fermentation of xylose and other nonglucose sugars, and "consolidated bioprocessing" in which cellulase production, cellulose hydrolysis, and fermentation of soluble carbohydrates to desired products occur in a single process step. With respect to product diversification, a distinction is made between replacement of a fossil resource-derived chemical with a biomass-derived chemical of identical composition and substitution of a biomass-derived chemical with equivalent functional characteristics but distinct composition. The substitution strategy involves larger transition issues but is seen as more promising in the long term. Metabolic engineering pursuant to the production of biocommodity products requires host organisms with properties such as the ability to use low-cost substrates, high product yield, competitive fitness, and robustness in industrial environments. In many cases, it is likely to be more successful to engineer a desired pathway into an organism having useful industrial properties rather than trying to engineer such often multi-gene properties into host organisms that do not have them naturally. Identification of host organisms with useful industrial properties and development of genetic systems for these organisms is a research challenge distinctive to biocommodity engineering. Chemical catalysis and separations technologies have important roles to play in downstream processing of biocommodity products and involve a distinctive set of challenges relative to petrochemical processing. At its current nascent state of development, the definition and advancement of the biocommodity field can benefit from integration at multiple levels. These include technical issues associated with integrating unit operations with each other, integrating production of individual products into a multi-product biorefinery, and integrating biorefineries into the broader resource, economic, and environmental systems in which they function. We anticipate that coproduction of multiple products, for example, production of fuels, chemicals, power, and/or feed, is likely to be essential for economic viability. Lifecycle analysis is necessary to verify the sustainability and environmental quality benefits of a particular biocommodity product or process. We see biocommodity engineering as a legitimate focus for graduate study, which is responsive to an established personnel demand in an industry that is expected to grow in the future. Graduate study in biocommodity engineering is supported by a distinctive blend of intellectual elements, including biotechnology, process engineering, and resource and environmental systems.

Distinctive activation and functionalization of hydrocarbon C-H bonds initiated by Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes.

PubMed

Baillie, Rhett A; Legzdins, Peter

2014-02-18

Converting hydrocarbon feedstocks into value-added chemicals continues to offer challenges to contemporary preparative chemists. A particularly important remaining challenge is the selective activation and functionalization of the C(sp(3))-H linkages of alkanes, which are relatively abundant but chemically inert. This Account outlines the discovery and development of C-H bond functionalization mediated by a family of tungsten organometallic nitrosyl complexes. Specifically, it describes how gentle thermolyses of any of four 18-electron Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes (Cp* = η(5)-C5Me5; η(3)-allyl = η(3)-H2CCHCHMe, η(3)-H2CCHCHSiMe3, η(3)-H2CCHCHPh, or η(3)-H2CCHCMe2) results in the loss of neopentane and the transient formation of a 16-electron intermediate species, Cp*W(NO)(η(2)-allene) and/or Cp*W(NO)(η(2)-diene). We have never detected any of these species spectroscopically, but we infer their existence based on trapping experiments with trimethylphosphine (PMe3) and labeling experiments using deuterated hydrocarbon substrates. This Account first summarizes the syntheses and properties of the four chiral Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes. It then outlines the various types of C-H activations we have effected with each of the 16-electron (η(2)-allene) or (η(2)-diene) intermediate nitrosyl complexes, and presents the results of mechanistic investigations of some of these processes. It next describes the characteristic chemical properties of the Cp*W(NO)(η(3)-allyl)(η(1)-hydrocarbyl) compounds formed by the single activations of C(sp(3))-H bonds, with particular emphasis on those reactions that result in the selective functionalization of the original hydrocarbon substrate. We are continuing development of methods to release the acyl ligands from the metal centers while keeping the Cp*W(NO)(η(3)-allyl) fragments intact, with the ultimate aim of achieving these distinctive conversions of alkanes into functionalized organics in a catalytic manner.

The Control and Treatment of Narcotics Use. Parole Decision Making.

ERIC Educational Resources Information Center

Glaser, Daniel; O'Leary, Vincent

After a brief discussion of the physiological effects of drugs on the human body, seven distinctive features of drug usage in the United States since the start of World War II are noted, and initiation into drug usage is described. The notion of a distinct personality type of addicts is not favored since terms used to characterize the type are not…

Neuronal migration disorders in microcephalic osteodysplastic primordial dwarfism type I/III

PubMed Central

Juric-Sekhar, Gordana; Kapur, Raj P.; Glass, Ian A.; Murray, Mitzi L.; Parnell, Shawn E.

2011-01-01

Microcephalic osteodysplastic primordial dwarfism (MOPD) is a rare microlissencephaly syndrome, with at least two distinct phenotypic and genetic types. MOPD type II is caused by pericentrin mutations, while types I and III appear to represent a distinct entity (MOPD I/III) with variably penetrant phenotypes and unknown genetic basis. The neuropathology of MOPD I/III is little understood, especially in comparison to other forms of lissencephaly. Here, we report postmortem brain findings in an 11-month-old female infant with MOPD I/III. The cerebral cortex was diffusely pachygyric, with a right parietal porencephalic lesion. Histologically, the cortex was abnormally thick and disorganized. Distinct malformations were observed in different cerebral lobes, as characterized using layer-specific neuronal markers. Frontal cortex was severely disorganized and coated with extensive leptomeningeal glioneuronal heterotopia. Temporal cortex had a relatively normal 6-layered pattern, despite cortical thickening. Occipital cortex was variably affected. The corpus callosum was extremely hypoplastic. Brainstem and cerebellar malformations were also present, as well as old necrotic foci. Findings in this case suggest that the cortical malformation in MOPD I/III is distinct from other forms of pachygyria–lissencephaly. PMID:20857301

Laser-Induced, Local Oxidation of Copper Nanoparticle Films During Raman Measurements

NASA Astrophysics Data System (ADS)

Hight Walker, Angela R.; Cheng, Guangjun; Calizo, Irene

2011-03-01

The optical properties of gold and silver nanoparticles and their films have been thoroughly investigated as surface enhanced Raman scattering (SERS) substrates and chemical reaction promoters. Similar to gold and silver nanoparticles, copper nanoparticles exhibit distinct plasmon absorptions in the visible region. The work on copper nanoparticles and their films is limited due to their oxidization in air. However, their high reactivity actually provides an opportunity to exploit the laser-induced thermal effect and chemical reactions of these nanoparticles. Here, we present our investigation of the local oxidation of a copper nanoparticle film induced by a visible laser source during Raman spectroscopic measurements. The copper nanoparticle film is prepared by drop-casting chemically synthesized copper colloid onto silicon oxide/silicon substrate. The local oxidation induced by visible lasers in Raman spectroscopy is monitored with the distinct scattering peaks for copper oxides. Optical microscopy and scanning electron microscopy have been used to characterize the laser-induced morphological changes in the film. The results of this oxidation process with different excitation wavelengths and different laser powers will be presented.

Towards reconstruction of overlapping fingerprints using plasma spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Jun-Ho; Choi, Soo-Jin; Yoh, Jack J.

2017-08-01

Chemical analysis is commonly used in the field of forensic science where the precise discrimination of primary evidence is of significant importance. Laser-Induced Breakdown Spectroscopy (LIBS) exceeds other spectroscopic methods in terms of the time required for pre- and post-sample preparation, the insensitivity to sample phase state be it solid, liquid, or gas, and the detection of two-dimensional spectral mapping from real time point measurements. In this research, fingerprint samples on various surface materials are considered in the chemical detection and reconstruction of fingerprints using the two-dimensional LIBS technique. Strong and distinct intensities of specific wavelengths represent visible ink, natural secretion of sweat, and contaminants from the environment, all of which can be present in latent fingerprints. The particular aim of the work presented here is to enhance the precision of the two-dimensional recreation of the fingerprints present on metal, plastic, and artificially prepared soil surface using LIBS with principal component analysis. By applying a distinct wavelength discrimination for two overlapping fingerprint samples, separation into two non-identical chemical fingerprints was successfully performed.

Inflammatory myoglandular polyp--a rare but distinct type of colorectal polyps.

PubMed

Becheanu, Gabriel; Stamm, Bernhard

2003-01-01

The aim of this paper was to report another example of a rare type of colorectal polyps, the inflammatory myoglandular polyp, and to reaffirm this type of polyp as a distinct entity. This solitary pedunculated polyp was detected after a single episode of rectal bleeding. It was situated in the sigmoid colon, measured 2.5 cm in greatest diameter, and was composed almost exclusively of smooth muscles and hyperplastic glands. The patient had neither chronic colitis nor diverticula. Clinical presentation, localization, and histology give this type of polyp a unique appearance and justify its designation as a separate entity.

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

Pomeroy, L.R.

There are three distinct but not mutually exclusive areas of research in this contract, studies of intrusions of the west wall of the Gulf Stream onto the outer continental shelf, studies of the flux of materials across nearshore density fronts, and advances in understanding of the planktonic food web of the continental shelf. Studies of frontal events on the outer and inner continental shelf involve distinctive physical and chemical regimes and have proven to require distinctive biological approaches. The studies of the food web run through our work on both of the frontal regimes, but certain aspects have become subjectsmore » in their own right. We have developed a simulation model of the flux of energy through the continental shelf food web which we believe to be more realistic than previous ones of its type. We have examined several of the many roles of dissolved organic compounds in sea water which originate either from release by phytoplankton, digestive processes or metabolites of zooplankton, or extracellular digestion of microorganisms. Methods have been developed under this contract to measure both the chelating capacity of naturally occurring organic materials and the copper concentration in the water. It has been possible to characterize the effects, both toxic and stimulatory, of copper on photosynthesis of naturally occurring phytoplankton populations. It is possible to characterize in considerable detail the course of biological events associated with meanders of the Gulf Stream. We are now in a position to explain the limits to biological productivity of the outer continental shelf of the southeastern US and the reasons why that biological production moves through the food web in the characteristic way that it does.« less

Nitrification rates in Arctic soils are associated with functionally distinct populations of ammonia-oxidizing archaea

PubMed Central

Alves, Ricardo J Eloy; Wanek, Wolfgang; Zappe, Anna; Richter, Andreas; Svenning, Mette M; Schleper, Christa; Urich, Tim

2013-01-01

The functioning of Arctic soil ecosystems is crucially important for global climate, and basic knowledge regarding their biogeochemical processes is lacking. Nitrogen (N) is the major limiting nutrient in these environments, and its availability is strongly dependent on nitrification. However, microbial communities driving this process remain largely uncharacterized in Arctic soils, namely those catalyzing the rate-limiting step of ammonia (NH3) oxidation. Eleven Arctic soils were analyzed through a polyphasic approach, integrating determination of gross nitrification rates, qualitative and quantitative marker gene analyses of ammonia-oxidizing archaea (AOA) and bacteria (AOB) and enrichment of AOA in laboratory cultures. AOA were the only NH3 oxidizers detected in five out of 11 soils and outnumbered AOB in four of the remaining six soils. The AOA identified showed great phylogenetic diversity and a multifactorial association with the soil properties, reflecting an overall distribution associated with tundra type and with several physico-chemical parameters combined. Remarkably, the different gross nitrification rates between soils were associated with five distinct AOA clades, representing the great majority of known AOA diversity in soils, which suggests differences in their nitrifying potential. This was supported by selective enrichment of two of these clades in cultures with different NH3 oxidation rates. In addition, the enrichments provided the first direct evidence for NH3 oxidation by an AOA from an uncharacterized Thaumarchaeota–AOA lineage. Our results indicate that AOA are functionally heterogeneous and that the selection of distinct AOA populations by the environment can be a determinant for nitrification activity and N availability in soils. PMID:23466705

Earth science: Extraordinary world

NASA Astrophysics Data System (ADS)

Day, James M. D.

2016-09-01

The isotopic compositions of objects that formed early in the evolution of the Solar System have been found to be similar to Earth's composition -- overturning notions of our planet's chemical distinctiveness. See Letters p.394 & p.399

Qualitatively Coherent Representation Makes Decision-Making Easier with Binary-Colored Multi-Attribute Tables: An Eye-Tracking Study

PubMed Central

Morii, Masahiro; Ideno, Takashi; Takemura, Kazuhisa; Okada, Mitsuhiro

2017-01-01

We aimed to identify the ways in which coloring cells affected decision-making in the context of binary-colored multi-attribute tables, using eye movement data. In our black-white attribute tables, the value of attributes was limited to two (with a certain threshold for each attribute) and each cell of the table was colored either black or white on the white background. We compared the two natural ways of systematic color assignment: “quantitatively coherent” ways and “qualitatively coherent” ways (namely, the ways in which the black-white distinction represented the quantitative amount distinction, and the ways in which the black-white distinction represented the quality distinction). The former consists of the following two types: (Type 1) “larger is black,” where the larger value-level was represented by black, and “smaller is white,” and (Type 2) “smaller is black.” The latter consisted of the following two types: (Type 3) “better is black,” and (Type 4) “worse is black.” We obtained the following two findings. [Result 1] The qualitatively coherent black-white tables (Types 3 and 4) made decision-making easier than the quantitatively coherent ones (Types 1 and 2). [Result 2] Among the two qualitatively coherent types, the “black is better” tables (Type 3) made decision making easier; in fact, the participants focused on the more important (black) cells in the case of “black is better” tables (Type 3) while they did not focus enough on the more important (white) ones in the case of the “white is better” tables (Type 4). We also examined some measures of eye movement patterns and showed that these measures supported our hypotheses. The data showed differences in the eye movement patterns between the first and second halves of each trial, which indicated the phased or combined decision strategies taken by the participants. PMID:28861020

Pump-probe imaging of pigmented cutaneous melanoma primary lesions gives insight into metastatic potential

PubMed Central

Robles, Francisco E.; Deb, Sanghamitra; Wilson, Jesse W.; Gainey, Christina S.; Selim, M. Angelica; Mosca, Paul J.; Tyler, Douglas S.; Fischer, Martin C.; Warren, Warren S.

2015-01-01

Metastatic melanoma is associated with a poor prognosis, but no method reliably predicts which melanomas of a given stage will ultimately metastasize and which will not. While sentinel lymph node biopsy (SLNB) has emerged as the most powerful predictor of metastatic disease, the majority of people dying from metastatic melanoma still have a negative SLNB. Here we analyze pump-probe microscopy images of thin biopsy slides of primary melanomas to assess their metastatic potential. Pump-probe microscopy reveals detailed chemical information of melanin with subcellular spatial resolution. Quantification of the molecular signatures without reference standards is achieved using a geometrical representation of principal component analysis. Melanin structure is analyzed in unison with the chemical information by applying principles of mathematical morphology. Results show that melanin in metastatic primary lesions has lower chemical diversity than non-metastatic primary lesions, and contains two distinct phenotypes that are indicative of aggressive disease. Further, the mathematical morphology analysis reveals melanin in metastatic primary lesions has a distinct “dusty” quality. Finally, a statistical analysis shows that the combination of the chemical information with spatial structures predicts metastatic potential with much better sensitivity than SLNB and high specificity, suggesting pump-probe microscopy can be an important tool to help predict the metastatic potential of melanomas. PMID:26417529

Computational and Statistical Analyses of Amino Acid Usage and Physico-Chemical Properties of the Twelve Late Embryogenesis Abundant Protein Classes

PubMed Central

Jaspard, Emmanuel; Macherel, David; Hunault, Gilles

2012-01-01

Late Embryogenesis Abundant Proteins (LEAPs) are ubiquitous proteins expected to play major roles in desiccation tolerance. Little is known about their structure - function relationships because of the scarcity of 3-D structures for LEAPs. The previous building of LEAPdb, a database dedicated to LEAPs from plants and other organisms, led to the classification of 710 LEAPs into 12 non-overlapping classes with distinct properties. Using this resource, numerous physico-chemical properties of LEAPs and amino acid usage by LEAPs have been computed and statistically analyzed, revealing distinctive features for each class. This unprecedented analysis allowed a rigorous characterization of the 12 LEAP classes, which differed also in multiple structural and physico-chemical features. Although most LEAPs can be predicted as intrinsically disordered proteins, the analysis indicates that LEAP class 7 (PF03168) and probably LEAP class 11 (PF04927) are natively folded proteins. This study thus provides a detailed description of the structural properties of this protein family opening the path toward further LEAP structure - function analysis. Finally, since each LEAP class can be clearly characterized by a unique set of physico-chemical properties, this will allow development of software to predict proteins as LEAPs. PMID:22615859

Two chemically distinct light-absorbing pools of urban organic aerosols: A comprehensive multidimensional analysis of trends.

PubMed

Paula, Andreia S; Matos, João T V; Duarte, Regina M B O; Duarte, Armando C

2016-02-01

The chemical and light-absorption dynamics of organic aerosols (OAs), a master variable in the atmosphere, have yet to be resolved. This study uses a comprehensive multidimensional analysis approach for exploiting simultaneously the compositional changes over a molecular size continuum and associated light-absorption (ultraviolet absorbance and fluorescence) properties of two chemically distinct pools of urban OAs chromophores. Up to 45% of aerosol organic carbon (OC) is soluble in water and consists of a complex mixture of fluorescent and UV-absorbing constituents, with diverse relative abundances, hydrophobic, and molecular weight (Mw) characteristics between warm and cold periods. In contrast, the refractory alkaline-soluble OC pool (up to 18%) is represented along a similar Mw and light-absorption continuum throughout the different seasons. Results suggest that these alkaline-soluble chromophores may actually originate from primary OAs sources in the urban site. This work shows that the comprehensive multidimensional analysis method is a powerful and complementary tool for the characterization of OAs fractions. The great diversity in the chemical composition and optical properties of OAs chromophores, including both water-soluble and alkaline-soluble OC, may be an important contribution to explain the contrasting photo-reactivity and atmospheric behavior of OAs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dynamic Triple-Mode Sorption and Outgassing in Materials.

PubMed

Sharma, Hom N; Harley, Stephen J; Sun, Yunwei; Glascoe, Elizabeth A

2017-06-07

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C-70 °C) by varying the water activity (0.0-0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis, especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.

Dynamic Triple-Mode Sorption and Outgassing in Materials

DOE PAGES

Sharma, Hom N.; Harley, Stephen J.; Sun, Yunwei; ...

2017-06-07

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C–70 °C) by varying the water activity (0.0–0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis,more » especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.« less

Dynamic Triple-Mode Sorption and Outgassing in Materials

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

Sharma, Hom N.; Harley, Stephen J.; Sun, Yunwei

Moisture uptake and outgassing can be detrimental to a system by altering the chemical and mechanical properties of materials within the system over time. In this work, we conducted isotherm experiments to investigate dynamic moisture sorption and desorption in markedly different materials, i.e., a polymeric material, Sylgard-184 and a ceramic aluminosilicate material, Zircar RS-1200, at different temperatures (30 °C–70 °C) by varying the water activity (0.0–0.90). Sylgard-184 showed a linear sorption and outgassing behavior with no-hysteresis over the entire temperature and water activity range considered here. Whereas, the sorption and outgassing of Zircar RS-1200 was highly non-linear with significant hysteresis,more » especially at higher water activities, at all temperatures considered here. The type of hysteresis suggested the presence of mesopores in Zircar RS-1200, whereas the lack of hysteresis in Sylgard-184 indicates that it has a nonporous structure. A diffusion model coupled with a dynamic, triple-mode sorption (Langmuir, Henry, and pooling modes) model employed in this study matched our experimental data very well and provides mechanistic insight into the processes. Our triple-mode sorption model was adaptive enough to (1) model these distinctly different materials and (2) predict sorption and outgassing under conditions that are distinctly different from the parameterization experiments.« less

Self-Assembly of Polysaccharides Gives Rise to Distinct Mechanical Signatures in Marine Gels

PubMed Central

Pletikapić, G.; Lannon, H.; Murvai, Ü.; Kellermayer, M.S.Z.; Svetličić, V.; Brujic, J.

2014-01-01

Marine-gel biopolymers were recently visualized at the molecular level using atomic force microscopy (AFM) to reveal fine fibril-forming networks with low to high degrees of cross-linking. In this work, we use force spectroscopy to quantify the intra- and intermolecular forces within the marine-gel network. Combining force measurements, AFM imaging, and the known chemical composition of marine gels allows us to identify the microscopic origins of distinct mechanical responses. At the single-fibril level, we uncover force-extension curves that resemble those of individual polysaccharide fibrils. They exhibit entropic elasticity followed by extensions associated with chair-to-boat transitions specific to the type of polysaccharide at high forces. Surprisingly, a low degree of cross-linking leads to sawtooth patterns that we attribute to the unraveling of polysaccharide entanglements. At a high degree of cross-linking, we observe force plateaus that arise from unzipping, as well as unwinding, of helical bundles. Finally, the complex 3D network structure gives rise to force staircases of increasing height that correspond to the hierarchical peeling of fibrils away from the junction zones. In addition, we show that these diverse mechanical responses also arise in reconstituted polysaccharide gels, which highlights their dominant role in the mechanical architecture of marine gels. PMID:25028877

THE ANABOLIC STEROIDS TESTOSTERONE PROPIONATE AND NANDROLONE, BUT NOT 17α-METHYLTESTOSTERONE, INDUCE CONDITIONED PLACE PREFERENCE IN ADULT MICE

PubMed Central

Parrilla-Carrero, Jeffrey; Figueroa, Orialis; Lugo, Alejandro; García-Sosa, Rebecca; Brito-Vargas, Paul; Cruz, Beatriz; Rivera, Melanis; Barreto-Estrada, Jennifer L.

2009-01-01

Anabolic androgenic steroids (AAS) are often misused by adolescents and athletes. Their effects vary according to chemical structure and metabolism, route of administration, and AAS regimen. In this study, adult C57Bl/6 male mice were systemically exposed to testosterone propionate (TP), nandrolone or 17α-methyltestosterone (17α-meT), type I, type II and type III AAS, respectively, in order to determine the hedonic or aversive properties of each drug. For this purpose, the conditioned place preference (CPP) test was employed at three different AAS doses (0.075, 0.75 and 7.5 mg/kg). Other behavioral domains monitored were light-dark transitions (side changes) and general activity. TP shifted place preference at all doses tested, and nandrolone shifted place preference at 0.75 and 7.5mg/kg, but not at 0.075 mg/kg, the lower dose tested. Conversely, mice receiving 17α-meT did not show alteration in the preference score. The lower dose of nandrolone did modify exploratory based-anxiety showing a decrease in light-dark transitions if compared to vehicle-treated animals, while mice treated with TP or 17α-meT were not affected. Our data suggest that when studying hedonic and rewarding properties of synthetic androgens, distinction has to be made based on type of AAS and metabolism. PMID:19028026

The anabolic steroids testosterone propionate and nandrolone, but not 17alpha-methyltestosterone, induce conditioned place preference in adult mice.

PubMed

Parrilla-Carrero, Jeffrey; Figueroa, Orialis; Lugo, Alejandro; García-Sosa, Rebecca; Brito-Vargas, Paul; Cruz, Beatriz; Rivera, Mélanis; Barreto-Estrada, Jennifer L

2009-02-01

Anabolic androgenic steroids (AAS) are often misused by adolescents and athletes. Their effects vary according to chemical structure and metabolism, route of administration, and AAS regimen. In this study, adult C57Bl/6 male mice were systemically exposed to testosterone propionate (TP), nandrolone or 17alpha-methyltestosterone (17alpha-meT), type I, type II and type III AAS, respectively, in order to determine the hedonic or aversive properties of each drug. For this purpose, the conditioned place preference (CPP) test was employed at three different AAS doses (0.075, 0.75 and 7.5 mg/kg). Other behavioral domains monitored were light-dark transitions (side changes) and general activity. TP shifted place preference at all doses tested, and nandrolone shifted place preference at 0.75 and 7.5 mg/kg, but not at 0.075 mg/kg, the lower dose tested. Conversely, mice receiving 17alpha-meT did not show alteration in the preference score. The lower dose of nandrolone did modify exploratory-based anxiety showing a decrease in light-dark transitions if compared to vehicle-treated animals, while mice treated with TP or 17alpha-meT were not affected. Our data suggest that when studying hedonic and rewarding properties of synthetic androgens, distinction has to be made based on type of AAS and metabolism.

Cannibalism of olivine-rich cumulate xenoliths during the 1998 eruption of Piton de la Fournaise (La Réunion hotspot): Implications for the generation of magma diversity

NASA Astrophysics Data System (ADS)

Salaün, A.; Villemant, B.; Semet, M. P.; Staudacher, T.

2010-12-01

Contrasting with its unusual isotopic homogeneity compared to other hotspot volcanoes, Piton de la Fournaise has produced a large diversity of basaltic magmas over its 0.5 Ma history: picrites and two types of transitional basalts with distinct petrological and chemical compositions. A minor group of evolved basalts (anomalous group of basalts or AGB) is enriched in both compatible (Mg, Fe, Ti, Cr, and Ni) and incompatible (K, Th, and La) elements and depleted in Ca and Si relative to the dominant group of evolved basalts. The 1998 eruption simultaneously produced the two basaltic types at two distinct vents (Hudson vent: AGB, Kapor vent: common basalt) but from the same feeding conduit. Glasses of both magmas are close in composition and belong to the single differentiation trend defined by all 1998-2007 glass compositions. Thermodynamic model (MELTS code) shows that AGB-type magmas cannot be produced by high pressure (> 1 GPa) clinopyroxene fractionation as previously proposed and that all melts of the 1998-2007 activity period are produced by low pressure (< 800 MPa) crystal fractionation from the most primitive basalt (MgO ~ 9%). Modal composition of 1998 lavas (mass balance calculation and SEM image analysis) and olivine crystal composition show that Hudson lavas have assimilated significant fractions of olivine xenocrysts contrary to Kapor lavas. In addition, the higher incompatible element contents of Hudson lavas suggest contamination by a differentiated (trachytic) melt. All AGB share the following characteristics: (i) evolved glass compositions, (ii) 5-10% olivine xenocrysts, and (iii) vents located in a narrow region at the summit of the edifice. They are interpreted as the result of the assimilation of olivine-rich xenoliths either by evolved melts or by basaltic melts contaminated by low fractions of differentiated melts produced from interstitial glass frequently coating cumulates minerals or resulting from partial melting of cumulates bearing pyroxene or plagioclase (wehrlitic to gabbroic cumulates). The scarcity of AGB magmas is attributed to their shallow transfer path in rarely intruded lateral zones of Piton de la Fournaise volcano: wehrlitic to gabbroic cumulates bodies are either heterogeneously distributed within the edifice or have been depleted in low melting point components in the 'Rift Zone' where most of the recent eruptive events are emplaced. These results emphasize the exceptional chemical homogeneity of the primary basaltic melt involved in volcanic activity of Piton de la Fournaise hotspot for 0.5 Ma and the increasingly recognized role of magma-wall rock interactions in erupted magma compositions.

Adolescents' Use of Basic, Intermediate, and Advanced Device Types for Vaping.

PubMed

Pepper, Jessica K; MacMonegle, Anna J; Nonnemaker, James M

2017-12-23

Advanced models of electronic vaping products (EVPs) likely pose a greater risk to adolescent health than basic or intermediate models because advanced models deliver nicotine more effectively and heat e-liquid to higher temperatures, producing more harmful chemical emissions. However, little is known about adolescents' risk factors for using different device types. We used social media to recruit an online sample of 1,508 U.S. adolescents aged 15-17 who reported past 30-day use of e-cigarettes. We assessed tobacco use, beliefs and knowledge about EVPs, and EVP use behavior, including the device type participants use most frequently. We used multinomial logistic regression to examine differences between adolescents who usually use intermediate versus basic and advanced versus basic devices. Most respondents usually used modifiable advanced devices (56.8%) rather than basic "cigalike" (14.5%) or pen-style intermediate (28.7%) devices. Use of multiple device types was common, particularly among those who primarily used basic devices. Younger age and less frequent vaping were associated with mainly using basic devices. Adolescents who were older, male, personally bought their main device, and had ever mixed e-liquids were at elevated risk for usually using advanced devices. Adolescents who primarily use basic devices may be newer users who are experimenting with multiple devices. Future research should examine which adolescents are most likely to transition to advanced devices in order to develop targeted interventions. Regulators should consider strategies to reduce access to all types of EVPs, such as better enforcement of the current ban on sales to minors. This research addresses two gaps in research on adolescent electronic vaping product use: (1) characterizing use of advanced devices as distinct from intermediate devices rather than grouping them together and (2) examining factors associated with use of specific device types. This study suggests that there are distinct profiles of adolescents who use primarily basic, intermediate, or advanced devices. Adolescents who most often use basic devices may be new users experimenting with vaping, whereas adolescents who most often use advanced devices appear to be buying devices for themselves and engaging in risky behaviors such as mixing their own e-liquid. © The Author(s) 2017. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Superfluidity and spin superfluidity in spinor Bose gases

NASA Astrophysics Data System (ADS)

Armaitis, J.; Duine, R. A.

2017-05-01

We show that spinor Bose gases subject to a quadratic Zeeman effect exhibit coexisting superfluidity and spin superfluidity, and study the interplay between these two distinct types of superfluidity. To illustrate that the basic principles governing these two types of superfluidity are the same, we describe the magnetization and particle-density dynamics in a single hydrodynamic framework. In this description spin and mass supercurrents are driven by their respective chemical potential gradients. As an application, we propose an experimentally accessible stationary state, where the two types of supercurrents counterflow and cancel each other, thus resulting in no mass transport. Furthermore, we propose a straightforward setup to probe spin superfluidity by measuring the in-plane magnetization angle of the whole cloud of atoms. We verify the robustness of these findings by evaluating the four-magnon collision time, and find that the time scale for coherent (superfluid) dynamics is separated from that of the slower incoherent dynamics by one order of magnitude. Comparing the atom and magnon kinetics reveals that while the former can be hydrodynamic, the latter is typically collisionless under most experimental conditions. This implies that, while our zero-temperature hydrodynamic equations are a valid description of spin transport in Bose gases, a hydrodynamic description that treats both mass and spin transport at finite temperatures may not be readily feasible.

Rhizobium etli asparaginase II

PubMed Central

Huerta-Saquero, Alejandro; Evangelista-Martínez, Zahaed; Moreno-Enriquez, Angélica; Perez-Rueda, Ernesto

2013-01-01

Bacterial l-asparaginase has been a universal component of therapies for childhood acute lymphoblastic leukemia since the 1970s. Two principal enzymes derived from Escherichia coli and Erwinia chrysanthemi are the only options clinically approved to date. We recently reported a study of recombinant l-asparaginase (AnsA) from Rhizobium etli and described an increasing type of AnsA family members. Sequence analysis revealed four conserved motifs with notable differences with respect to the conserved regions of amino acid sequences of type I and type II l-asparaginases, particularly in comparison with therapeutic enzymes from E. coli and E. chrysanthemi. These differences suggested a distinct immunological specificity. Here, we report an in silico analysis that revealed immunogenic determinants of AnsA. Also, we used an extensive approach to compare the crystal structures of E. coli and E. chrysantemi asparaginases with a computational model of AnsA and identified immunogenic epitopes. A three-dimensional model of AsnA revealed, as expected based on sequence dissimilarities, completely different folding and different immunogenic epitopes. This approach could be very useful in transcending the problem of immunogenicity in two major ways: by chemical modifications of epitopes to reduce drug immunogenicity, and by site-directed mutagenesis of amino acid residues to diminish immunogenicity without reduction of enzymatic activity. PMID:22895060

Rhizobium etli asparaginase II: an alternative for acute lymphoblastic leukemia (ALL) treatment.

PubMed

Huerta-Saquero, Alejandro; Evangelista-Martínez, Zahaed; Moreno-Enriquez, Angélica; Perez-Rueda, Ernesto

2013-01-01

Bacterial L-asparaginase has been a universal component of therapies for childhood acute lymphoblastic leukemia since the 1970s. Two principal enzymes derived from Escherichia coli and Erwinia chrysanthemi are the only options clinically approved to date. We recently reported a study of recombinant L-asparaginase (AnsA) from Rhizobium etli and described an increasing type of AnsA family members. Sequence analysis revealed four conserved motifs with notable differences with respect to the conserved regions of amino acid sequences of type I and type II L-asparaginases, particularly in comparison with therapeutic enzymes from E. coli and E. chrysanthemi. These differences suggested a distinct immunological specificity. Here, we report an in silico analysis that revealed immunogenic determinants of AnsA. Also, we used an extensive approach to compare the crystal structures of E. coli and E. chrysantemi asparaginases with a computational model of AnsA and identified immunogenic epitopes. A three-dimensional model of AsnA revealed, as expected based on sequence dissimilarities, completely different folding and different immunogenic epitopes. This approach could be very useful in transcending the problem of immunogenicity in two major ways: by chemical modifications of epitopes to reduce drug immunogenicity, and by site-directed mutagenesis of amino acid residues to diminish immunogenicity without reduction of enzymatic activity.

Chemical depth profiles of the GaAs/native oxide interface

NASA Technical Reports Server (NTRS)

Grunthaner, P. J.; Vasquez, R. P.; Grunthaner, F. J.

1980-01-01

The final-state oxidation products and their distribution in thin native oxides (30-40 A) on GaAs have been studied using X-ray photoelectron spectroscopy in conjunction with chemical depth profiling. Extended room-temperature-oxidation conditions have been chosen to allow the native oxide to attain its equilibrium composition and structure. The work emphasizes the use of chemical depth-profiling methods which make it possible to examine the variation in chemical reactivity of the oxide structure. A minimum of two distinct regions of Ga2O3 with differing chemical reactivity is observed. Chemical shift data indicate the presence of As2O3 in the oxide together with an elemental As overlayer at the interface. A change in relative charge transfer between oxygen and both arsenic and gallium-oxide species is observed in the region of the interface.

Paraduodenal Pancreatitis: Imaging and Pathologic Correlation of 47 Cases Elucidates Distinct Subtypes and the Factors Involved in its Etiopathogenesis.

PubMed

Muraki, Takashi; Kim, Grace E; Reid, Michelle D; Mittal, Pardeep; Bedolla, Gabriela; Memis, Bahar; Pehlivanoglu, Burcin; Freedman, Alexa; Erbarut Seven, Ipek; Choi, Hyejeong; Kooby, David; Maithel, Shishir K; Sarmiento, Juan M; Krasinskas, Alyssa; Adsay, Volkan

2017-10-01

Clinicopathologic characteristics of paraduodenal (groove) pancreatitis (PDP) remain to be fully unraveled. In this study, 47 PDPs with preoperative enhanced images available were subjected to detailed comparative analysis in conjunction with pathologic findings. PDP were predominantly in males (3:1) with a mean age of 50 years, and 60% had a preoperative diagnosis of cancer. Mean lesional size was 3.1 cm. Three distinct subtypes were identified by imaging. Solid-tumoral (type-1) with groove-predominant (type-1A, 36%) forming a distinct solid band between the duodenum and pancreas often with histologic microabscesses (69% vs. 33% in others), and pancreas-involving (type-1B, 19%) forming a pseudotumoral mass spanning into the head-groove area, always diagnosed preoperatively as "cancer," but often lacked parenchymal atrophy of the body (44% vs. 92%). Cyst-forming (type-2) had groove-predominant (type-2A, 15%), often accompanied by Brunner gland hyperplasia, and pancreas-predominant (type-2B, 15%) were in younger (mean: 44 y) females (57% vs. 18%) and had less alcohol/tobacco abuse (50/33% vs. 81/69%). Ill-defined (type-3; 15%) often had main pancreatic duct dilatation (mean: 5.6 vs. 2.8 mm). The capricious presentations of PDP could be attributed to variable effects of different mechanistic and precipitative etiopathogenetic factors such as disturbed accessory duct outflow (dilated Santorini duct, 87%), aggravated by alcohol (77%) with superimposed stasis in the main ampulla (previous cholecystectomy, 47%; choledocholithiasis, 9%), strictured Wirsung duct (68%), and some likely exacerbated by ischemia (hypertension [59%], tobacco abuse [64%], arteriosclerosis in the tissue [23%]). In conclusion, our study identified 3 distinct types of PDP and each may reflect different pathogenetic contributing factors.

Four alpha ganglion cell types in mouse retina: Function, structure, and molecular signatures

PubMed Central

Sanes, Joshua R.

2017-01-01

The retina communicates with the brain using ≥30 parallel channels, each carried by axons of distinct types of retinal ganglion cells. In every mammalian retina one finds so-called "alpha" ganglion cells (αRGCs), identified by their large cell bodies, stout axons, wide and mono-stratified dendritic fields, and high levels of neurofilament protein. In the mouse, three αRGC types have been described based on responses to light steps: On-sustained, Off-sustained, and Off-transient. Here we employed a transgenic mouse line that labels αRGCs in the live retina, allowing systematic targeted recordings. We characterize the three known types and identify a fourth, with On-transient responses. All four αRGC types share basic aspects of visual signaling, including a large receptive field center, a weak antagonistic surround, and absence of any direction selectivity. They also share a distinctive waveform of the action potential, faster than that of other RGC types. Morphologically, they differ in the level of dendritic stratification within the IPL, which accounts for their response properties. Molecularly, each type has a distinct signature. A comparison across mammals suggests a common theme, in which four large-bodied ganglion cell types split the visual signal into four channels arranged symmetrically with respect to polarity and kinetics. PMID:28753612

9 CFR 11.3 - Scar rule.

Code of Federal Regulations, 2013 CFR

2013-01-01

..., excessive loss of hair. 3,4 [Reserved] 5 Granuloma is defined as any one of a rather large group of fairly distinctive focal lesions that are formed as a result of inflammatory reactions caused by biological, chemical...

9 CFR 11.3 - Scar rule.

Code of Federal Regulations, 2014 CFR

2014-01-01

..., excessive loss of hair. 3 4 [Reserved] 5 Granuloma is defined as any one of a rather large group of fairly distinctive focal lesions that are formed as a result of inflammatory reactions caused by biological, chemical...

9 CFR 11.3 - Scar rule.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., excessive loss of hair. 3,4 [Reserved] 5 Granuloma is defined as any one of a rather large group of fairly distinctive focal lesions that are formed as a result of inflammatory reactions caused by biological, chemical...

9 CFR 11.3 - Scar rule.

Code of Federal Regulations, 2011 CFR

2011-01-01

..., excessive loss of hair. 3,4 [Reserved] 5 Granuloma is defined as any one of a rather large group of fairly distinctive focal lesions that are formed as a result of inflammatory reactions caused by biological, chemical...

9 CFR 11.3 - Scar rule.

Code of Federal Regulations, 2012 CFR

2012-01-01

..., excessive loss of hair. 3,4 [Reserved] 5 Granuloma is defined as any one of a rather large group of fairly distinctive focal lesions that are formed as a result of inflammatory reactions caused by biological, chemical...

Individual Aerosol Particle Types Produced by Savanna Burning

NASA Astrophysics Data System (ADS)

Posfai, M.; Simonics, R.; Li, J.; Hobbs, P. V.; Buseck, P. R.; Buseck, P. R.

2001-12-01

We used analytical transmission electron microscopy (TEM) to study individual aerosol particles that were collected on the University of Washington Convair-580 research aircraft over southern Africa during the Safari2000 Dry Season Experiment. Our goals were to study the compositions, morphologies, and mixing states of carbonaceous particles, in order to better understand the physical and chemical properties of biomass smoke on the individual-particle level. The compositions of single particles were determined using energy-dispersive x-ray spectrometry (EDS) and electron energy-loss spectroscopy (EELS). Energy-loss maps obtained with the TEM are useful for studying the spatial distribution of light elements such as carbon within the particles; thus, they provide a detailed picture of complex particles. Carbonaceous particles were assigned into three main groups on the basis of morphology and composition: "organic particles with inorganic inclusions," "tar balls," and "soot." Soot is recognized by its characteristic morphology and microstructure. The distinction between "organic particles with inorganic inclusions" and "tar balls" is somewhat arbitrary, since the two criteria that are used for their distinction (composition and aspect ratio) change continually. The relative concentrations of the three major particle types vary with the type of fire and distance from fire. In the plume of a smoldering fire west of Beria (August 31) the relative concentration of tar balls increased with aging of the plume. Tar balls have a fairly narrow size distribution with a maximum between 100 and 200 nm (diameter). The inorganic K-salt inclusions (KCl, K2SO4, KNO3) within "organic particles" should make these particles hygroscopic, regardless of the properties of the organic compounds. Aging causes the conversion of KCl into K2SO4, KNO3. Aerosol production from flaming and smoldering fires was compared over Kruger National Park on August 17; more soot and more Cl-rich inclusions in organic particles were produced by the flaming fire than by the smoldering fire. Further sets of samples from other flights of Safari2000 are being studied.

Biogeography of photosynthetic light-harvesting genes in marine phytoplankton.

PubMed

Bibby, Thomas S; Zhang, Yinan; Chen, Min

2009-01-01

Photosynthetic light-harvesting proteins are the mechanism by which energy enters the marine ecosystem. The dominant prokaryotic photoautotrophs are the cyanobacterial genera Prochlorococcus and Synechococcus that are defined by two distinct light-harvesting systems, chlorophyll-bound protein complexes or phycobilin-bound protein complexes, respectively. Here, we use the Global Ocean Sampling (GOS) Project as a unique and powerful tool to analyze the environmental diversity of photosynthetic light-harvesting genes in relation to available metadata including geographical location and physical and chemical environmental parameters. All light-harvesting gene fragments and their metadata were obtained from the GOS database, aligned using ClustalX and classified phylogenetically. Each sequence has a name indicative of its geographic location; subsequent biogeographical analysis was performed by correlating light-harvesting gene budgets for each GOS station with surface chlorophyll concentration. Using the GOS data, we have mapped the biogeography of light-harvesting genes in marine cyanobacteria on ocean-basin scales and show that an environmental gradient exists in which chlorophyll concentration is correlated to diversity of light-harvesting systems. Three functionally distinct types of light-harvesting genes are defined: (1) the phycobilisome (PBS) genes of Synechococcus; (2) the pcb genes of Prochlorococcus; and (3) the iron-stress-induced (isiA) genes present in some marine Synechococcus. At low chlorophyll concentrations, where nutrients are limited, the Pcb-type light-harvesting system shows greater genetic diversity; whereas at high chlorophyll concentrations, where nutrients are abundant, the PBS-type light-harvesting system shows higher genetic diversity. We interpret this as an environmental selection of specific photosynthetic strategy. Importantly, the unique light-harvesting system isiA is found in the iron-limited, high-nutrient low-chlorophyll region of the equatorial Pacific. This observation demonstrates the ecological importance of isiA genes in enabling marine Synechococcus to acclimate to iron limitation and suggests that the presence of this gene can be a natural biomarker for iron limitation in oceanic environments.

The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam on board Curiosity: Potassic Sedimentary Rocks, Gale Crater

DOE PAGES

Le Deit, L.; Mangold, N.; Forni, O.; ...

2016-05-13

The Mars Science Laboratory rover Curiosity encountered potassium-rich clastic sedimentary rocks at two sites in Gale Crater, the waypoints Cooperstown and Kimberley. These rocks include several distinct meters thick sedimentary outcrops ranging from fine sandstone to conglomerate, interpreted to record an ancient fluvial or fluvio-deltaic depositional system. Furthermore, from ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) chemical analyses, this suite of sedimentary rocks has an overall mean K 2O abundance that is more than 5 times higher than that of the average Martian crust. The combined analysis of ChemCam data with stratigraphic and geographic locations then reveals that the mean K 2Omore » abundance increases upward through the stratigraphic section. Chemical analyses across each unit can be represented as mixtures of several distinct chemical components, i.e., mineral phases, including K-bearing minerals, mafic silicates, Fe-oxides, and Fe-hydroxide/oxyhydroxides. Possible K-bearing minerals include alkali feldspar (including anorthoclase and sanidine) and K-bearing phyllosilicate such as illite. Mixtures of different source rocks, including a potassium-rich rock located on the rim and walls of Gale Crater, are the likely origin of observed chemical variations within each unit. Physical sorting may have also played a role in the enrichment in K in the Kimberley formation. The occurrence of these potassic sedimentary rocks provides additional evidence for the chemical diversity of the crust exposed at Gale Crater.« less

The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam on board Curiosity: Potassic Sedimentary Rocks, Gale Crater

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

Le Deit, L.; Mangold, N.; Forni, O.

The Mars Science Laboratory rover Curiosity encountered potassium-rich clastic sedimentary rocks at two sites in Gale Crater, the waypoints Cooperstown and Kimberley. These rocks include several distinct meters thick sedimentary outcrops ranging from fine sandstone to conglomerate, interpreted to record an ancient fluvial or fluvio-deltaic depositional system. Furthermore, from ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) chemical analyses, this suite of sedimentary rocks has an overall mean K 2O abundance that is more than 5 times higher than that of the average Martian crust. The combined analysis of ChemCam data with stratigraphic and geographic locations then reveals that the mean K 2Omore » abundance increases upward through the stratigraphic section. Chemical analyses across each unit can be represented as mixtures of several distinct chemical components, i.e., mineral phases, including K-bearing minerals, mafic silicates, Fe-oxides, and Fe-hydroxide/oxyhydroxides. Possible K-bearing minerals include alkali feldspar (including anorthoclase and sanidine) and K-bearing phyllosilicate such as illite. Mixtures of different source rocks, including a potassium-rich rock located on the rim and walls of Gale Crater, are the likely origin of observed chemical variations within each unit. Physical sorting may have also played a role in the enrichment in K in the Kimberley formation. The occurrence of these potassic sedimentary rocks provides additional evidence for the chemical diversity of the crust exposed at Gale Crater.« less

Regional transport of a chemically distinctive dust: Gypsum from White Sands, New Mexico (USA)

NASA Astrophysics Data System (ADS)

White, Warren H.; Hyslop, Nicole P.; Trzepla, Krystyna; Yatkin, Sinan; Rarig, Randy S.; Gill, Thomas E.; Jin, Lixin

2015-03-01

The White Sands complex, a National Monument and adjoining Missile Range in southern New Mexico, occupies the dry bed of an ice-age lake where an active gypsum dunefield abuts erodible playa sediments. Aerosols entrained from White Sands are sometimes visible on satellite images as distinct, light-colored plumes crossing the Sacramento Mountains to the east and northeast. The IMPROVE network (Interagency Monitoring of PROtected Visual Environments) operates long-term aerosol samplers at two sites east of the Sacramento range. In recent years a spring pulse of sulfate aerosol has appeared at these sites, eclipsing the regional summer peak resulting from atmospheric reactions of sulfur dioxide emissions. A significant fraction of this spring sulfate is contributed by gypsum and other salts from White Sands, with much of the sulfur in coarse particles and concentrations of calcium and strontium above regional levels. The increase in these gypsiferous species coincides with a drought following a period of above-average precipitation. White Sands and the IMPROVE samplers together provide a natural laboratory: a climatically sensitive dust source that is both well characterized and chemically distinct from its surroundings, with a signature that remains identifiable at long-term observatories 100-200 km downwind.

Modular and Orthogonal Synthesis of Hybrid Polymers and Networks

PubMed Central

Liu, Shuang; Dicker, Kevin T.; Jia, Xinqiao

2015-01-01

Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions. PMID:25572255

Botulinum toxin type A induces changes in the chemical coding of substance P-immunoreactive dorsal root ganglia sensory neurons supplying the porcine urinary bladder.

PubMed

Bossowska, Agnieszka; Lepiarczyk, Ewa; Mazur, Urszula; Janikiewicz, Paweł; Markiewicz, Włodzimierz

2015-11-16

Botulinum toxin (BTX) is a potent neurotoxin which blocks acetylcholine release from nerve terminals, and therefore leads to cessation of somatic motor and/or parasympathetic transmission. Recently it has been found that BTX also interferes with sensory transmission, thus, the present study was aimed at investigating the neurochemical characterization of substance P-immunoreactive (SP-IR) bladder-projecting sensory neurons (BPSN) after the toxin treatment. Investigated neurons were visualized with retrograde tracing method and their chemical profile was disclosed with double-labelling immunohistochemistry using antibodies against SP, calcitonin gene-related peptide (CGRP), pituitary adenylate cyclase activating polypeptide (PACAP), neuronal nitric oxide synthase (nNOS), galanin (GAL), calbindin (CB), and somatostatin (SOM). In the control group (n = 6), 45% of the total population of BPSN were SP-IR. Nearly half of these neurons co-expressed PACAP or CGRP (45% and 35%, respectively), while co-localization of SP with GAL, nNOS, SOM or CB was found less frequently (3.7%, 1.8%, 1.2%, and 0.7%, respectively). In BTX-treated pigs (n = 6), toxin-injections caused a decrease in the number of SP-IR cells containing CGRP, SOM or CB (16.2%, 0.5%, and 0%, respectively) and a distinct increase in these nerve cells immunopositive to GAL (27.2%). The present study demonstrates that BTX significantly modifies the chemical phenotypes of SP-IR BPSN.

Dispersive Raman spectroscopy allows the identification and quantification of melanin types

PubMed Central

Galván, Ismael; Jorge, Alberto

2015-01-01

Melanins are the most prevalent pigments in animals and are involved in visual communication by producing colored traits that often evolve as intraspecific signals of quality. Identifying and quantifying melanins are therefore essential to understand the function and evolution of melanin-based signals. However, the analysis of melanins is difficult due to their insolubility and the lack of simple methods that allow the identification of their chemical forms. We recently proposed the use of Raman spectroscopy as a simple, noninvasive technique that can be used to identify and quantify melanins in feathers and hairs. Contrarily, other authors later stated that melanins are characterized by a lack of defined Raman signals. Here, we use confocal Raman microscopy to confirm previous analyses showing that the two main chemical forms of melanins (eumelanin and pheomelanin) exhibit distinct Raman signal and compare different excitation wavelengths to analyze synthetic pheomelanin and natural melanins in feathers of different species of birds. Our analyses indicate that only laser excitation wavelengths below 1064 nm are useful for the analysis of melanins by Raman spectroscopy, and only 780-nm laser in the case of melanins in feathers. These findings show that the capacity of Raman spectroscopy to distinguish different chemical forms of melanins depends on laser power and integration time. As a consequence, Raman spectroscopy should be applied after preliminar analyses using a range of these parameters, especially in fragile biological tissues such as feathers. PMID:25897382

Differential undertaking response of a lower termite to congeneric and conspecific corpses

PubMed Central

Sun, Qian; Haynes, Kenneth F.; Zhou, Xuguo

2013-01-01

Undertaking behaviour is an essential activity in social insects. Corpses are often recognized by a postmortem change in a chemical signature. Reticulitermes flavipes responded to corpses within minutes of death. This undertaking behaviour did not change with longer postmortem time (24 h); however, R. flavipes exhibited distinctively different behaviours toward dead termites from various origins. Corpses of the congeneric species, Reticulitermes virginicus, were buried onsite by workers with a large group of soldiers guarding the burial site due to the risk of interspecific competition; while dead conspecifics, regardless of colony origin, were pulled back into the holding chamber for nutrient recycling and hygienic purposes. The burial task associated with congeneric corpses was coupled with colony defence and involved ten times more termites than retrieval of conspecific corpses. Our findings suggest elicitation of undertaking behaviour depends on the origin of corpses which is associated with different types of risk. PMID:23598990

Three case studies of the GasNet model in discrete domains.

PubMed

Santos, C L; de Oliveira, P P; Husbands, P; Souza, C R

2001-06-01

A new neural network model - the GasNet - has been recently reported in the literature, which, in addition to the traditional electric type, point-to-point communication between units, also uses communication through a diffilsable chemical modulator. Here we assess the applicability of this model in three different scenarios, the XOR problem, a food gathering task for a simulated robot, and a docking task for a virtual spaceship. All of them represent discrete domains, a contrast with the one where the GasNet was originally introduced, which had an essentially continuous nature. These scenarios are well-known benchmark problems from the literature and, since they exhibit varying degrees of complexity, they impose distinct performance demands on the GasNet. The experiments were primarily intended to better understand the model, by extending the original problem domain where GasNet was introduced. The results reported point at some difficulties with the current GasNet model.

Feasibility basis for use of new solid household waste processing equipment

NASA Astrophysics Data System (ADS)

Vertakova, Y. V.; Zvyagintsev, G. L.; Babich, T. N.; Polozhentseva, Y. S.

2017-10-01

Economic efficiency assessment of innovative organizational project of solid household waste processing enterprise (SHW) is given. A distinctive feature of this project is new mining and chemical technology use of waste depolymerization. The proved feature is fuel-resource production in portion modules of tubular type. They are patented and approved under laboratory conditions. The main ways of SHW processing in the world including Russia are described. Advantages and disadvantages are revealed. Comparative analysis is carried out. Technology prioritization is a result of this analysis. During organization of such enterprise, it was proved that not only SHW processing is a result of its functioning. The other result is environmentally friendly production using secondary raw materials. These products can be sold and can have bring income. Main investment and current expenses necessary for the offered project implementation are defined. This allows making economic assessment of innovative enterprise efficiency.

The effect of polymorphism on powder compaction and dissolution properties of chemically equivalent oxytetracycline hydrochloride powders.

PubMed

Liebenberg, W; de Villiers, M M; Wurster, D E; Swanepoel, E; Dekker, T G; Lötter, A P

1999-09-01

In South Africa, oxytetracycline is identified as an essential drug; many generic products are on the market, and many more are being developed. In this study, six oxytetracycline hydrochloride powders were obtained randomly from manufacturers, and suppliers were compared. It was found that compliance to a pharmacopoeial monograph was insufficient to ensure the optimum dissolution performance of a simple tablet formulation. Comparative physicochemical raw material analysis showed no major differences with regard to differential scanning calorimetry (DSC), infrared (IR) spectroscopy, powder dissolution, and particle size. However, the samples could be divided into two distinct types with respect to X-ray powder diffraction (XRD) and thus polymorphism. The two polymorphic forms had different dissolution properties in water or 0.1 N hydrochloride acid. This difference became substantial when the dissolution from tablets was compared. The powders containing form A were less soluble than that containing form B.

Morphology and mixing state of individual freshly emitted wildfire carbonaceous particles.

PubMed

China, Swarup; Mazzoleni, Claudio; Gorkowski, Kyle; Aiken, Allison C; Dubey, Manvendra K

2013-01-01

Biomass burning is one of the largest sources of carbonaceous aerosols in the atmosphere, significantly affecting earth's radiation budget and climate. Tar balls, abundant in biomass burning smoke, absorb sunlight and have highly variable optical properties, typically not accounted for in climate models. Here we analyse single biomass burning particles from the Las Conchas fire (New Mexico, 2011) using electron microscopy. We show that the relative abundance of tar balls (80%) is 10 times greater than soot particles (8%). We also report two distinct types of tar balls; one less oxidized than the other. Furthermore, the mixing of soot particles with other material affects their optical, chemical and physical properties. We quantify the morphology of soot particles and classify them into four categories: ~50% are embedded (heavily coated), ~34% are partly coated, ~12% have inclusions and~4% are bare. Inclusion of these observations should improve climate model performances.

The Remote Sensing of Mineral Aerosols and their Impact on Phytoplankton Productivity

NASA Technical Reports Server (NTRS)

Tindale, Neil W.

1997-01-01

The overall objective of this experiment was to test the iron hypothesis does the addition of iron to nutrient rich surface waters enhance productivity? Our specific objectives in this experiment included sampling and studying the marine aerosol size and type (which are related to chemical reactivity) during the PlumEx cruise to determine the importance of local (Galapagos Islands) versus long-range sources of atmospheric material. Detailed results of single particle analysis of our samples are being prepared for publication in two papers. We collect aerosol samples and they have been analyzed for trace metals and other elements. We are mapped aerosol distribution and the desert source areas around the Arabian Sea region. We did record a clear relationship between the aerosol radiance and synoptic weather patterns with distinct signals over the ocean northwest and southwest of Australia. While the interpretation was limited an aerosol climatology pattern was presented.

Intramolecular bonds resolved on a semiconductor surface

NASA Astrophysics Data System (ADS)

Sweetman, Adam; Jarvis, Samuel P.; Rahe, Philipp; Champness, Neil R.; Kantorovich, Lev; Moriarty, Philip

2014-10-01

Noncontact atomic force microscopy (NC-AFM) is now routinely capable of obtaining submolecular resolution, readily resolving the carbon backbone structure of planar organic molecules adsorbed on metal substrates. Here we show that the same resolution may also be obtained for molecules adsorbed on a reactive semiconducting substrate. Surprisingly, this resolution is routinely obtained without the need for deliberate tip functionalization. Intriguingly, we observe two chemically distinct apex types capable of submolecular imaging. We characterize our tip apices by "inverse imaging" of the silicon adatoms of the Si (111)-7×7 surface and support our findings with detailed density functional theory (DFT) calculations. We also show that intramolecular resolution on individual molecules may be readily obtained at 78 K, rather than solely at 5 K as previously demonstrated. Our results suggest a wide range of tips may be capable of producing intramolecular contrast for molecules adsorbed on semiconductor surfaces, leading to a much broader applicability for submolecular imaging protocols.

Xenoliths in the CM2 Carbonaceous Chondrite LON 94101: Implications for Complex Mixing on the Asteroidal Parent Body

NASA Technical Reports Server (NTRS)

Lindgren, P.; Lee, M. R.; Sofe, M.; Zolensky, M. E.

2011-01-01

Xenoliths are foreign clasts that oc-cur in various classes of meteorites, e.g. [1,2,3]. A re-cent study reveals the presence of several distinct classes of xenoliths in regolith-bearing meteorites, in-cluding in over 20 different carbonaceous chondrites [4]. The most common types of xenoliths are fine-grained hydrous clasts, often referred to as C1 or CI clasts in the literature, although their mineralogy is actually more similar to hydrous micrometeorites [5,6]. Xenoliths in meteorites present an opportunity to study material not yet classified or available as separate meteorites, and can provide additional information on processes in the dynamic early history of the Solar Sys-tem. Here we have performed chemical and mineralogi-cal analyses of xenoliths in the CM2 carbonaceous chondrite LON 94101, using scanning electron micro-scopy (SEM) and transmission electron microscopy (TEM).

A new meaning for “Gin & Tonic”

PubMed Central

Mody, Istvan; Glykys, Joseph; Wei, Weizheng

2007-01-01

Gamma-aminobutyric acid (GABA) is the main chemical inhibitory neurotransmitter in the brain. In the central nervous system (CNS) it acts on two distinct types of receptor: an ion channel, i.e., an “ionotropic” receptor permeable to Cl- and HCO3- (GABAA receptors) and a G-protein coupled “metabotropic” receptor that is linked to various effector mechanisms (GABAB receptors). This review will summarize novel developments in the physiology and pharmacology of GABAA receptors (GABAARs), specifically those found outside synapses. The focus will be on a particular combination of GABAAR subunits responsible for mediating tonic inhibition and sensitive to concentrations of ethanol legally considered to be sobriety impairing. Since the same receptors are also a preferred target for the metabolites of steroid hormones synthesized in the brain (neurosteroids), the ethanol-sensitive tonic inhibition may be a common pathway for interactions between the effects of alcohol and those of ovarian and stress-related neurosteroids. PMID:17521846

Nanomechanics of Protein Unfolding outside Protease Nanopores

NASA Astrophysics Data System (ADS)

Luan, Binquan; Zhou, Ruhong

Protein folding and unfolding have been the subject of active research for decades. Most of previous studies in protein unfolding were focused on temperature, chemical and/or force (such as in AFM) induced denaturations. Recent studies on the functional roles of proteasomes (such as ClpXP) revealed a novel unfolding process in cell, during which a target protein is mechanically unfolded and pulled into a confined, pore-like geometry for degradation. While the proteasome nanomachine has been extensively studied, the mechanism for unfolding proteins with the proteasome pore is still poorly understood. Here, we investigate the mechanical unfolding process of ubiquitin with (or really outside) an idealized proteasome pore, and compare such process with that in the AFM pulling experiment. Unexpectedly, the required force by a proteosome can be much smaller than that by the AFM. Simulation results also unveiled different nanomechanics, tearing fracture vs. shearing friction, in these two distinct types of mechanical unfoldings.

Digital microfluidics: A promising technique for biochemical applications

NASA Astrophysics Data System (ADS)

Wang, He; Chen, Liguo; Sun, Lining

2017-12-01

Digital microfluidics (DMF) is a versatile microfluidics technology that has significant application potential in the areas of automation and miniaturization. In DMF, discrete droplets containing samples and reagents are controlled to implement a series of operations via electrowetting-on-dielectric. This process works by applying electrical potentials to an array of electrodes coated with a hydrophobic dielectric layer. Unlike microchannels, DMF facilitates precise control over multiple reaction processes without using complex pump, microvalve, and tubing networks. DMF also presents other distinct features, such as portability, less sample consumption, shorter chemical reaction time, flexibility, and easier combination with other technology types. Due to its unique advantages, DMF has been applied to a broad range of fields (e.g., chemistry, biology, medicine, and environment). This study reviews the basic principles of droplet actuation, configuration design, and fabrication of the DMF device, as well as discusses the latest progress in DMF from the biochemistry perspective.

Generalized Rainich conditions, generalized stress-energy conditions, and the Hawking-Ellis classification

NASA Astrophysics Data System (ADS)

Martín–Moruno, Prado; Visser, Matt

2017-11-01

The (generalized) Rainich conditions are algebraic conditions which are polynomial in the (mixed-component) stress-energy tensor. As such they are logically distinct from the usual classical energy conditions (NEC, WEC, SEC, DEC), and logically distinct from the usual Hawking-Ellis (Segré-Plebański) classification of stress-energy tensors (type I, type II, type III, type IV). There will of course be significant inter-connections between these classification schemes, which we explore in the current article. Overall, we shall argue that it is best to view the (generalized) Rainich conditions as a refinement of the classical energy conditions and the usual Hawking-Ellis classification.

Memory and consciousness: trace distinctiveness in memory retrievals.

PubMed

Brunel, Lionel; Oker, Ali; Riou, Benoit; Versace, Rémy

2010-12-01

The aim of this article was to provide experimental evidence that classical dissociation between levels of consciousness associated with memory retrieval (i.e., implicit or explicit) can be explained in terms of task dependency and distinctiveness of traces. In our study phase, we manipulated the level of isolation (partial vs. global) of the memory trace by means of an isolation paradigm (isolated words among non-isolated words). We then tested these two types of isolation in a series of tasks of increasing complexity: a lexical decision task, a recognition task, and a free recall task. The main result of this study was that distinctiveness effects were observed as a function of the type of isolation (level of isolation) and the nature of the task. We concluded that trace distinctiveness improves subsequent access to the trace, while the level of trace distinctiveness also appears to determine the possibility of conscious or explicit retrieval. Copyright © 2010 Elsevier Inc. All rights reserved.

New small-molecule inhibitor class targeting human immunodeficiency virus type 1 virion maturation.

PubMed

Blair, Wade S; Cao, Joan; Fok-Seang, Juin; Griffin, Paul; Isaacson, Jason; Jackson, R Lynn; Murray, Edward; Patick, Amy K; Peng, Qinghai; Perros, Manos; Pickford, Chris; Wu, Hua; Butler, Scott L

2009-12-01

A new small-molecule inhibitor class that targets virion maturation was identified from a human immunodeficiency virus type 1 (HIV-1) antiviral screen. PF-46396, a representative molecule, exhibits antiviral activity against HIV-1 laboratory strains and clinical isolates in T-cell lines and peripheral blood mononuclear cells (PBMCs). PF-46396 specifically inhibits the processing of capsid (CA)/spacer peptide 1 (SP1) (p25), resulting in the accumulation of CA/SP1 (p25) precursor proteins and blocked maturation of the viral core particle. Viral variants resistant to PF-46396 contain a single amino acid substitution in HIV-1 CA sequences (CAI201V), distal to the CA/SP1 cleavage site in the primary structure, which we demonstrate is sufficient to confer significant resistance to PF-46396 and 3-O-(3',3'-dimethylsuccinyl) betulinic acid (DSB), a previously described maturation inhibitor. Conversely, a single amino substitution in SP1 (SP1A1V), which was previously associated with DSB in vitro resistance, was sufficient to confer resistance to DSB and PF-46396. Further, the CAI201V substitution restored CA/SP1 processing in HIV-1-infected cells treated with PF-46396 or DSB. Our results demonstrate that PF-46396 acts through a mechanism that is similar to DSB to inhibit the maturation of HIV-1 virions. To our knowledge, PF-46396 represents the first small-molecule HIV-1 maturation inhibitor that is distinct in chemical class from betulinic acid-derived maturation inhibitors (e.g., DSB), demonstrating that molecules of diverse chemical classes can inhibit this mechanism.

Microstructure of a safe-end dissimilar metal weld joint (SA508-52-316L) prepared by narrow-gap GTAW

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

Ming, Hongliang

The microstructure, residual strain and interfacial chemical composition distribution of a safe-end dissimilar metal weld joint (DMWJ, SA508-52-316L) prepared by narrow-gap gas-tungsten arc welding (NG-GTAW) were studied by optical microscope (OM) and scanning electron microscope equipped with an energy dispersive X-ray microanalysis (SEM/EDX) and an electron back scattering diffraction (EBSD) system. Complex microstructure and chemical composition distribution are found, especially at the SA508-52 interface and the 52-316L interface. In brief, a complicated microstructure transition exists within the SA508 heat affected zone (HAZ); the residual strain, the fraction of high angle random grain boundaries and low angle boundaries decrease with increasingmore » the distance from the fusion boundary in 316L HAZ; neither typical type II boundary nor obvious carbon-depleted zone is found near the SA508-52 interface; dramatic and complicated changes of the contents of the main elements, Fe, Cr and Ni, are observed at the distinct interfaces, especially at the SA508-52 interface. No carbon concentration is found at the SA508-52 interface. - Highlights: •Residual strain and GBCD change as a function of the distance from FB in 316L HAZ. •Neither type II boundary nor obvious carbon-depleted zone is found in SA508 HAZ. •No carbon concentration is found at the SA508-52 interface. •The middle part of the DMWJ has the highest residual strain.« less

Chemical Probes for Molecular Imaging and Detection of Hydrogen Sulfide and Reactive Sulfur Species in Biological Systems

PubMed Central

2014-01-01

Hydrogen sulfide (H2S), a gaseous species produced by both bacteria and higher eukaryotic organisms, including mammalian vertebrates, has attracted attention in recent years for its contributions to human health and disease. H2S has been proposed as a cytoprotectant and gasotransmitter in many tissue types, including mediating vascular tone in blood vessels as well as neuromodulation in the brain. The molecular mechanisms dictating how H2S affects cellular signaling and other physiological events remain insufficiently understood. Furthermore, the involvement of H2S in metal-binding interactions and formation of related RSS such as sulfane sulfur may contribute to other distinct signaling pathways. Owing to its widespread biological roles and unique chemical properties, H2S is an appealing target for chemical biology approaches to elucidate its production, trafficking, and downstream function. In this context, reaction-based fluorescent probes offer a versatile set of screening tools to visualize H2S pools in living systems. Three main strategies used in molecular probe development for H2S detection include azide and nitro group reduction, nucleophilic attack, and CuS precipitation. Each of these approaches exploit the strong nucleophilicity and reducing potency of H2S to achieve selectivity over other biothiols. In addition, a variety of methods have been developed for the detection of other reactive sulfur species (RSS), including sulfite and bisulfite, as well as sulfane sulfur species and related modifications such as S-nitrosothiols. Access to this growing chemical toolbox of new molecular probes for H2S and related RSS sets the stage for applying these developing technologies to probe reactive sulfur biology in living systems. PMID:25474627

Chemical property based sequence characterization of PpcA and its homolog proteins PpcB-E: A mathematical approach

PubMed Central

Pal Choudhury, Pabitra

2017-01-01

Periplasmic c7 type cytochrome A (PpcA) protein is determined in Geobacter sulfurreducens along with its other four homologs (PpcB-E). From the crystal structure viewpoint the observation emerges that PpcA protein can bind with Deoxycholate (DXCA), while its other homologs do not. But it is yet to be established with certainty the reason behind this from primary protein sequence information. This study is primarily based on primary protein sequence analysis through the chemical basis of embedded amino acids. Firstly, we look for the chemical group specific score of amino acids. Along with this, we have developed a new methodology for the phylogenetic analysis based on chemical group dissimilarities of amino acids. This new methodology is applied to the cytochrome c7 family members and pinpoint how a particular sequence is differing with others. Secondly, we build a graph theoretic model on using amino acid sequences which is also applied to the cytochrome c7 family members and some unique characteristics and their domains are highlighted. Thirdly, we search for unique patterns as subsequences which are common among the group or specific individual member. In all the cases, we are able to show some distinct features of PpcA that emerges PpcA as an outstanding protein compared to its other homologs, resulting towards its binding with deoxycholate. Similarly, some notable features for the structurally dissimilar protein PpcD compared to the other homologs are also brought out. Further, the five members of cytochrome family being homolog proteins, they must have some common significant features which are also enumerated in this study. PMID:28362850

Reactions of methamidophos with mammalian cholinesterase.

DOT National Transportation Integrated Search

1978-07-01

The lethality of methamidophos, a phosphoramidothioate, to rats (i.p. LD50, 15 mg/kg), is similar to that of such potent organophosphate compounds as parathion and paraoxon. Certain distinctive features of its chemical structure, and reported failure...

Riparian control of stream-water chemistry: Implications for hydrochemical basin models

USGS Publications Warehouse

Hooper, R.P.; Aulenbach, Brent T.; Burns, Douglas A.; McDonnell, J.; Freer, J.; Kendall, C.; Beven, K.

1998-01-01

End-member mixing analysis has been used to determine the hydrological structure for basin hydrochemical models at several catchments. Implicit in this use is the assumption that controlling end members have been identified, and that these end members represent distinct landscape locations. At the Panola Mountain Research Watershed, the choice of controlling end members was supported when a large change in the calcium and sulphate concentration of one of the end members was reflected in the stream water. More extensive sampling of groundwater and soil water indicated, however, that the geographic extent of the contributing end members was limited to the riparian zone. Hillslope solutions were chemically distinct from the riparian solutions and did not appear to make a large contribution to streamflow. The dominant control of the riparian zone on stream-water chemistry suggests that hydrological flow paths cannot be inferred from stream-water chemical dynamics.

Diagnosis of middle atmosphere chemistry-dynamics interactions

NASA Astrophysics Data System (ADS)

Zhu, X.; Swartz, W. H.; Garcia, R. R.; Chartier, A.; Yee, J. H.; Yue, J.

2017-12-01

We apply the recently developed middle atmosphere climate feedback-response analysis method (MCFRAM) to diagnosing the temperature variations associated with chemistry-dynamics interactions in the middle atmosphere. By using output fields from the Whole Atmosphere Community Climate Model (WACCM) coupled with the measurements, we identify and isolate the distinctive characteristics of different components in the observed temperature variations. Both the temperature trends associated with the anthropogenic forcing and temperature changes associated with natural and internal feedback processes are quantified based on MCFRAM defined partial temperature changes corresponding to localized radiative heating, non-localized chemical heating, eddy transport, and transport by the mean meridional circulation of energy and chemical species. In addition, the temperature responses to variations of CO2, O3, and solar flux have distinctly different spatial structures that can be systematically categorized by the eigenmodes of the generalized damping matrix derived from MCFRAM.

Not All Analogies Are Created Equal: Associative and Categorical Analogy Processing following Brain Damage

ERIC Educational Resources Information Center

Schmidt, Gwenda L.; Cardillo, Eileen R.; Kranjec, Alexander; Lehet, Matthew; Widick, Page; Chatterjee, Anjan

2012-01-01

Current research on analogy processing assumes that different conceptual relations are treated similarly. However, just as words and concepts are related in distinct ways, different kinds of analogies may employ distinct types of relationships. An important distinction in how words are related is the difference between associative (dog-bone) and…

Levels of theory and types of theoretical explanation in theoretical physics

NASA Astrophysics Data System (ADS)

Flores, Francisco J.

In Newtonian physics, there is a clear distinction between a 'framework theory', a collection of general physical principles and definitions of physical terms, and theories that describe specific causal interactions such as gravitation, i.e., 'interaction theories'. I argue that this distinction between levels of theory can also be found in the context of Special Relativity and that recognizing it is essential for a philosophical account of how laws are explained in this theory. As a case study, I consider the history of derivations of mass-energy equivalence which shows, I argue, that there are two distinct types of theoretical explanations (i.e., explanations of laws) in physics. One type is best characterized by the 'top-down' account of scientific explanation, while the other is more accurately described by the 'bottom-up' account. What is significant, I argue, is that the type of explanation a law receives depends on whether it is part of the framework theory or part of an interaction theory. The former only receive 'top-down' explanations while the latter can also receive 'bottom- up' explanations. Thus, I argue that current debates regarding 'top-down' vs 'bottom-up' views of scientific explanation can be clarified by recognizing the distinction between two levels of physical theory.

Environmental Variability, Bowhead Whale Distributions, and Inupiat Subsistence Whaling in the Coastal Arctic Ocean

NASA Astrophysics Data System (ADS)

Ashjian, C. J.; Campbell, R. G.; George, J. C.; Moore, S. E.; Okkonen, S. R.; Sherr, B. F.; Sherr, E. B.

2006-12-01

The annual migration of bowhead whales (Balaena mysticetus) past Barrow, Alaska has provided subsistence hunting opportunities to Native whalers for centuries. Bowheads regularly feed along the Arctic coast near Barrow in autumn, presumably to utilize recurrent aggregations of their zooplankton prey (e.g., copepods, euphausiids). Oceanographic field-sampling on the narrow continental shelf near Barrow and in Elson Lagoon was conducted during mid-August to mid-September of 2005 and 2006 to describe the different water mass types and plankton communities, to identify exchange of water and material between the shelf and lagoon and offshore, and to identify biological and physical mechanisms of plankton aggregation. High spatial resolution profiles of temperature, salinity, fluorescence, optical backscatter, and C-DOM were collected using an Acrobat undulating towed vehicle in the lagoon and across the shelf from near-shore to the ~150 m isobath. Discrete sampling for nutrients, chlorophyll a, and phytoplankton, and microzooplankton and mesozooplankton abundance and composition was conducted in distinct water types and across frontal boundaries identified from the high-resolution data. The distributions of bowhead whales were documented using aerial surveys. Inter-annual and shorter-term (days to weeks) variability in the distribution of water masses and intrinsic biological properties was observed. Distinct hydrographic and biological-chemical regions were located across the shelf that may contribute to the formation of bowhead whale prey aggregations. The lagoon system is an important interface between the ocean and land and may be critical to the formation of nearshore bowhead whale prey aggregations. Results from the field sampling will be coupled to biological-physical modeling and retrospective analyses to understand the response of this complex environment-whale-human system to climate variability.

Manoyl oxide (13R), the biosynthetic precursor of forskolin, is synthesized in specialized root cork cells in Coleus forskohlii.

PubMed

Pateraki, Irini; Andersen-Ranberg, Johan; Hamberger, Britta; Heskes, Allison Maree; Martens, Helle Juel; Zerbe, Philipp; Bach, Søren Spanner; Møller, Birger Lindberg; Bohlmann, Jörg; Hamberger, Björn

2014-03-01

Forskolin, a complex labdane diterpenoid found in the root of Coleus forskohlii (Lamiaceae), has received attention for its broad range of pharmacological activities, yet the biosynthesis has not been elucidated. We detected forskolin in the root cork of C. forskohlii in a specialized cell type containing characteristic structures with histochemical properties consistent with oil bodies. Organelle purification and chemical analysis confirmed the localization of forskolin and of its simplest diterpene precursor backbone, (13R) manoyl oxide, to the oil bodies. The labdane diterpene backbone is typically synthesized by two successive reactions catalyzed by two distinct classes of diterpene synthases. We have recently described the identification of a small gene family of diterpene synthase candidates (CfTPSs) in C. forskohlii. Here, we report the functional characterization of four CfTPSs using in vitro and in planta assays. CfTPS2, which synthesizes the intermediate copal-8-ol diphosphate, in combination with CfTPS3 resulted in the stereospecific formation of (13R) manoyl oxide, while the combination of CfTPS1 and CfTPS3 or CfTPS4 led to formation of miltiradiene, precursor of abietane diterpenoids in C. forskohlii. Expression profiling and phylogenetic analysis of the CfTPS family further support the functional diversification and distinct roles of the individual diterpene synthases and the involvement of CfTPS1 to CfTPS4 in specialized metabolism and of CfTPS14 and CfTPS15 in general metabolism. Our findings pave the way toward the discovery of the remaining components of the pathway to forskolin, likely localized in this specialized cell type, and support a role of oil bodies as storage organelles for lipophilic bioactive metabolites.

Manoyl Oxide (13R), the Biosynthetic Precursor of Forskolin, Is Synthesized in Specialized Root Cork Cells in Coleus forskohlii1[W][OPEN

PubMed Central

Pateraki, Irini; Andersen-Ranberg, Johan; Hamberger, Britta; Heskes, Allison Maree; Martens, Helle Juel; Zerbe, Philipp; Bach, Søren Spanner; Møller, Birger Lindberg; Bohlmann, Jörg; Hamberger, Björn

2014-01-01

Forskolin, a complex labdane diterpenoid found in the root of Coleus forskohlii (Lamiaceae), has received attention for its broad range of pharmacological activities, yet the biosynthesis has not been elucidated. We detected forskolin in the root cork of C. forskohlii in a specialized cell type containing characteristic structures with histochemical properties consistent with oil bodies. Organelle purification and chemical analysis confirmed the localization of forskolin and of its simplest diterpene precursor backbone, (13R) manoyl oxide, to the oil bodies. The labdane diterpene backbone is typically synthesized by two successive reactions catalyzed by two distinct classes of diterpene synthases. We have recently described the identification of a small gene family of diterpene synthase candidates (CfTPSs) in C. forskohlii. Here, we report the functional characterization of four CfTPSs using in vitro and in planta assays. CfTPS2, which synthesizes the intermediate copal-8-ol diphosphate, in combination with CfTPS3 resulted in the stereospecific formation of (13R) manoyl oxide, while the combination of CfTPS1 and CfTPS3 or CfTPS4 led to formation of miltiradiene, precursor of abietane diterpenoids in C. forskohlii. Expression profiling and phylogenetic analysis of the CfTPS family further support the functional diversification and distinct roles of the individual diterpene synthases and the involvement of CfTPS1 to CfTPS4 in specialized metabolism and of CfTPS14 and CfTPS15 in general metabolism. Our findings pave the way toward the discovery of the remaining components of the pathway to forskolin, likely localized in this specialized cell type, and support a role of oil bodies as storage organelles for lipophilic bioactive metabolites. PMID:24481136

Multimodal fluorescence microscopy of prion strain specific PrP deposits stained by thiophene-based amyloid ligands.

PubMed

Magnusson, Karin; Simon, Rozalyn; Sjölander, Daniel; Sigurdson, Christina J; Hammarström, Per; Nilsson, K Peter R

2014-01-01

The disease-associated prion protein (PrP) forms aggregates which vary in structural conformation yet share an identical primary sequence. These variations in PrP conformation are believed to manifest in prion strains exhibiting distinctly different periods of disease incubation as well as regionally specific aggregate deposition within the brain. The anionic luminescent conjugated polythiophene (LCP), polythiophene acetic acid (PTAA) has previously been used to distinguish PrP deposits associated with distinct mouse adapted strains via distinct fluorescence emission profiles from the dye. Here, we employed PTAA and 3 structurally related chemically defined luminescent conjugated oligothiophenes (LCOs) to stain brain tissue sections from mice inoculated with 2 distinct prion strains. Our results showed that in addition to emission spectra, excitation, and fluorescence lifetime imaging microscopy (FLIM) can fruitfully be assessed for optical distinction of PrP deposits associated with distinct prion strains. Our findings support the theory that alterations in LCP/LCO fluorescence are due to distinct conformational restriction of the thiophene backbone upon interaction with PrP aggregates associated with distinct prion strains. We foresee that LCP and LCO staining in combination with multimodal fluorescence microscopy might aid in detecting structural differences among discrete protein aggregates and in linking protein conformational features with disease phenotypes for a variety of neurodegenerative proteinopathies.

Multimodal fluorescence microscopy of prion strain specific PrP deposits stained by thiophene-based amyloid ligands

PubMed Central

Magnusson, Karin; Simon, Rozalyn; Sjölander, Daniel; Sigurdson, Christina J; Hammarström, Per; Nilsson, K Peter R

2014-01-01

The disease-associated prion protein (PrP) forms aggregates which vary in structural conformation yet share an identical primary sequence. These variations in PrP conformation are believed to manifest in prion strains exhibiting distinctly different periods of disease incubation as well as regionally specific aggregate deposition within the brain. The anionic luminescent conjugated polythiophene (LCP), polythiophene acetic acid (PTAA) has previously been used to distinguish PrP deposits associated with distinct mouse adapted strains via distinct fluorescence emission profiles from the dye. Here, we employed PTAA and 3 structurally related chemically defined luminescent conjugated oligothiophenes (LCOs) to stain brain tissue sections from mice inoculated with 2 distinct prion strains. Our results showed that in addition to emission spectra, excitation, and fluorescence lifetime imaging microscopy (FLIM) can fruitfully be assessed for optical distinction of PrP deposits associated with distinct prion strains. Our findings support the theory that alterations in LCP/LCO fluorescence are due to distinct conformational restriction of the thiophene backbone upon interaction with PrP aggregates associated with distinct prion strains. We foresee that LCP and LCO staining in combination with multimodal fluorescence microscopy might aid in detecting structural differences among discrete protein aggregates and in linking protein conformational features with disease phenotypes for a variety of neurodegenerative proteinopathies. PMID:25495506

The origin and dynamic evolution of chemical information transfer

PubMed Central

Steiger, Sandra; Schmitt, Thomas; Schaefer, H. Martin

2011-01-01

Although chemical communication is the most widespread form of communication, its evolution and diversity are not well understood. By integrating studies of a wide range of terrestrial plants and animals, we show that many chemicals are emitted, which can unintentionally provide information (cues) and, therefore, act as direct precursors for the evolution of intentional communication (signals). Depending on the content, design and the original function of the cue, there are predictable ways that selection can enhance the communicative function of chemicals. We review recent progress on how efficacy-based selection by receivers leads to distinct evolutionary trajectories of chemical communication. Because the original function of a cue may channel but also constrain the evolution of functional communication, we show that a broad perspective on multiple selective pressures acting upon chemicals provides important insights into the origin and dynamic evolution of chemical information transfer. Finally, we argue that integrating chemical ecology into communication theory may significantly enhance our understanding of the evolution, the design and the content of signals in general. PMID:21177681

In Silico Screening-Level Prioritization of 8468 Chemicals Produced in OECD Countries to Identify Potential Planetary Boundary Threats.

PubMed

Reppas-Chrysovitsinos, Efstathios; Sobek, Anna; MacLeod, Matthew

2018-01-01

Legislation such as the Stockholm Convention and REACH aim to identify and regulate the production and use of chemicals that qualify as persistent organic pollutants (POPs) and very persistent and very bioaccumulative (vPvB) chemicals, respectively. Recently, a series of studies on planetary boundary threats proposed seven chemical hazard profiles that are distinct from the POP and vPvB profiles. We previously defined two exposure-based hazard profiles; airborne persistent contaminants (APCs) and waterborne persistent contaminants (WPCs) that correspond to two profiles of chemicals that are planetary boundary threats. Here, we extend our method to screen a database of chemicals consisting of 8648 substances produced within the OECD countries. We propose a new scoring scheme to disentangle the POP, vPvB, APC and WPC profiles by focusing on the spatial range of exposure potential, discuss the relationship between high exposure hazard and elemental composition of chemicals, and identify chemicals with high exposure hazard potential.

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

Techtmann, Stephen M.; Fortney, Julian L.; Ayers, Kati A.

The waters of the Eastern Mediterranean are characterized by unique physical and chemical properties within separate water masses occupying different depths. Distinct water masses are present throughout the oceans, which drive thermohaline circulation. These water masses may contain specific microbial assemblages. The goal of this study was to examine the effect of physical and geological phenomena on the microbial community of the Eastern Mediterranean water column. Chemical measurements were combined with phospholipid fatty acid (PLFA) analysis and high-throughput 16S rRNA sequencing to characterize the microbial community in the water column at five sites. We demonstrate that the chemistry and microbialmore » community of the water column were stratified into three distinct water masses. The salinity and nutrient concentrations vary between these water masses. Nutrient concentrations increased with depth, and salinity was highest in the intermediate water mass. Our PLFA analysis indicated different lipid classes were abundant in each water mass, suggesting that distinct groups of microbes inhabit these water masses. 16S rRNA gene sequencing confirmed the presence of distinct microbial communities in each water mass. Taxa involved in autotrophic nitrogen cycling were enriched in the intermediate water mass suggesting that microbes in this water mass may be important to the nitrogen cycle of the Eastern Mediterranean. The Eastern Mediterranean also contains numerous active hydrocarbon seeps. We sampled above the North Alex Mud Volcano, in order to test the effect of these geological features on the microbial community in the adjacent water column. The community in the waters overlaying the mud volcano was distinct from other communities collected at similar depths and was enriched in known hydrocarbon degrading taxa. Furthermore, our results demonstrate that physical phenomena such stratification as well as geological phenomena such as mud volcanoes strongly affect microbial community structure in the Eastern Mediterranean water column.« less

USSR Report, Chemistry

DTIC Science & Technology

1985-08-19

No 2, Mar-Apr 85) 15 Factors Which Determine Activity of Catalysts of Various Chemical Types in Hydrogen Oxidation Reactions . Part 1: Oxidation ...Factors Which Determine Activity of Catalysts of Various Chemical Types in Hydrogen Oxidation Reactions . Part 2: Oxidation and Isotope Exchange of...FACTORS WHICH DETERMINE ACTIVITY OF CATALYSTS OF VARIOUS CHEMICAL TYPES IN HYDROGEN OXIDATION REACTIONS . PART 1: OXIDATION AND ISOTOPE EXCHANGE OF

Halogen bonds in some dihalogenated phenols: applications to crystal engineering.

PubMed

Mukherjee, Arijit; Desiraju, Gautam R

2014-01-01

3,4-Dichlorophenol (1) crystallizes in the tetragonal space group I41/a with a short axis of 3.7926 (9) Å. The structure is unique in that both type I and type II Cl⋯Cl interactions are present, these contact types being distinguished by the angle ranges of the respective C-Cl⋯Cl angles. The present study shows that these two types of contacts are utterly different. The crystal structures of 4-bromo-3-chlorophenol (2) and 3-bromo-4-chlorophenol (3) have been determined. The crystal structure of (2) is isomorphous to that of (1) with the Br atom in the 4-position participating in a type II interaction. However, the monoclinic P21/c packing of compound (3) is different; while the structure still has O-H⋯O hydrogen bonds, the tetramer O-H⋯O synthon seen in (1) and (2) is not seen. Rather than a type I Br⋯Br interaction which would have been mandated if (3) were isomorphous to (1) and (2), Br forms a Br⋯O contact wherein its electrophilic character is clearly evident. Crystal structures of the related compounds 4-chloro-3-iodophenol (4) and 3,5-dibromophenol (5) were also determined. A computational survey of the structural landscape was undertaken for (1), (2) and (3), using a crystal structure prediction protocol in space groups P21/c and I41/a with the COMPASS26 force field. While both tetragonal and monoclinic structures are energetically reasonable for all compounds, the fact that (3) takes the latter structure indicates that Br prefers type II over type I contacts. In order to differentiate further between type I and type II halogen contacts, which being chemically distinct are expected to have different distance fall-off properties, a variable-temperature crystallography study was performed on compounds (1), (2) and (4). Length variations with temperature are greater for type II contacts compared with type I. The type II Br⋯Br interaction in (2) is stronger than the corresponding type II Cl⋯Cl interaction in (1), leading to elastic bending of the former upon application of mechanical stress, which contrasts with the plastic deformation of (1). The observation of elastic deformation in (2) is noteworthy; in that it finds an explanation based on the strengths of the respective halogen bonds, it could also be taken as a good starting model for future property design. Cl/Br isostructurality is studied with the Cambridge Structural Database and it is indicated that this isostructurality is based on shape and size similarity of Cl and Br, rather than arising from any chemical resemblance.

The unique chemistry of Eastern Mediterranean water masses selects for distinct microbial communities by depth.

PubMed

Techtmann, Stephen M; Fortney, Julian L; Ayers, Kati A; Joyner, Dominique C; Linley, Thomas D; Pfiffner, Susan M; Hazen, Terry C

2015-01-01

The waters of the Eastern Mediterranean are characterized by unique physical and chemical properties within separate water masses occupying different depths. Distinct water masses are present throughout the oceans, which drive thermohaline circulation. These water masses may contain specific microbial assemblages. The goal of this study was to examine the effect of physical and geological phenomena on the microbial community of the Eastern Mediterranean water column. Chemical measurements were combined with phospholipid fatty acid (PLFA) analysis and high-throughput 16S rRNA sequencing to characterize the microbial community in the water column at five sites. We demonstrate that the chemistry and microbial community of the water column were stratified into three distinct water masses. The salinity and nutrient concentrations vary between these water masses. Nutrient concentrations increased with depth, and salinity was highest in the intermediate water mass. Our PLFA analysis indicated different lipid classes were abundant in each water mass, suggesting that distinct groups of microbes inhabit these water masses. 16S rRNA gene sequencing confirmed the presence of distinct microbial communities in each water mass. Taxa involved in autotrophic nitrogen cycling were enriched in the intermediate water mass suggesting that microbes in this water mass may be important to the nitrogen cycle of the Eastern Mediterranean. The Eastern Mediterranean also contains numerous active hydrocarbon seeps. We sampled above the North Alex Mud Volcano, in order to test the effect of these geological features on the microbial community in the adjacent water column. The community in the waters overlaying the mud volcano was distinct from other communities collected at similar depths and was enriched in known hydrocarbon degrading taxa. Our results demonstrate that physical phenomena such stratification as well as geological phenomena such as mud volcanoes strongly affect microbial community structure in the Eastern Mediterranean water column.

The Unique Chemistry of Eastern Mediterranean Water Masses Selects for Distinct Microbial Communities by Depth

PubMed Central

Techtmann, Stephen M.; Fortney, Julian L.; Ayers, Kati A.; Joyner, Dominique C.; Linley, Thomas D.; Pfiffner, Susan M.; Hazen, Terry C.

2015-01-01

The waters of the Eastern Mediterranean are characterized by unique physical and chemical properties within separate water masses occupying different depths. Distinct water masses are present throughout the oceans, which drive thermohaline circulation. These water masses may contain specific microbial assemblages. The goal of this study was to examine the effect of physical and geological phenomena on the microbial community of the Eastern Mediterranean water column. Chemical measurements were combined with phospholipid fatty acid (PLFA) analysis and high-throughput 16S rRNA sequencing to characterize the microbial community in the water column at five sites. We demonstrate that the chemistry and microbial community of the water column were stratified into three distinct water masses. The salinity and nutrient concentrations vary between these water masses. Nutrient concentrations increased with depth, and salinity was highest in the intermediate water mass. Our PLFA analysis indicated different lipid classes were abundant in each water mass, suggesting that distinct groups of microbes inhabit these water masses. 16S rRNA gene sequencing confirmed the presence of distinct microbial communities in each water mass. Taxa involved in autotrophic nitrogen cycling were enriched in the intermediate water mass suggesting that microbes in this water mass may be important to the nitrogen cycle of the Eastern Mediterranean. The Eastern Mediterranean also contains numerous active hydrocarbon seeps. We sampled above the North Alex Mud Volcano, in order to test the effect of these geological features on the microbial community in the adjacent water column. The community in the waters overlaying the mud volcano was distinct from other communities collected at similar depths and was enriched in known hydrocarbon degrading taxa. Our results demonstrate that physical phenomena such stratification as well as geological phenomena such as mud volcanoes strongly affect microbial community structure in the Eastern Mediterranean water column. PMID:25807542

The unique chemistry of Eastern Mediterranean water masses selects for distinct microbial communities by depth

DOE PAGES

Techtmann, Stephen M.; Fortney, Julian L.; Ayers, Kati A.; ...

2015-03-25

The waters of the Eastern Mediterranean are characterized by unique physical and chemical properties within separate water masses occupying different depths. Distinct water masses are present throughout the oceans, which drive thermohaline circulation. These water masses may contain specific microbial assemblages. The goal of this study was to examine the effect of physical and geological phenomena on the microbial community of the Eastern Mediterranean water column. Chemical measurements were combined with phospholipid fatty acid (PLFA) analysis and high-throughput 16S rRNA sequencing to characterize the microbial community in the water column at five sites. We demonstrate that the chemistry and microbialmore » community of the water column were stratified into three distinct water masses. The salinity and nutrient concentrations vary between these water masses. Nutrient concentrations increased with depth, and salinity was highest in the intermediate water mass. Our PLFA analysis indicated different lipid classes were abundant in each water mass, suggesting that distinct groups of microbes inhabit these water masses. 16S rRNA gene sequencing confirmed the presence of distinct microbial communities in each water mass. Taxa involved in autotrophic nitrogen cycling were enriched in the intermediate water mass suggesting that microbes in this water mass may be important to the nitrogen cycle of the Eastern Mediterranean. The Eastern Mediterranean also contains numerous active hydrocarbon seeps. We sampled above the North Alex Mud Volcano, in order to test the effect of these geological features on the microbial community in the adjacent water column. The community in the waters overlaying the mud volcano was distinct from other communities collected at similar depths and was enriched in known hydrocarbon degrading taxa. Furthermore, our results demonstrate that physical phenomena such stratification as well as geological phenomena such as mud volcanoes strongly affect microbial community structure in the Eastern Mediterranean water column.« less

PHARMACEUTICALS AND PERSONAL CARE PRODUCTS (PPCPS) AS ENVIRONMENTAL POLLUTANTS

EPA Science Inventory

The occurrence of pharmaceuticals and personal care products (PPCPs) as trace environmental pollutants is a multifaceted issue whose scope of concerns continues to expand. PPCPs comprise thousands of distinct chemicals from numerous therapeutic and consumer classes. They typical...

Reliable discrimination of high explosive and chemical/biological artillery using acoustic UGS

NASA Astrophysics Data System (ADS)

Hohil, Myron E.; Desai, Sachi

2005-10-01

The Army is currently developing acoustic overwatch sensor systems that will provide extended range surveillance, detection, and identification for force protection and tactical security on the battlefield. A network of such sensors remotely deployed in conjunction with a central processing node (or gateway) will provide early warning and assessment of enemy threats, near real-time situational awareness to commanders, and may reduce potential hazards to the soldier. In contrast, the current detection of chemical/biological (CB) agents expelled into a battlefield environment is limited to the response of chemical sensors that must be located within close proximity to the CB agent. Since chemical sensors detect hazardous agents through contact, the sensor range to an airburst is the key-limiting factor in identifying a potential CB weapon attack. The associated sensor reporting latencies must be minimized to give sufficient preparation time to field commanders, who must assess if an attack is about to occur, has occurred, or if occurred, the type of agent that soldiers might be exposed to. The long-range propagation of acoustic blast waves from heavy artillery blasts, which are typical in a battlefield environment, introduces a feature for using acoustics and other disparate sensor technologies for the early detection and identification of CB threats. Employing disparate sensor technologies implies that warning of a potential CB attack can be provided to the solider more rapidly and from a safer distance when compared to that which conventional methods allow. This capability facilitates the necessity of classifying the types of rounds that have burst in a specified region in order to give both warning and provide identification of CB agents found in the area. In this paper, feature extraction methods based on the discrete wavelet transform (DWT) and multiresolution analysis facilitate the development of a robust classification algorithm that affords reliable discrimination between conventional and simulated chemical/biological artillery rounds using acoustic signals produced during detonation. Distinct characteristics arise within the different airburst signatures because high explosive warheads emphasize concussive and shrapnel effects, while chemical/biological warheads are designed to disperse their contents over large areas, therefore employing a slower burning, less intense explosive to mix and spread their contents. The ensuing blast waves are readily characterized by variations in the corresponding peak pressure and rise time of the blast, differences in the ratio of positive pressure amplitude to the negative amplitude, and variations in the overall duration of the resulting waveform. We show that, highly reliable discrimination (> 98%) between conventional and potentially chemical/biological artillery is achieved at ranges exceeding 3km. A feedforward neural network classifier, trained on a feature space derived from the distribution of wavelet coefficients found within different levels of the multiresolution decomposition yields.

Clustering the Orion B giant molecular cloud based on its molecular emission.

PubMed

Bron, Emeric; Daudon, Chloé; Pety, Jérôme; Levrier, François; Gerin, Maryvonne; Gratier, Pierre; Orkisz, Jan H; Guzman, Viviana; Bardeau, Sébastien; Goicoechea, Javier R; Liszt, Harvey; Öberg, Karin; Peretto, Nicolas; Sievers, Albrecht; Tremblin, Pascal

2018-02-01

Previous attempts at segmenting molecular line maps of molecular clouds have focused on using position-position-velocity data cubes of a single molecular line to separate the spatial components of the cloud. In contrast, wide field spectral imaging over a large spectral bandwidth in the (sub)mm domain now allows one to combine multiple molecular tracers to understand the different physical and chemical phases that constitute giant molecular clouds (GMCs). We aim at using multiple tracers (sensitive to different physical processes and conditions) to segment a molecular cloud into physically/chemically similar regions (rather than spatially connected components), thus disentangling the different physical/chemical phases present in the cloud. We use a machine learning clustering method, namely the Meanshift algorithm, to cluster pixels with similar molecular emission, ignoring spatial information. Clusters are defined around each maximum of the multidimensional Probability Density Function (PDF) of the line integrated intensities. Simple radiative transfer models were used to interpret the astrophysical information uncovered by the clustering analysis. A clustering analysis based only on the J = 1 - 0 lines of three isotopologues of CO proves suffcient to reveal distinct density/column density regimes ( n H ~ 100 cm -3 , ~ 500 cm -3 , and > 1000 cm -3 ), closely related to the usual definitions of diffuse, translucent and high-column-density regions. Adding two UV-sensitive tracers, the J = 1 - 0 line of HCO + and the N = 1 - 0 line of CN, allows us to distinguish two clearly distinct chemical regimes, characteristic of UV-illuminated and UV-shielded gas. The UV-illuminated regime shows overbright HCO + and CN emission, which we relate to a photochemical enrichment effect. We also find a tail of high CN/HCO + intensity ratio in UV-illuminated regions. Finer distinctions in density classes ( n H ~ 7 × 10 3 cm -3 ~ 4 × 10 4 cm -3 ) for the densest regions are also identified, likely related to the higher critical density of the CN and HCO + (1 - 0) lines. These distinctions are only possible because the high-density regions are spatially resolved. Molecules are versatile tracers of GMCs because their line intensities bear the signature of the physics and chemistry at play in the gas. The association of simultaneous multi-line, wide-field mapping and powerful machine learning methods such as the Meanshift clustering algorithm reveals how to decode the complex information available in these molecular tracers.

Aerosol source apportionment based on multi-wavelength photoacoustic light absorption measurements: a simulation method for system's optimisation

NASA Astrophysics Data System (ADS)

Simon, Károly; Ajtai, Tibor; Kiss-Albert, Gergely; Utry, Noémi; Pintér, Máté; Szabó, Gábor; Bozóki, Zoltán

2017-04-01

Aerosol source apportionment is currently one of the outstanding challenges for environmental monitoring. In most cases atmospheric aerosol is a heterogeneous mixture as it typically originates from various sources. Consequently, each aerosol type has distinct chemical and physical properties. Contrary to chemical properties, optical absorption and size distribution of airborne particles can be measured in real time with high time resolution i.e. their measurement facilitates real time source apportionment (Favez et al (2009), Ajtai et al (2011), Favez et al (2010)). The wavelength dependency of the optical absorption coefficient (OAC) is usually characterised by the Absorption Angström Exponent (AAE). So far, the selection of light sources (lasers) into a photoacoustic aerosol measuring system was based on rule of thumb type estimations only. Recently, we proposed a simulation method that can be used to estimate the accuracy of aerosol source apportionment in case of a dual wavelength photoacoustic system (Simon et al., (2017)). This simulation is based on the assumption that the atmospheric aerosol load is dominated by two distinct sources and each of them is strongly light absorbing with specific AAE values. This is a typical scenario e.g. for urban measurements under wintry conditions when dominating aerosol sources are fossil fuel and wood burning with characteristic AAE 1 and 2, respectively. The wavelength pair of 405 and 1064 nm was found to be optimal for source apportionment in this case. In the presented study we investigated the situation when there are aerosol components with only slightly different AAE values and searched for a photoacoustic system which is optimal for distinguishing these components. Ajtai, T.; Filep, Á.; Utry, N.; Schnaiter, M.; Linke, C.; Bozóki, Z.; Szabó, G. and Leisner T. (2011) Journal of Aerosol Science 42, 859-866. Favez, O.; Cachier, H.; Sciare, J.; Sarda-Estève, R. and Martinon, L. (2009) Atmospheric Environment 43, 3640-3644. Favez, O.; El Haddad, I.; Piot, C.; Boréave, A.; Abidi, E.; Marchand, N.; Jaffrezo, J. L.; Besombes, J. L.; Personnaz, M. B.; Sciare, J.; Wortham, H.; George, C. and D'Anna, B. (2010), Atmos. Chem. Phys. 10, 5295-5314. Simon, K.A.; Ajtai, T; Gulyas, G; Utry, N; Pinter, M; Szabo, G. and Bozoki, Bozoki, Z. (2017), Journal of Aerosol Science 104, 10-15.

DNA-Encoded Chemical Libraries: A Selection System Based on Endowing Organic Compounds with Amplifiable Information.

PubMed

Neri, Dario; Lerner, Richard A

2018-06-20

The discovery of organic ligands that bind specifically to proteins is a central problem in chemistry, biology, and the biomedical sciences. The encoding of individual organic molecules with distinctive DNA tags, serving as amplifiable identification bar codes, allows the construction and screening of combinatorial libraries of unprecedented size, thus facilitating the discovery of ligands to many different protein targets. Fundamentally, one links powers of genetics and chemical synthesis. After the initial description of DNA-encoded chemical libraries in 1992, several experimental embodiments of the technology have been reduced to practice. This review provides a historical account of important milestones in the development of DNA-encoded chemical libraries, a survey of relevant ongoing research activities, and a glimpse into the future.

Discovery of new antimalarial chemotypes through chemical methodology and library development.

PubMed

Brown, Lauren E; Chih-Chien Cheng, Ken; Wei, Wan-Guo; Yuan, Pingwei; Dai, Peng; Trilles, Richard; Ni, Feng; Yuan, Jing; MacArthur, Ryan; Guha, Rajarshi; Johnson, Ronald L; Su, Xin-zhuan; Dominguez, Melissa M; Snyder, John K; Beeler, Aaron B; Schaus, Scott E; Inglese, James; Porco, John A

2011-04-26

In an effort to expand the stereochemical and structural complexity of chemical libraries used in drug discovery, the Center for Chemical Methodology and Library Development at Boston University has established an infrastructure to translate methodologies accessing diverse chemotypes into arrayed libraries for biological evaluation. In a collaborative effort, the NIH Chemical Genomics Center determined IC(50)'s for Plasmodium falciparum viability for each of 2,070 members of the CMLD-BU compound collection using quantitative high-throughput screening across five parasite lines of distinct geographic origin. Three compound classes displaying either differential or comprehensive antimalarial activity across the lines were identified, and the nascent structure activity relationships (SAR) from this experiment used to initiate optimization of these chemotypes for further development.

A statistical approach to root system classification.

PubMed

Bodner, Gernot; Leitner, Daniel; Nakhforoosh, Alireza; Sobotik, Monika; Moder, Karl; Kaul, Hans-Peter

2013-01-01

Plant root systems have a key role in ecology and agronomy. In spite of fast increase in root studies, still there is no classification that allows distinguishing among distinctive characteristics within the diversity of rooting strategies. Our hypothesis is that a multivariate approach for "plant functional type" identification in ecology can be applied to the classification of root systems. The classification method presented is based on a data-defined statistical procedure without a priori decision on the classifiers. The study demonstrates that principal component based rooting types provide efficient and meaningful multi-trait classifiers. The classification method is exemplified with simulated root architectures and morphological field data. Simulated root architectures showed that morphological attributes with spatial distribution parameters capture most distinctive features within root system diversity. While developmental type (tap vs. shoot-borne systems) is a strong, but coarse classifier, topological traits provide the most detailed differentiation among distinctive groups. Adequacy of commonly available morphologic traits for classification is supported by field data. Rooting types emerging from measured data, mainly distinguished by diameter/weight and density dominated types. Similarity of root systems within distinctive groups was the joint result of phylogenetic relation and environmental as well as human selection pressure. We concluded that the data-define classification is appropriate for integration of knowledge obtained with different root measurement methods and at various scales. Currently root morphology is the most promising basis for classification due to widely used common measurement protocols. To capture details of root diversity efforts in architectural measurement techniques are essential.

The first Fe-based Na+-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19

DOE PAGES

Kan, W. H.; Huq, A.; Manthiram, A.

2015-05-15

We report the synthesis, structure, and electrochemistry of the first Na +-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19. The Fe-based cathode has a reversible capacity of ca. 70 mAh g -1; ca. 1.7 Na + ions per formula can be inserted/extracted at an average voltage of 2.5 V versus Na +/Na.

Phylogeographic Evidence for 2 Genetically Distinct Zoonotic Plasmodium knowlesi Parasites, Malaysia.

PubMed

Yusof, Ruhani; Ahmed, Md Atique; Jelip, Jenarun; Ngian, Hie Ung; Mustakim, Sahlawati; Hussin, Hani Mat; Fong, Mun Yik; Mahmud, Rohela; Sitam, Frankie Anak Thomas; Japning, J Rovie-Ryan; Snounou, Georges; Escalante, Ananias A; Lau, Yee Ling

2016-08-01

Infections of humans with the zoonotic simian malaria parasite Plasmodium knowlesi occur throughout Southeast Asia, although most cases have occurred in Malaysia, where P. knowlesi is now the dominant malaria species. This apparently skewed distribution prompted an investigation of the phylogeography of this parasite in 2 geographically separated regions of Malaysia, Peninsular Malaysia and Malaysian Borneo. We investigated samples collected from humans and macaques in these regions. Haplotype network analyses of sequences from 2 P. knowlesi genes, type A small subunit ribosomal 18S RNA and cytochrome c oxidase subunit I, showed 2 genetically distinct divergent clusters, 1 from each of the 2 regions of Malaysia. We propose that these parasites represent 2 distinct P. knowlesi types that independently became zoonotic. These types would have evolved after the sea-level rise at the end of the last ice age, which separated Malaysian Borneo from Peninsular Malaysia.

Phylogeographic Evidence for 2 Genetically Distinct Zoonotic Plasmodium knowlesi Parasites, Malaysia

PubMed Central

Yusof, Ruhani; Ahmed, Md Atique; Jelip, Jenarun; Ngian, Hie Ung; Mustakim, Sahlawati; Hussin, Hani Mat; Fong, Mun Yik; Mahmud, Rohela; Sitam, Frankie Anak Thomas; Japning, J. Rovie-Ryan; Snounou, Georges; Escalante, Ananias A.

2016-01-01

Infections of humans with the zoonotic simian malaria parasite Plasmodium knowlesi occur throughout Southeast Asia, although most cases have occurred in Malaysia, where P. knowlesi is now the dominant malaria species. This apparently skewed distribution prompted an investigation of the phylogeography of this parasite in 2 geographically separated regions of Malaysia, Peninsular Malaysia and Malaysian Borneo. We investigated samples collected from humans and macaques in these regions. Haplotype network analyses of sequences from 2 P. knowlesi genes, type A small subunit ribosomal 18S RNA and cytochrome c oxidase subunit I, showed 2 genetically distinct divergent clusters, 1 from each of the 2 regions of Malaysia. We propose that these parasites represent 2 distinct P. knowlesi types that independently became zoonotic. These types would have evolved after the sea-level rise at the end of the last ice age, which separated Malaysian Borneo from Peninsular Malaysia. PMID:27433965

Distinct domains within the NITROGEN LIMITATION ADAPTATION protein mediate its subcellular localization and function in the nitrate-dependent phosphate homeostasis pathway

USDA-ARS?s Scientific Manuscript database

The NITROGEN LIMITATION ADAPTATION (NLA) protein is a RING-type E3 ubiquitin ligase that plays an essential role in the regulation of nitrogen and phosphate homeostasis. NLA is localized to two distinct subcellular sites, the plasma membrane and nucleus, and contains four distinct domains: i) a RING...

Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity.

PubMed

Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T; Finkel, Michael; Blowes, David W; Cirpka, Olaf A

2016-09-01

Transport of reactive solutes in groundwater is affected by physical and chemical heterogeneity of the porous medium, leading to complex spatio-temporal patterns of concentrations and reaction rates. For certain cases of bioreactive transport, it could be shown that the concentrations of reactive constituents in multi-dimensional domains are approximately aligned with isochrones, that is, lines of identical travel time, provided that the chemical properties of the matrix are uniform. We extend this concept to combined physical and chemical heterogeneity by additionally considering the time that a water parcel has been exposed to reactive materials, the so-called exposure time. We simulate bioreactive transport in a one-dimensional domain as function of time and exposure time, rather than space. Subsequently, we map the concentrations to multi-dimensional heterogeneous domains by means of the mean exposure time at each location in the multi-dimensional domain. Differences in travel and exposure time at a given location are accounted for as time difference. This approximation simplifies reactive-transport simulations significantly under conditions of steady-state flow when reactions are restricted to specific locations. It is not expected to be exact in realistic applications because the underlying assumption, such as neglecting transverse mixing altogether, may not hold. We quantify the error introduced by the approximation for the hypothetical case of a two-dimensional, binary aquifer made of highly-permeable, non-reactive and low-permeable, reactive materials releasing dissolved organic matter acting as electron donor for aerobic respiration and denitrification. The kinetically controlled reactions are catalyzed by two non-competitive bacteria populations, enabling microbial growth. Even though the initial biomass concentrations were uniform, the interplay between transport, non-uniform electron-donor supply, and bio-reactions led to distinct spatial patterns of the two types of biomass at late times. Results obtained by mapping the exposure-time based results to the two-dimensional domain are compared with simulations based on the two-dimensional, spatially explicit advection-dispersion-reaction equation. Once quasi-steady state has been reached, we find a good agreement in terms of the chemical-compound concentrations between the two approaches inside the reactive zones, whereas the exposure-time based model is not able to capture reactions occurring in the zones with zero electron-donor release. We conclude that exposure-time models provide good approximations of nonlinear bio-reactive transport when transverse mixing is not the overall controlling process and all reactions are essentially restricted to distinct reactive zones. Copyright © 2016 Elsevier B.V. All rights reserved.

Precondensed matter - Key to the early solar system

NASA Technical Reports Server (NTRS)

Clayton, D. D.

1978-01-01

Explicit astrophysical details are developed for the hypothesis that chemical and isotopic anomalies in primitive solar-system samples reflect routine initial chemical conditions within precondensed matter. The central feature of this theory concerns the chemical state of presolar dust, which is regarded as never having been vaporized in the region where the most chemically primitive samples (carbonaceous meteorites) accumulated. It is suggested that the initial chemical state of heavy atoms during meteorite and planetary accumulation was distributed between a refractory-mineral component from high-temperature condensation and a volatile component resulting from cold matter adhering to preexisting grains. Thermal conditions in the solar nebula are considered along with the existence of supernova condensates and other thermal condensates in the interstellar dust. Fractionation into volatile and refractory elements is idealized in terms of four distinct interstellar components, and the fractionated precondensed matter is described.

Highly sensitive and selective sugar detection by terahertz nano-antennas

NASA Astrophysics Data System (ADS)

Lee, Dong-Kyu; Kang, Ji-Hun; Lee, Jun-Seok; Kim, Hyo-Seok; Kim, Chulki; Hun Kim, Jae; Lee, Taikjin; Son, Joo-Hiuk; Park, Q.-Han; Seo, Minah

2015-10-01

Molecular recognition and discrimination of carbohydrates are important because carbohydrates perform essential roles in most living organisms for energy metabolism and cell-to-cell communication. Nevertheless, it is difficult to identify or distinguish various carbohydrate molecules owing to the lack of a significant distinction in the physical or chemical characteristics. Although there has been considerable effort to develop a sensing platform for individual carbohydrates selectively using chemical receptors or an ensemble array, their detection and discrimination limits have been as high in the millimolar concentration range. Here we show a highly sensitive and selective detection method for the discrimination of carbohydrate molecules using nano-slot-antenna array-based sensing chips which operate in the terahertz (THz) frequency range (0.5-2.5 THz). This THz metamaterial sensing tool recognizes various types of carbohydrate molecules over a wide range of molecular concentrations. Strongly localized and enhanced terahertz transmission by nano-antennas can effectively increase the molecular absorption cross sections, thereby enabling the detection of these molecules even at low concentrations. We verified the performance of nano-antenna sensing chip by both THz spectra and images of transmittance. Screening and identification of various carbohydrates can be applied to test even real market beverages with a high sensitivity and selectivity.

Aerosol Emissions from Great Lakes Harmful Algal Blooms

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

May, Nathaniel W.; Olson, Nicole E.; Panas, Mark

In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the chemical species present in lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, a laboratory LSA generator produced aerosols from freshwater samples collected from Lake Michigan and Lake Erie during HAB and non-bloom conditions. Particles were analyzed for size and chemical composition by single particle mass spectrometry, electron microscopy, and fluorescence microscopy, with three distinct types of LSA identified with varying levels of organic carbon and biological material associated with calcium salts. LSAmore » autofluorescence increases with blue-green algae concentration, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of LSA with biological mass spectral markers also increases with particle diameter (greater than 0.5 μm), showing that HABs have size-dependent impacts on aerosol composition. The highest number fraction of LSA enriched in organic carbon were observed in particles less than 0.5 μm in diameter. Understanding the transfer of organic and biogenic material from freshwater to the atmosphere via LSA particles is crucial for determining health and climate effects due to HABs.« less

Low-temperature water-rock interactions in bedrock aquifers of southern Rhode Island: Results of laboratory simulations

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

Veeger, A.I.; Moulton, K.L.

1993-03-01

The nature of low-temperature chemical reactions occurring in bedrock aquifers of southern Rhode Island was investigated in the laboratory using flow-through columns. Crushed samples of Narragansett Pier Granite (NPG), Scituate Granite Gneiss (SGG), Hope Valley Alaskite Gneiss (HVAG) and Ten Rod Granite Gneiss (TRGG) were placed in flow-through columns. Water was circulated through the columns at a 3 ml/min and maintained at 25 C and at equilibrium with atmospheric carbon dioxide. Samples were collected from the columns at increasing time intervals and were analyzed for pH, conductivity, major cations and anions, and silica. The leachate compositions show that distinctive chemicalmore » differences can be expected in ground water that flows through each of these different rock types. Chemical modeling of the leachate solutions shows that reactions involving plagioclase feldspar (albiteoligoclase), reactive accessory minerals such as sphene, and, to a lesser degree, potassium feldspar and biotite, dominate the solution chemistry, with amorphous oxides and aluminosilicates formed as products of the weathering reactions. Small concentrations of reactive minerals may profoundly affect the composition of the leachate. Batch experiments using mineral separates revealed that the calcium in the NPG leachate was almost entirely attributable to sphene which comprises less than 1% of the rock.« less

Removal of pesticides from white and red wines by microfiltration.

PubMed

Doulia, Danae S; Anagnos, Efstathios K; Liapis, Konstantinos S; Klimentzos, Demetrios A

2016-11-05

The aim of this work is the investigation of microfiltration in removing pesticides from a white and a red Greek wine. Six membranes with pore size 0.45μm were investigated. Two mixtures of 23 and 9 pesticides, and single pesticide solutions were added in the wine. The pesticides tested belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the filtered fortified wine. Distinct behavior was exhibited by each membrane. Cellulose acetate and cellulose nitrate showed higher mean pesticide removal for both wines, followed by polyethersulfone, regenerated cellulose, and polyamides. The filtration effectiveness was correlated to the membrane type and to the pesticide chemical structure and properties (octanol-water partition coefficient, water solubility) and compared for the wines tested. In most cases, the more hydrophobic pesticides (pyrethroids and aldrin) showed higher removal from red wine than white wine. Adsorption on membranes was increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecule. The removal of each pesticide from its single solution was generally higher than that from its mixtures, allowing the estimation of the antagonistic and synergistic effects of pesticides in the mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging.

PubMed

Li, Ming; Jia, Bin; Ding, Liying; Hong, Feng; Ouyang, Yongzhong; Chen, Rui; Zhou, Shumin; Chen, Huanwen; Fang, Xiang

2013-09-01

Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS), which was operated in either a gasless, solvent-free or methanol vapor-assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI-MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI-MS imaging differentiated a 10-min old from two 4 h old samples. Non-destructive forensic analysis of forged signatures either handwritten or computer-assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI-MS. The experimental results show that DAPCI-MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications. © 2013 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.

Highly sensitive and selective sugar detection by terahertz nano-antennas

PubMed Central

Lee, Dong-Kyu; Kang, Ji-Hun; Lee, Jun-Seok; Kim, Hyo-Seok; Kim, Chulki; Hun Kim, Jae; Lee, Taikjin; Son, Joo-Hiuk; Park, Q-Han; Seo, Minah

2015-01-01

Molecular recognition and discrimination of carbohydrates are important because carbohydrates perform essential roles in most living organisms for energy metabolism and cell-to-cell communication. Nevertheless, it is difficult to identify or distinguish various carbohydrate molecules owing to the lack of a significant distinction in the physical or chemical characteristics. Although there has been considerable effort to develop a sensing platform for individual carbohydrates selectively using chemical receptors or an ensemble array, their detection and discrimination limits have been as high in the millimolar concentration range. Here we show a highly sensitive and selective detection method for the discrimination of carbohydrate molecules using nano-slot-antenna array-based sensing chips which operate in the terahertz (THz) frequency range (0.5–2.5 THz). This THz metamaterial sensing tool recognizes various types of carbohydrate molecules over a wide range of molecular concentrations. Strongly localized and enhanced terahertz transmission by nano-antennas can effectively increase the molecular absorption cross sections, thereby enabling the detection of these molecules even at low concentrations. We verified the performance of nano-antenna sensing chip by both THz spectra and images of transmittance. Screening and identification of various carbohydrates can be applied to test even real market beverages with a high sensitivity and selectivity. PMID:26494203

Methylation of zebularine investigated using density functional theory calculations.

PubMed

Selvam, Lalitha; Chen, Fang Fang; Wang, Feng

2011-07-30

Deoxyribonucleic acid (DNA) methylation is an epigenetic phenomenon, which adds methyl groups into DNA. This study reveals methylation of a nucleoside antibiotic drug 1-(β-D-ribofuranosyl)-2-pyrimidinone (zebularine or zeb) with respect to its methylated analog, 1-(β-D-ribofuranosyl)-5-methyl-2-pyrimidinone (d5) using density functional theory calculations in valence electronic space. Very similar infrared spectra suggest that zeb and d5 do not differ by types of the chemical bonds, but distinctly different Raman spectra of the nucleoside pair reveal that the impact caused by methylation of zeb can be significant. Further valence orbital-based information details on valence electronic structural changes caused by methylation of zebularine. Frontier orbitals in momentum space and position space of the molecules respond differently to methylation. Based on the additional methyl electron density concentration in d5, orbitals affected by the methyl moiety are classified into primary and secondary contributors. Primary methyl contributions include MO8 (57a), MO18 (47a), and MO37 (28a) of d5, which concentrates on methyl and the base moieties, suggest certain connection to their Frontier orbitals. The primary and secondary methyl affected orbitals provide useful information on chemical bonding mechanism of the methylation in zebularine. Copyright © 2011 Wiley Periodicals, Inc.

Growth of ultrananocrystalline diamond film by DC Arcjet plasma enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Chen, G. C.; Li, B.; Yan, Z. Q.; Liu, J.; Lu, F. X.; Ye, H.

2012-06-01

Self-standing diamond films were grown by DC Arcjet plasma enhanced chemical vapor deposition (CVD). The feed gasses were Ar/H2/CH4, in which the flow ratio of CH4 to H2 (F/F) was varied from 5% to 20%. Two distinct morphologies were observed by scanning electron microscope (SEM), i.e. the "pineapple-like" morphology and the "cauliflower-like" morphology. It was found that the morphologies of the as-grown films are strongly dependent on the flow ratio of CH4 to H2 in the feed gasses. High resolution transmission electron microscope (HRTEM) survey results revealed that there were nanocrystalline grains within the "pineapple-like" films whilst there were ultrananocrystalline grains within "cauliflower-like" films. X-ray diffraction (XRD) results suggested that (110) crystalline plane was the dominant surface in the "cauliflower-like" films whilst (100) crystalline plane was the dominant surface in the "pineapple-like" films. Raman spectroscopy revealed that nanostructured carbon features could be observed in both types of films. Plasma diagnosis was carried out in order to understand the morphology dependent growth mechanism. It could be concluded that the film morphology was strongly influenced by the density of gas phases. The gradient of C2 radical was found to be different along the growth direction under the different growth conditions.

Chemistry of Apollo 11 low-K mare basalts

NASA Technical Reports Server (NTRS)

Rhodes, J. M.; Blanchard, D. P.

1980-01-01

A reexamination of the bulk major and trace element geochemistry of Apollo 11 low-K mare basalts is presented. New analyses are given for seven previously unanalyzed samples (10003, 10020, 10044, 10047, 10050, 10058, and 10062) and for two low-K basalts (10029 and 10092) and one high-K basalt (10071) for which comprehensive compositional data were previously lacking. The data show that three distinct magma types have been sampled, as proposed by Beaty and Albee (1978), and that these magma types are unrelated by near-surface crystal fractionation. Each magma type is characterized by distinctive magmaphile element ratios, which enable previously unclassified samples (10050 and 10062) to be assigned to an appropriate magma type.

Analysis of CD44-Hyaluronan Interactions in an Artificial Membrane System

PubMed Central

Wolny, Patricia M.; Banerji, Suneale; Gounou, Céline; Brisson, Alain R.; Day, Anthony J.; Jackson, David G.; Richter, Ralf P.

2010-01-01

CD44 is a major cell surface receptor for the large polydisperse glycosaminoglycan hyaluronan (HA). Binding of the long and flexible HA chains is thought to be stabilized by the multivalent nature of the sugar molecule. In addition, high and low molecular weight forms of HA provoke distinct proinflammatory and anti-inflammatory effects upon binding to CD44 and can deliver either proliferative or antiproliferative signals in appropriate cell types. Despite the importance of such interactions, however, neither the stoichiometry of multivalent HA binding at the cell surface nor the molecular basis for functional distinction between different HA size categories is understood. Here we report on the design of a supported lipid bilayer system that permits quantitative analysis of multivalent binding through presentation of CD44 in a stable, natively oriented manner and at controlled density. Using this system in combination with biophysical techniques, we show that the amount of HA binding to bilayers that are densely coated with CD44 increases as a function of HA size, with half-maximal saturation at ∼30 kDa. Moreover, reversible binding was confined to the smaller HA species (molecular weight of ≤10 kDa), whereas the interaction was essentially irreversible with larger polymers. The amount of bound HA decreased with decreasing receptor surface density, but the stability of binding was not affected. From a physico-chemical perspective, the binding properties of HA share many similarities with the typical behavior of a flexible polymer as it adsorbs onto a homogeneously attractive surface. These findings provide new insight into the multivalent nature of CD44-HA interactions and suggest a molecular basis for the distinct biological properties of different size fractions of hyaluronan. PMID:20663884

Identification and Characterization of Influenza Virus Entry Inhibitors through Dual Myxovirus High-Throughput Screening.

PubMed

Weisshaar, Marco; Cox, Robert; Morehouse, Zachary; Kumar Kyasa, Shiva; Yan, Dan; Oberacker, Phil; Mao, Shuli; Golden, Jennifer E; Lowen, Anice C; Natchus, Michael G; Plemper, Richard K

2016-08-15

Influenza A virus (IAV) infections cause major morbidity and mortality, generating an urgent need for novel antiviral therapeutics. We recently established a dual myxovirus high-throughput screening protocol that combines a fully replication-competent IAV-WSN strain and a respiratory syncytial virus reporter strain for the simultaneous identification of IAV-specific, paramyxovirus-specific, and broad-spectrum inhibitors. In the present study, this protocol was applied to a screening campaign to assess a diverse chemical library with over 142,000 entries. Focusing on IAV-specific hits, we obtained a hit rate of 0.03% after cytotoxicity testing and counterscreening. Three chemically distinct hit classes with nanomolar potency and favorable cytotoxicity profiles were selected. Time-of-addition, minigenome, and viral entry studies demonstrated that these classes block hemagglutinin (HA)-mediated membrane fusion. Antiviral activity extends to an isolate from the 2009 pandemic and, in one case, another group 1 subtype. Target identification through biolayer interferometry confirmed binding of all hit compounds to HA. Resistance profiling revealed two distinct escape mechanisms: primary resistance, associated with reduced compound binding, and secondary resistance, associated with unaltered binding. Secondary resistance was mediated, unusually, through two different pairs of cooperative mutations, each combining a mutation eliminating the membrane-proximal stalk N-glycan with a membrane-distal change in HA1 or HA2. Chemical synthesis of an analog library combined with in silico docking extracted a docking pose for the hit classes. Chemical interrogation spotlights IAV HA as a major druggable target for small-molecule inhibition. Our study identifies novel chemical scaffolds with high developmental potential, outlines diverse routes of IAV escape from entry inhibition, and establishes a path toward structure-aided lead development. This study is one of the first to apply a fully replication-competent third-generation IAV reporter strain to a large-scale high-throughput screen (HTS) drug discovery campaign, allowing multicycle infection and screening in physiologically relevant human respiratory cells. A large number of potential druggable targets was thus chemically interrogated, but mechanistic characterization, positive target identification, and resistance profiling demonstrated that three chemically promising and structurally distinct hit classes selected for further analysis all block HA-mediated membrane fusion. Viral escape from inhibition could be achieved through primary and secondary resistance mechanisms. In silico docking predicted compound binding to a microdomain located at the membrane-distal site of the prefusion HA stalk that was also previously suggested as a target site for chemically unrelated HA inhibitors. This study identifies an unexpected chemodominance of the HA stalk microdomain for small-molecule inhibitors in IAV inhibitor screening campaigns and highlights a novel mechanism of cooperative resistance to IAV entry blockers. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Identification and Characterization of Influenza Virus Entry Inhibitors through Dual Myxovirus High-Throughput Screening

PubMed Central

Weisshaar, Marco; Cox, Robert; Morehouse, Zachary; Kumar Kyasa, Shiva; Yan, Dan; Oberacker, Phil; Mao, Shuli; Lowen, Anice C.; Natchus, Michael G.

2016-01-01

ABSTRACT Influenza A virus (IAV) infections cause major morbidity and mortality, generating an urgent need for novel antiviral therapeutics. We recently established a dual myxovirus high-throughput screening protocol that combines a fully replication-competent IAV-WSN strain and a respiratory syncytial virus reporter strain for the simultaneous identification of IAV-specific, paramyxovirus-specific, and broad-spectrum inhibitors. In the present study, this protocol was applied to a screening campaign to assess a diverse chemical library with over 142,000 entries. Focusing on IAV-specific hits, we obtained a hit rate of 0.03% after cytotoxicity testing and counterscreening. Three chemically distinct hit classes with nanomolar potency and favorable cytotoxicity profiles were selected. Time-of-addition, minigenome, and viral entry studies demonstrated that these classes block hemagglutinin (HA)-mediated membrane fusion. Antiviral activity extends to an isolate from the 2009 pandemic and, in one case, another group 1 subtype. Target identification through biolayer interferometry confirmed binding of all hit compounds to HA. Resistance profiling revealed two distinct escape mechanisms: primary resistance, associated with reduced compound binding, and secondary resistance, associated with unaltered binding. Secondary resistance was mediated, unusually, through two different pairs of cooperative mutations, each combining a mutation eliminating the membrane-proximal stalk N-glycan with a membrane-distal change in HA1 or HA2. Chemical synthesis of an analog library combined with in silico docking extracted a docking pose for the hit classes. Chemical interrogation spotlights IAV HA as a major druggable target for small-molecule inhibition. Our study identifies novel chemical scaffolds with high developmental potential, outlines diverse routes of IAV escape from entry inhibition, and establishes a path toward structure-aided lead development. IMPORTANCE This study is one of the first to apply a fully replication-competent third-generation IAV reporter strain to a large-scale high-throughput screen (HTS) drug discovery campaign, allowing multicycle infection and screening in physiologically relevant human respiratory cells. A large number of potential druggable targets was thus chemically interrogated, but mechanistic characterization, positive target identification, and resistance profiling demonstrated that three chemically promising and structurally distinct hit classes selected for further analysis all block HA-mediated membrane fusion. Viral escape from inhibition could be achieved through primary and secondary resistance mechanisms. In silico docking predicted compound binding to a microdomain located at the membrane-distal site of the prefusion HA stalk that was also previously suggested as a target site for chemically unrelated HA inhibitors. This study identifies an unexpected chemodominance of the HA stalk microdomain for small-molecule inhibitors in IAV inhibitor screening campaigns and highlights a novel mechanism of cooperative resistance to IAV entry blockers. PMID:27252534

A simple theory of molecular organization in fullerene-containing liquid crystals

NASA Astrophysics Data System (ADS)

Peroukidis, S. D.; Vanakaras, A. G.; Photinos, D. J.

2005-10-01

Systematic efforts to synthesize fullerene-containing liquid crystals have produced a variety of successful model compounds. We present a simple molecular theory, based on the interconverting shape approach [Vanakaras and Photinos, J. Mater. Chem. 15, 2002 (2005)], that relates the self-organization observed in these systems to their molecular structure. The interactions are modeled by dividing each molecule into a number of submolecular blocks to which specific interactions are assigned. Three types of blocks are introduced, corresponding to fullerene units, mesogenic units, and nonmesogenic linkage units. The blocks are constrained to move on a cubic three-dimensional lattice and molecular flexibility is allowed by retaining a number of representative conformations within the block representation of the molecule. Calculations are presented for a variety of molecular architectures including twin mesogenic branch monoadducts of C60, twin dendromesogenic branch monoadducts, and conical (badminton shuttlecock) multiadducts of C60. The dependence of the phase diagrams on the interaction parameters is explored. In spite of its many simplifications and the minimal molecular modeling used (three types of chemically distinct submolecular blocks with only repulsive interactions), the theory accounts remarkably well for the phase behavior of these systems.

Alpine glacier-fed turbid lakes are discontinuous cold polymictic rather than dimictic

PubMed Central

Peter, Hannes; Sommaruga, Ruben

2017-01-01

Abstract Glacier retreat as a consequence of climate change influences freshwater ecosystems in manifold ways, yet the physical and chemical bases of these effects are poorly studied. Here, we characterize how water temperature differs between alpine lakes with and without direct glacier influence on seasonal and diurnal timescales. Using high temporal resolution monitoring of temperature in 4 lakes located in a catchment influenced by glacier retreat, we reported unexpectedly high surface temperatures, even in proglacial lakes located 2600 m a.s.l. Cold glacier meltwater and low nighttime air temperatures caused a distinct diurnal pattern of water temperature in the water column of glacier-influenced lakes. Precipitation onto glacier surfaces apparently leads to rapid cooling of the glacier-fed lakes and disrupts the thermal stratification with several mixing events during the summer. Taken together, these mechanisms contribute to the unique seasonal and diurnal dynamics of glacier-influenced lakes that contrast with the typical dimictic pattern of clear alpine lakes and represent an example of discontinuous cold polymictic lake type. This work contributes to the basic description of how climate and meteorology affect the physical properties of an increasingly common lake type. PMID:28690780

Spectroscopic studies of model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Koehler, Birgit G.; Middlebrook, Ann M.

1993-01-01

Fourier transform infrared (FTIR) spectroscopy has been used to study nitric-acid/ice films representative of type I polar stratospheric clouds (PSCs). These studies reveal that in addition to amorphous nitric acid/ice mixtures, there are three stable stoichiometric hydrates of nitric acid: nitric-acid monohydrate (NAM), dihydrate (NAD), and trihydrate (NAT). We also observe two distinct crystalline forms of the trihydrate, which we denote alpha- and beta-NAT. These two forms appear to differ in their concentration of crystalline defects, but not in their chemical composition. In addition to probing the composition of type I PSCs, we have also used FTIR spectroscopy to study the interaction of HCl with model PSC films. In this work we find that for HCl pressures in the range 10 exp -5 to 10 exp -7 Torr, HCl is taken up by ice at 155 K to form a thin layer of HCl.6H2O. At 193 K, the uptake of HCl by ice was consistent with less than or equal to monolayer coverage. Uptake of HCl by alpha and beta-NAT at 175 K was also consistent with less than or equal to monolayer coverage.

Observed, unknown distributions of clinical chemical quantities should be considered to be log-normal: a proposal.

PubMed

Haeckel, Rainer; Wosniok, Werner

2010-10-01

The distribution of many quantities in laboratory medicine are considered to be Gaussian if they are symmetric, although, theoretically, a Gaussian distribution is not plausible for quantities that can attain only non-negative values. If a distribution is skewed, further specification of the type is required, which may be difficult to provide. Skewed (non-Gaussian) distributions found in clinical chemistry usually show only moderately large positive skewness (e.g., log-normal- and χ(2) distribution). The degree of skewness depends on the magnitude of the empirical biological variation (CV(e)), as demonstrated using the log-normal distribution. A Gaussian distribution with a small CV(e) (e.g., for plasma sodium) is very similar to a log-normal distribution with the same CV(e). In contrast, a relatively large CV(e) (e.g., plasma aspartate aminotransferase) leads to distinct differences between a Gaussian and a log-normal distribution. If the type of an empirical distribution is unknown, it is proposed that a log-normal distribution be assumed in such cases. This avoids distributional assumptions that are not plausible and does not contradict the observation that distributions with small biological variation look very similar to a Gaussian distribution.

Insights into proton translocation in cbb3 oxidase from MD simulations.

PubMed

Carvalheda, Catarina A; Pisliakov, Andrei V

2017-05-01

Heme-copper oxidases are membrane protein complexes that catalyse the final step of the aerobic respiration, namely the reduction of oxygen to water. The energy released during catalysis is coupled to the active translocation of protons across the membrane, which contributes to the establishment of an electrochemical gradient that is used for ATP synthesis. The distinctive C-type (or cbb 3 ) cytochrome c oxidases, which are mostly present in proteobacteria, exhibit a number of unique structural and functional features, including high catalytic activity at low oxygen concentrations. At the moment, the functioning mechanism of C-type oxidases, in particular the proton transfer/pumping mechanism presumably via a single proton channel, is still poorly understood. In this work we used all-atom molecular dynamics simulations and continuum electrostatics calculations to obtain atomic-level insights into the hydration and dynamics of a cbb 3 oxidase. We provide the details of the water dynamics and proton transfer pathways for both the "chemical" and "pumped" protons, and show that formation of protonic connections is strongly affected by the protonation state of key residues, namely H243, E323 and H337. Copyright © 2017 Elsevier B.V. All rights reserved.

Differences between the bacterial community structures of first- and multi-year Arctic sea ice in the Lincoln Sea.

NASA Astrophysics Data System (ADS)

Hatam, I.; Beckers, J. F.; Haas, C.; Lanoil, B. D.

2014-12-01

The Arctic sea ice composition is shifting from predominantly thick perennial ice (multiyear ice -MYI) to thinner, seasonal ice (first year ice -FYI). The effects of the shift on the Arctic ecosystem and macro-organisms of the Arctic Ocean have been the focus of many studies and have also been extensively debated in the public domain. The effect of this shift on the microbial constituents of the Arctic sea ice has been grossly understudied, although it is a vast habitat for a microbial community that plays a key role in the biogeochemical cycles and energy flux of the Arctic Ocean. MYI and FYI differ in many chemical and physical attributes (e.g. bulk salinity, brine volume, thickness and age), therefore comparing and contrasting the structure and composition of microbial communities from both ice types will be crucial to our understanding of the challenges that the Arctic Ocean ecosystem faces as MYI cover continues to decline. Here, we contend that due to the differences in abiotic conditions, differences in bacterial community structure will be greater between samples from different ice types than within samples from the same ice type. We also argue that since FYI is younger, its community structure will be closer to that of the surface sea water (SW). To test this hypotheses, we extracted DNA and used high throughput sequencing to sequence V1-V3 regions of the bacterial 16s rRNA gene from 10 sea ice samples (5 for each ice type) and 4 surface sea water (SW) collected off the shore of Northern Ellesmere Island, NU, CAN, during the month of May from 2010-2012. Our results showed that observed richness was higher in FYI than MYI. FYI and MYI shared 26% and 36% of their observed richness respectively. While FYI shared 23% of its observed richness with SW, MYI only shared 17%. Both ice types showed similar levels of endemism (61% of the observed richness). This high level of endemism results in the grouping of microbial communities from MYI, FYI, and SW to three distinct groups when looking at membership (jclass dissimilarity index, tested by AMOVA). However, when looking at composition (θYC dissimilarity index) while communities from MYI and SW samples still clustered as two distinct groups, communities from FYI samples show no significant clustering (tested by AMOVA).

Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

NASA Astrophysics Data System (ADS)

Wurtz, Jean David; Lee, Chiu Fan

2018-02-01

Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

Mantle convection and plate tectonics: toward an integrated physical and chemical theory

PubMed

Tackley

2000-06-16

Plate tectonics and convection of the solid, rocky mantle are responsible for transporting heat out of Earth. However, the physics of plate tectonics is poorly understood; other planets do not exhibit it. Recent seismic evidence for convection and mixing throughout the mantle seems at odds with the chemical composition of erupted magmas requiring the presence of several chemically distinct reservoirs within the mantle. There has been rapid progress on these two problems, with the emergence of the first self-consistent models of plate tectonics and mantle convection, along with new geochemical models that may be consistent with seismic and dynamical constraints on mantle structure.

Type, Content, and Source of Social Support Perceived by Women during Pregnancy: Evidence from Matlab, Bangladesh

PubMed Central

Paul, Moni; Sibley, Lynn M.

2011-01-01

Specific and contextualized data on social support during distinct health events are needed to improve social support interventions. This study identified the type, content, and source of social support perceived by women during pregnancy. In-depth interviews with 25 women, aged 18-49 years, living in Matlab, Bangladesh, were conducted. The findings demonstrated that women perceived, the receipt of eight distinct types of support. The four most frequently-mentioned types included: practical help with routine activities, information/advice, emotional support and assurance, as well as the provision of resources and material goods. Sources varied by type of support and most frequently included-—mothers, mothers-in-law, sisters-in-law, and husbands. Examples depicting the content of each type of support revealed culturally-specific issues that can inform community-based social support interventions. PMID:21608426

Electrochemical Probing through a Redox Capacitor To Acquire Chemical Information on Biothiols

PubMed Central

2016-01-01

The acquisition of chemical information is a critical need for medical diagnostics, food/environmental monitoring, and national security. Here, we report an electrochemical information processing approach that integrates (i) complex electrical inputs/outputs, (ii) mediators to transduce the electrical I/O into redox signals that can actively probe the chemical environment, and (iii) a redox capacitor that manipulates signals for information extraction. We demonstrate the capabilities of this chemical information processing strategy using biothiols because of the emerging importance of these molecules in medicine and because their distinct chemical properties allow evaluation of hypothesis-driven information probing. We show that input sequences can be tailored to probe for chemical information both qualitatively (step inputs probe for thiol-specific signatures) and quantitatively. Specifically, we observed picomolar limits of detection and linear responses to concentrations over 5 orders of magnitude (1 pM–0.1 μM). This approach allows the capabilities of signal processing to be extended for rapid, robust, and on-site analysis of chemical information. PMID:27385047

Electrochemical Probing through a Redox Capacitor To Acquire Chemical Information on Biothiols.

PubMed

Liu, Zhengchun; Liu, Yi; Kim, Eunkyoung; Bentley, William E; Payne, Gregory F

2016-07-19

The acquisition of chemical information is a critical need for medical diagnostics, food/environmental monitoring, and national security. Here, we report an electrochemical information processing approach that integrates (i) complex electrical inputs/outputs, (ii) mediators to transduce the electrical I/O into redox signals that can actively probe the chemical environment, and (iii) a redox capacitor that manipulates signals for information extraction. We demonstrate the capabilities of this chemical information processing strategy using biothiols because of the emerging importance of these molecules in medicine and because their distinct chemical properties allow evaluation of hypothesis-driven information probing. We show that input sequences can be tailored to probe for chemical information both qualitatively (step inputs probe for thiol-specific signatures) and quantitatively. Specifically, we observed picomolar limits of detection and linear responses to concentrations over 5 orders of magnitude (1 pM-0.1 μM). This approach allows the capabilities of signal processing to be extended for rapid, robust, and on-site analysis of chemical information.

Unique organization and unprecedented diversity of the Bacteroides (Pseudobacteroides) cellulosolvens cellulosome system

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

Zhivin, Olga; Dassa, Bareket; Moraïs, Sarah

The organization of the B. cellulosolvens cellulosome is unique compared to previously described cellulosome systems. In contrast to all other known cellulosomes, the cohesin types are reversed for all scaffoldins i.e., the type II cohesins are located on the enzyme-integrating primary scaffoldin, whereas the type I cohesins are located on the anchoring scaffoldins. Many of the type II dockerin-bearing ORFs include X60 modules, which are known to stabilize type II cohesin–dockerin interactions. In the present work, we focused on revealing the architectural arrangement of cellulosome structure in this bacterium by examining numerous interactions between the various cohesin and dockerin modules.more » In total, we cloned and expressed 43 representative cohesins and 27 dockerins. The results revealed various possible architectures of cell-anchored and cell-free cellulosomes, which serve to assemble distinctive cellulosome types via three distinct cohesin–dockerin specificities: type I, type II, and a novel-type designated R (distinct from type III interactions, predominant in ruminococcal cellulosomes). The results of this study provide novel insight into the architecture and function of the most intricate and extensive cellulosomal system known today, thereby extending significantly our overall knowledge base of cellulosome systems and their components. The robust cellulosome system of B. cellulosolvens, with its unique binding specificities and reversal of cohesin–dockerin types, has served to amend our view of the cellulosome paradigm. Revealing new cellulosomal interactions and arrangements is critical for designing high-efficiency artificial cellulosomes for conversion of plant-derived cellulosic biomass towards improved production of biofuels.« less

Unique organization and unprecedented diversity of the Bacteroides (Pseudobacteroides) cellulosolvens cellulosome system

DOE PAGES

Zhivin, Olga; Dassa, Bareket; Moraïs, Sarah; ...

2017-09-07

The organization of the B. cellulosolvens cellulosome is unique compared to previously described cellulosome systems. In contrast to all other known cellulosomes, the cohesin types are reversed for all scaffoldins i.e., the type II cohesins are located on the enzyme-integrating primary scaffoldin, whereas the type I cohesins are located on the anchoring scaffoldins. Many of the type II dockerin-bearing ORFs include X60 modules, which are known to stabilize type II cohesin–dockerin interactions. In the present work, we focused on revealing the architectural arrangement of cellulosome structure in this bacterium by examining numerous interactions between the various cohesin and dockerin modules.more » In total, we cloned and expressed 43 representative cohesins and 27 dockerins. The results revealed various possible architectures of cell-anchored and cell-free cellulosomes, which serve to assemble distinctive cellulosome types via three distinct cohesin–dockerin specificities: type I, type II, and a novel-type designated R (distinct from type III interactions, predominant in ruminococcal cellulosomes). The results of this study provide novel insight into the architecture and function of the most intricate and extensive cellulosomal system known today, thereby extending significantly our overall knowledge base of cellulosome systems and their components. The robust cellulosome system of B. cellulosolvens, with its unique binding specificities and reversal of cohesin–dockerin types, has served to amend our view of the cellulosome paradigm. Revealing new cellulosomal interactions and arrangements is critical for designing high-efficiency artificial cellulosomes for conversion of plant-derived cellulosic biomass towards improved production of biofuels.« less

Electronic BeeSpace

ERIC Educational Resources Information Center

Stone, David; Buell, James; Naeger, Nicholas

2011-01-01

Recent press coverage of the decrease in worldwide honeybee population (Kaplan 2010) has significantly increased public awareness of its ecological and economic importance. In addition, honeybees' social nature, novel method of gender determination, distinctive caste system, and behaviorally and chemically based language make them immediately…

PHARMACEUTICALS AND PERSONAL CARE PRODUCTS: DIVERSE GALAXY OF ENVIRONMENTAL POLLUTANTS

EPA Science Inventory

The occurrence of pharmaceuticals and personal care products (PPCPs) as trace environmental pollutants is a multifaceted issue whose scope of concerns continues to expand. PPCPs comprise thousands of distinct chemicals from numerous therapeutic and consumer classes. They typical...

Aroma types of flue-cured tobacco in China: spatial distribution and association with climatic factors

NASA Astrophysics Data System (ADS)

Yang, Chao; Wu, Wei; Wu, Shu-Cheng; Liu, Hong-Bin; Peng, Qing

2014-02-01

Aroma types of flue-cured tobacco (FCT) are classified into light, medium, and heavy in China. However, the spatial distribution of FCT aroma types and the relationships among aroma types, chemical parameters, and climatic variables were still unknown at national scale. In the current study, multi-year averaged chemical parameters (total sugars, reducing sugars, nicotine, total nitrogen, chloride, and K2O) of FCT samples with grade of C3F and climatic variables (mean, minimum and maximum temperatures, rainfall, relative humidity, and sunshine hours) during the growth periods were collected from main planting areas across China. Significant relationships were found between chemical parameters and climatic variables ( p < 0.05). A spatial distribution map of FCT aroma types were produced using support vector machine algorithms and chemical parameters. Significant differences in chemical parameters and climatic variables were observed among the three aroma types based on one-way analysis of variance ( p < 0.05). Areas with light aroma type had significantly lower values of mean, maximum, and minimum temperatures than regions with medium and heavy aroma types ( p < 0.05). Areas with heavy aroma type had significantly lower values of rainfall and relative humidity and higher values of sunshine hours than regions with light and medium aroma types ( p < 0.05). The output produced by classification and regression trees showed that sunshine hours, rainfall, and maximum temperature were the most important factors affecting FCT aroma types at national scale.

Distribution and Phase Association of Some Major and Trace Elements in the Arabian Gulf Sediments

NASA Astrophysics Data System (ADS)

Basaham, A. S.; El-Sayed, M. A.

1998-02-01

Twenty-four sediment samples were collected from the Arabian Gulf (ROPME Sea) and analysed for their grain size distribution and carbonate contents as well as the major elements Ca, Mg, Fe and Al and macro and trace elements Mn, Sr, Ba, Zn, Cu, Cr, V, Ni and Hg. Concentration of trace elements are found comparable to previous data published for samples taken before and after the Gulf War, and reflect the natural background level. Grain size analyses, aluminium and carbonate measurements support the presence of two major sediment types: (1) a terrigenous, fine-grained and Al rich type predominating along the Iranian side; and (2) a coarse-grained and carbonate rich type predominating along the Arabian side of the Gulf. Investigation of the correlation of the elements analysed with the sediment type indicates that they could be grouped under two distinct associations: (1) carbonate association including Ca and Sr; and (2) terrigenous association comprising Al, Fe, Mg, Ba, Mn, Zn, Cu, Cr, V, Ni and Hg. Element/Al ratios calculated for the mud non-carbonate fraction indicate that the Euphrates and Tigris rivers have minor importance as sediment sources to the Gulf. Most of the elements have exceptionally high aluminium ratios in sediments containing more than 85-90% carbonate. These sediments are restricted to the southern and south-eastern part of the area where depth is shallow and temperature and salinity are high. Both biological accumulation and chemical and biochemical coprecipitation could be responsible for this anomaly.

Unique Action of Interleukin-18 on T Cells and Other Immune Cells.

PubMed

Nakanishi, Kenji

2018-01-01

Interleukin (IL)-18 was originally discovered as a factor that enhances interferon (IFN)-γ production by anti-CD3-stimulated Th1 cells, particularly in association with IL-12. IL-12 is a cytokine that induces development of Th1 cells. IL-18 cannot induce Th1 cell development, but has the capacity to activate established Th1 cells to produce IFN-γ in the presence of IL-12. Thus, IL-18 is regarded as a proinflammatory cytokine that facilitates type 1 responses. However, in the absence of IL-12 but presence of IL-2, IL-18 stimulates natural killer cells, NKT cells, and even established Th1 cells to produce IL-3, IL-9, and IL-13. Thus, IL-18 also facilitates type 2 responses. This unique function of IL-18 contributes to infection-associated allergic diseases. Together with IL-3, IL-18 stimulates mast cells and basophils to produce IL-4, IL-13, and chemical mediators such as histamine. Thus, IL-18 also induces innate-type allergic inflammation. IL-18 belongs to the IL-1 family of cytokines, which share similar molecular structures, receptors structures, and signal transduction pathways. Nevertheless, IL-18 shows a unique function by binding to a specific receptor expressed on distinct types of cells. In this review article, I will focus on the unique features of IL-18 in lymphocytes, basophils, and mast cells, particularly in comparison with IL-33.

Magma batches in the Timber Mountain magmatic system, Southwestern Nevada Volcanic Field, Nevada, USA

NASA Astrophysics Data System (ADS)

Mills, James G.; Saltoun, Benjamin W.; Vogel, Thomas A.

1997-09-01

The common occurrence of compositionally and mineralogically zoned ash flow sheets, such as those of the Timber Mountain Group, provides evidence that the source magma bodies were chemically and thermally zoned. The Rainier Mesa and Ammonia Tanks tuffs of the Timber Mountain Group are both large volume (1200 and 900 km 3, respectively) chemically zoned (57-78 wt.% SiO 2) ash flow sheets. Evidence of distinct magma batches in the Timber Mountain system are based on: (1) major- and trace-element variations of whole pumice fragments; (2) major-element variations in phenocrysts; (3) major-element variations in glass matrix; and (4) emplacement temperatures calculated from Fe-Ti oxides and feldspars. There are three distinct groups of pumice fragments in the Rainier Mesa Tuff: a low-silica group and two high-silica groups (a low-Th and a high-Th group). These groups cannot be related by crystal fractionation. The low-silica portion of the Rainier Mesa Tuff is distinct from the low-silica portion of the overlying Ammonia Tanks Tuff, even though the age difference is less than 200,000 years. Three distinct groups occur in the Ammonia Tanks Tuff: a low-silica, intermediate-silica and a high-silica group. Part of the high-silica group may be due to mixing of the two high-silica Rainier Mesa groups. The intermediate-silica group may be due to mixing of the low- and high-silica Ammonia Tanks groups. Three distinct emplacement temperatures occur in the Rainier Mesa Tuff (869, 804, 723 °C) that correspond to the low-silica, high-Th and low-Th magma batches, respectively. These temperature differences could not have been maintained for any length of time in the magma chamber (cf. Turner, J.S., Campbell, I.H., 1986. Convection and mixing in magma chambers. Earth-Sci. Rev. 23, 255-352; Martin, D., Griffiths, R.W., Campbell, I.H., 1987. Compositional and thermal convection in magma chambers. Contrib. Mineral. Petrol. 96, 465-475) and therefore eruption must have occurred soon after emplacement of the magma batches into the chamber. Emplacement temperatures of the pumice fragments from the Ammonia Tanks Tuff show a continuous gradient of temperatures with composition. This continuous temperature gradient is consistent with the model of storage of magma batches in the Ammonia Tanks group that have undergone both thermal and chemical diffusion.

The origin of soil organic matter controls its composition and bioreactivity across a mesic boreal forest latitudinal gradient.

PubMed

Kohl, Lukas; Philben, Michael; Edwards, Kate A; Podrebarac, Frances A; Warren, Jamie; Ziegler, Susan E

2018-02-01

Warmer climates have been associated with reduced bioreactivity of soil organic matter (SOM) typically attributed to increased diagenesis; the combined biological and physiochemical transformation of SOM. In addition, cross-site studies have indicated that ecosystem regime shifts, associated with long-term climate warming, can affect SOM properties through changes in vegetation and plant litter production thereby altering the composition of soil inputs. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming, however, remains poorly understood. To address this issue we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids analysis), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. The observed climate effects on vascular plant litter chemistry, however, explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer relative to cooler forests. These results indicate that climate change induced decreases in the proportion of moss inputs not only impacts SOM chemistry but also increases the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils. © 2017 John Wiley & Sons Ltd.

Epitaxial CdSe-Au nanocrystal heterostructures by thermal annealing.

PubMed

Figuerola, Albert; van Huis, Marijn; Zanella, Marco; Genovese, Alessandro; Marras, Sergio; Falqui, Andrea; Zandbergen, Henny W; Cingolani, Roberto; Manna, Liberato

2010-08-11

The thermal evolution of a collection of heterogeneous CdSe-Au nanosystems (Au-decorated CdSe nanorods, networks, vertical assemblies) prepared by wet-chemical approaches was monitored in situ in the transmission electron microscope. In contrast to interfaces that are formed during kinetically controlled wet chemical synthesis, heating under vacuum conditions results in distinct and well-defined CdSe/Au interfaces, located at the CdSe polar surfaces. The high quality of these interfaces should make the heterostructures more suitable for use in nanoscale electronic devices.

Polarimetry of nacre in iridescent shells

NASA Astrophysics Data System (ADS)

Metzler, R. A.; Burgess, C.; Regan, B.; Spano, S.; Galvez, E. J.

2014-09-01

We investigate the light transmitted or reflected from nacre (mother of pearl) taken from the iridescent shell of the bivalve Pinctad a fucata. These nacre surfaces have a rich structure, composed of aragonite crystals arranged as tablets or bricks, 5 μm wide and 400-500 nm thick, surrounded by 30nm thick organic mortar. The light reflected from these shell surfaces, or transmitted through thin polished layers, is rich in its polarization content, exhibiting a space dependent variation in the state of polarization with a high density of polarization singularities. Our goal is to use the polarization information to infer the structure of the biominerals and the role of the organic layer in determining the orientation of the crystals. In the experiments we send the light from a laser with a uniform state of polarization onto the shell, and analyze the light that is either transmitted or reflected, depending on the type of experiment, imaging it after its passage through polarization filters. We use the images from distinct filters to obtain the Stokes parameters, and hence the state of polarization, of each image point. We also construct the Mueller matrix for each imaged point, via 36 measurements. We do this for distinct physical and chemical treatments of the shell sample. Preliminary data shows that the organic layer may be responsible for organizing a multi-crystalline arrangement of aragonite tablets.

Self-assembly of polysaccharides gives rise to distinct mechanical signatures in marine gels.

PubMed

Pletikapić, G; Lannon, H; Murvai, Ü; Kellermayer, M S Z; Svetličić, V; Brujic, J

2014-07-15

Marine-gel biopolymers were recently visualized at the molecular level using atomic force microscopy (AFM) to reveal fine fibril-forming networks with low to high degrees of cross-linking. In this work, we use force spectroscopy to quantify the intra- and intermolecular forces within the marine-gel network. Combining force measurements, AFM imaging, and the known chemical composition of marine gels allows us to identify the microscopic origins of distinct mechanical responses. At the single-fibril level, we uncover force-extension curves that resemble those of individual polysaccharide fibrils. They exhibit entropic elasticity followed by extensions associated with chair-to-boat transitions specific to the type of polysaccharide at high forces. Surprisingly, a low degree of cross-linking leads to sawtooth patterns that we attribute to the unraveling of polysaccharide entanglements. At a high degree of cross-linking, we observe force plateaus that arise from unzipping, as well as unwinding, of helical bundles. Finally, the complex 3D network structure gives rise to force staircases of increasing height that correspond to the hierarchical peeling of fibrils away from the junction zones. In addition, we show that these diverse mechanical responses also arise in reconstituted polysaccharide gels, which highlights their dominant role in the mechanical architecture of marine gels. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Extending Miles & Snow's strategy choice typology to the German hospital sector.

PubMed

Helmig, Bernd; Hinz, Vera; Ingerfurth, Stefan

2014-12-01

Hospitals' strategy choices represent highly relevant factors that affect organizational performance and survival. This study assesses the differences among hospitals' strategic choices. This strategy definition and assessment reflects the typology proposed by Miles and Snow, who distinguish four strategy types: defender, analyzer, prospector, and reactor. Synthesis of empirical evidence from previous studies that have applied Miles and Snow's typology in the hospital sector using various methodological approaches and measures provides hints for industry-specific patterns and avenues for further research. Taking an extended view of strategic choice, the authors conduct an empirical survey of a sample of 178 German hospitals. The authors apply a multi-item measure of the Miles and Snow strategy types in the hospital sector and identify hybrid strategy types that deviate from the four strategy types defined by Miles and Snow. Overall, seven distinct strategy types emerge from this analysis. There exist three distinct hybrid types in particular. Strategy choice is systematically related to hospital size and teaching status but not to ownership and location. The significant variance in performance for the seven different strategy types justifies the distinction between them. The results support the idea of industry-specific strategy choices. Policy makers should analyze the structural context in which hospitals operate and intervene through political and regulatory means. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Improvement of the Owner Distinction Method for Healing-Type Pet Robots

NASA Astrophysics Data System (ADS)

Nambo, Hidetaka; Kimura, Haruhiko; Hara, Mirai; Abe, Koji; Tajima, Takuya

In order to decrease human stress, Animal Assisted Therapy which applies pets to heal humans is attracted. However, since animals are insanitary and unsafe, it is difficult to practically apply animal pets in hospitals. For the reason, on behalf of animal pets, pet robots have been attracted. Since pet robots would have no problems in sanitation and safety, they are able to be applied as a substitute for animal pets in the therapy. In our previous study where pet robots distinguish their owners like an animal pet, we used a puppet type pet robot which has pressure type touch sensors. However, the accuracy of our method was not sufficient to practical use. In this paper, we propose a method to improve the accuracy of the distinction. The proposed method can be applied for capacitive touch sensors such as installed in AIBO in addition to pressure type touch sensors. Besides, this paper shows performance of the proposed method from experimental results and confirms the proposed method has improved performance of the distinction in the conventional method.

Biochemical Characterization of Prion Strains in Bank Voles

PubMed Central

Pirisinu, Laura; Marcon, Stefano; Di Bari, Michele Angelo; D’Agostino, Claudia; Agrimi, Umberto; Nonno, Romolo

2013-01-01

Prions exist as different strains exhibiting distinct disease phenotypes. Currently, the identification of prion strains is still based on biological strain typing in rodents. However, it has been shown that prion strains may be associated with distinct PrPSc biochemical types. Taking advantage of the availability of several prion strains adapted to a novel rodent model, the bank vole, we investigated if any prion strain was actually associated with distinctive PrPSc biochemical characteristics and if it was possible to univocally identify strains through PrPSc biochemical phenotypes. We selected six different vole-adapted strains (three human-derived and three animal-derived) and analyzed PrPSc from individual voles by epitope mapping of protease resistant core of PrPSc (PrPres) and by conformational stability and solubility assay. Overall, we discriminated five out of six prion strains, while two different scrapie strains showed identical PrPSc types. Our results suggest that the biochemical strain typing approach here proposed was highly discriminative, although by itself it did not allow us to identify all prion strains analyzed. PMID:25437201

Neoproterozoic cap-dolostone deposition in stratified glacial meltwater plume

NASA Astrophysics Data System (ADS)

Liu, Chao; Wang, Zhengrong; Raub, Timothy D.; Macdonald, Francis A.; Evans, David A. D.

2014-10-01

Neoproterozoic cap carbonates host distinctive geochemical and sedimentological features that reflect prevailing conditions in the aftermath of Snowball Earth. Interpretation of these features has remained contentious, with hypotheses hinging upon timescale and synchronicity of deposition, and whether or not geochemical signatures of cap carbonates represent those of a well-mixed ocean. Here we present new high-resolution Sr and Mg isotope results from basal Ediacaran cap dolostones in South Australia and Mongolia. Least-altered Sr and Mg isotope compositions of carbonates are identified through a novel incremental leaching technique that monitors the purity of a carbonate sample and the effects of diagenesis. These data can be explained by the formation of these cap dolostones involving two chemically distinct solutions, a glacial meltwater plume enriched in radiogenic Sr, and a saline ocean residue with relatively lower 87Sr/86Sr ratios. Model simulations suggest that these water bodies remained dynamically stratified during part of cap-dolostone deposition, most likely lasting for ∼8 thousand years. Our results can potentially reconcile previous conflicts between timescales estimated from physical mixing models and paleomagnetic constraints. Geochemical data from cap carbonates used to interpret the nature of Snowball Earth and its aftermath should be recast in terms of a chemically distinct meltwater plume.

Recent trends and important developments in propolis research

PubMed Central

2005-01-01

The newest developments in propolis pharmacological research are summarized. The problem regarding biological studies, caused by the chemical variability of propolis, is discussed. The most important trends and developments in recent propolis research are outlined: biological studies performed with chemically characterized samples, bioassay-guided studies of active principles and comparative biological studies of propolis of different origin and chemical composition. These types of studies are extremely valuable with respect to propolis standardization and practical applications in therapy. They will allow scientists to connect a particular chemical propolis type to a specific type of biological activity and formulate recommendations for practitioners. PMID:15841275

Method for solid state crystal growth

DOEpatents

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Floquet Weyl semimetals in light-irradiated type-II and hybrid line-node semimetals

NASA Astrophysics Data System (ADS)

Chen, Rui; Zhou, Bin; Xu, Dong-Hui

2018-04-01

Type-II Weyl semimetals have recently attracted intensive research interest because they host Lorentz-violating Weyl fermions as quasiparticles. The discovery of type-II Weyl semimetals evokes the study of type-II line-node semimetals (LNSMs) whose linear dispersion is strongly tilted near the nodal ring. We present here a study on the circularly polarized light-induced Floquet states in type-II LNSMs, as well as those in hybrid LNSMs that have a partially overtilted linear dispersion in the vicinity of the nodal ring. We illustrate that two distinct types of Floquet Weyl semimetal (WSM) states can be induced in periodically driven type-II and hybrid LNSMs, and the type of Floquet WSMs can be tuned by the direction and intensity of the incident light. We construct phase diagrams of light-irradiated type-II and hybrid LNSMs which are quite distinct from those of light-irradiated type-I LNSMs. Moreover, we show that photoinduced Floquet type-I and type-II WSMs can be characterized by the emergence of different anomalous Hall conductivities.

Silicon Cluster Tool | Photovoltaic Research | NREL

Science.gov Websites

Material Deposition/Device Fabrication Very-high-frequency plasma-enhanced chemical vapor deposition (VHF PECVD) for microcrystalline silicon (µc-Si:H) Combinatorial plasma-enhanced chemical vapor deposition (Combi-PECVD) for p-type a-Si:H Plasma-enhanced chemical vapor deposition (PECVD) for n-type a-Si:H