Isolation, purification and chemical composition of insoluble collagen from Guerin epithelioma.

PubMed

Bańkowski, E; Galasiński, W; Gindzieẃski, A; Rzeczycki, W

1975-01-01

1. The insoluble collagen from Guerin epithelioma was isolated and its chemical composition was determined. The unusually high histidine content is accompanied in tumour collagen by a relatively small amount of lysine and arginine. 2. The isolated protein was strongly bound to glycoprotein, which could not be removed by EDTA treatment unless this procedure was preceded by digestion of the complex with trypsin.

Identification Of (Bright) Carbon-Enhanced Metal-Poor Stars With J-Plus Photometry

NASA Astrophysics Data System (ADS)

Placco, Vinicius

2017-10-01

The chemical composition of our bodies, the Earth, the Sun, and the Universe is complex, and the end result of the formation and evolution of numerous stellar generations that contributed all of the elements heavier than helium. One way to understand the possible pathways that led to such complexity is to determine the chemical abundance patterns of ancient low-metallicity stars in the Halo of our Galaxy. However, it is impossible to observe each of the 100 billion stars in the Milky Way in sufficient detail to assess its chemical composition. Hence, astronomers have developed efficient ways to pre-select the most interesting stars for further high-resolution follow-up, based on the understanding that the colors of stars in specific regions of the optical spectrum are affected in predictable ways by changes in their chemical composition. I will discuss the importance of the J-PLUS photometry in selecting low-metallicity and carbon-enhanced stars, using its 12 magnitudes, which will fully exploit this approach, in a manner superior to all previous such efforts.

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Chemical Evolution of a Protoplanetary Disk

NASA Astrophysics Data System (ADS)

Semenov, Dmitry A.

2011-12-01

In this paper we review recent progress in our understanding of the chemical evolution of protoplanetary disks. Current observational constraints and theoretical modeling on the chemical composition of gas and dust in these systems are presented. Strong variations of temperature, density, high-energy radiation intensities in these disks, both radially and vertically, result in a peculiar disk chemical structure, where a variety of processes are active. In hot, dilute and heavily irradiated atmosphere only the most photostable simple radicals and atoms and atomic ions exist, formed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich ion-molecule and radical-radical chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex polyatomic (organic) species are synthesized. Dynamical processes affect disk chemical composition by enriching it in abundances of complex species produced via slow surface processes, which will become detectable with ALMA.

Physical and Chemical Properties of Anthropogenic Aerosols: An Overview

EPA Science Inventory

Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...

UHPC and NSFRC in Severe Environmental Conditions

NASA Astrophysics Data System (ADS)

Rehacek, S.; Citek, D.; Kolisko, J.

2017-10-01

Structure and properties of cement composite are time-varying characteristics, depending among others on environmental conditions. The key idea is a struggle for complex research of joint effect of physical, chemical and dynamic loads on the internal structure of cement composite and understanding the correlation between changes in microstructure and macro-scale properties. During the experimental program, specimens will be exposed to combined influence of freeze-thaw cycles, aggressive chemical agents and dynamic loading. The aim is to create a theoretical basis for design of effective cement composites meant to be used in severe environmental conditions.

Approach of automatic 3D geological mapping: the case of the Kovdor phoscorite-carbonatite complex, NW Russia.

PubMed

Kalashnikov, A O; Ivanyuk, G Yu; Mikhailova, J A; Sokharev, V A

2017-07-31

We have developed an approach for automatic 3D geological mapping based on conversion of chemical composition of rocks to mineral composition by logical computation. It allows to calculate mineral composition based on bulk rock chemistry, interpolate the mineral composition in the same way as chemical composition, and, finally, build a 3D geological model. The approach was developed for the Kovdor phoscorite-carbonatite complex containing the Kovdor baddeleyite-apatite-magnetite deposit. We used 4 bulk rock chemistry analyses - Fe magn , P 2 O 5 , CO 2 and SiO 2 . We used four techniques for prediction of rock types - calculation of normative mineral compositions (norms), multiple regression, artificial neural network and developed by logical evaluation. The two latter became the best. As a result, we distinguished 14 types of phoscorites (forsterite-apatite-magnetite-carbonate rock), carbonatite and host rocks. The results show good convergence with our petrographical studies of the deposit, and recent manually built maps. The proposed approach can be used as a tool of a deposit genesis reconstruction and preliminary geometallurgical modelling.

Progress in the Analysis of Complex Atmospheric Particles

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

Laskin, Alexander; Gilles, Mary K.; Knopf, Daniel A.

2016-06-16

This manuscript presents an overview on recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surfaces interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multi-modal chemical characterization of particles with both molecularmore » and lateral specificity. When combined, they provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore environmental effects of air-surface interactions.« less

Progress in the analysis of complex atmospheric particles

DOE PAGES

Laskin, Alexander; Gilles, Mary K.; Knopf, Daniel A.; ...

2016-06-01

This study presents an overview of recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surface interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multimodal chemical characterization of particles with both molecularmore » and lateral specificity. When combined, these approaches provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore the environmental effects of air-surface interactions.« less

Computer program determines chemical equilibria in complex systems

NASA Technical Reports Server (NTRS)

Gordon, S.; Zeleznik, F. J.

1966-01-01

Computer program numerically solves nonlinear algebraic equations for chemical equilibrium based on iteration equations independent of choice of components. This program calculates theoretical performance for frozen and equilibrium composition during expansion and Chapman-Jouguet flame properties, studies combustion, and designs hardware.

Chemical composition of preen wax reflects major histocompatibility complex similarity in songbirds.

PubMed

Slade, J W G; Watson, M J; Kelly, T R; Gloor, G B; Bernards, M A; MacDougall-Shackleton, E A

2016-11-16

In jawed vertebrates, genes of the major histocompatibility complex (MHC) play a key role in immunity by encoding cell-surface proteins that recognize and bind non-self antigens. High variability at MHC suggests that these loci may also function in social signalling such as mate choice and kin recognition. This requires that MHC genotype covaries with some perceptible phenotypic trait. In mammals and fish, MHC is signalled chemically through volatile and non-volatile peptide odour cues, facilitating MHC-dependent mate choice and other behaviours. In birds, despite evidence for MHC-dependent mating, candidate mechanisms for MHC signalling remain largely unexplored. However, feather preen wax has recently been implicated as a potential source of odour cues. We examined whether the chemical composition of preen wax correlates with MHC class IIβ genotypes of wild song sparrows (Melospiza melodia). Pairwise chemical distance reflected amino acid distance at MHC for male-female dyads, although not for same-sex dyads. Chemical diversity did not reflect MHC diversity. We used gas chromatography-mass spectrometry (GC-MS) to characterize preen wax compounds, and identified four wax esters that best reflect MHC similarity. Provided songbirds can detect variation in preen wax composition, this cue may allow individuals to assess MHC compatibility of potential mates. © 2016 The Author(s).

[Tissue-specific nucleoprotein complexes].

PubMed

Riadnova, I Iu; Shataeva, L K; Khavinson, V Kh

2000-01-01

A method of isolation of native nucleorprotein complexes from cattle cerebral cortex, thymus, and liver was developed. Compositions of these complexes were studied by means of gel-chromatography and ion-exchange chromatography. These preparations were shown to consist of several fractions of proteins and their complexes differ by molecular mass and electro-chemical properties. Native nucleoprotein complexes revealed high tissue specific activity, which was not species-specific.

Analysis of the chemical and physical properties of combustion aerosols: Properties overview

EPA Science Inventory

Aerosol chemical composition is remarkably complex. Combustion aerosols can comprise tens of thousands of organic compounds and fragments, refractory carbon, metals, cations, anions, salts, and other inorganic phases and substituents [Hays et al., 2004]. Aerosol organic matter no...

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

DOE PAGES

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.; ...

2017-11-17

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

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

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Deciphering the Complex Chemistry of Deep-Ocean Particles Using Complementary Synchrotron X-ray Microscope and Microprobe Instruments.

PubMed

Toner, Brandy M; German, Christopher R; Dick, Gregory J; Breier, John A

2016-01-19

The reactivity and mobility of natural particles in aquatic systems have wide ranging implications for the functioning of Earth surface systems. Particles in the ocean are biologically and chemically reactive, mobile, and complex in composition. The chemical composition of marine particles is thought to be central to understanding processes that convert globally relevant elements, such as C and Fe, among forms with varying bioavailability and mobility in the ocean. The analytical tools needed to measure the complex chemistry of natural particles are the subject of this Account. We describe how a suite of complementary synchrotron radiation instruments with nano- and micrometer focusing, and X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) capabilities are changing our understanding of deep-ocean chemistry and life. Submarine venting along mid-ocean ridges creates hydrothermal plumes where dynamic particle-forming reactions occur as vent fluids mix with deep-ocean waters. Whether plumes are net sources or sinks of elements in ocean budgets depends in large part on particle formation, reactivity, and transport properties. Hydrothermal plume particles have been shown to host microbial communities and exhibit complex size distributions, aggregation behavior, and composition. X-ray microscope and microprobe instruments can address particle size and aggregation, but their true strength is in measuring chemical composition. Plume particles comprise a stunning array of inorganic and organic phases, from single-crystal sulfides to poorly ordered nanophases and polymeric organic matrices to microbial cells. X-ray microscopes and X-ray microprobes with elemental imaging, XAS, and XRD capabilities are ideal for investigating these complex materials because they can (1) measure the chemistry of organic and inorganic constituents in complex matrices, usually within the same particle or aggregate, (2) provide strong signal-to-noise data with exceedingly small amounts of material, (3) simplify the chemical complexity of particles or sets of particles with a focused-beam, providing spatial resolution over 6 orders of magnitude (nanometer to millimeter), (4) provide elemental specificity for elements in the soft-, tender-, and hard-X-ray energies, (5) switch rapidly among elements of interest, and (6) function in the presence of water and gases. Synchrotron derived data sets are discussed in the context of important advances in deep-ocean technology, sample handling and preservation, molecular microbiology, and coupled physical-chemical-biological modeling. Particle chemistry, size, and morphology are all important in determining whether particles are reactive with dissolved constituents, provide substrates for microbial respiration and growth, and are delivered to marine sediments or dispersed by deep-ocean currents.

Arsenic distribution and valence state variation studied by fast hierarchical length-scale morphological, compositional, and speciation imaging at the Nanoscopium, Synchrotron Soleil

NASA Astrophysics Data System (ADS)

Somogyi, Andrea; Medjoubi, Kadda; Sancho-Tomas, Maria; Visscher, P. T.; Baranton, Gil; Philippot, Pascal

2017-09-01

The understanding of real complex geological, environmental and geo-biological processes depends increasingly on in-depth non-invasive study of chemical composition and morphology. In this paper we used scanning hard X-ray nanoprobe techniques in order to study the elemental composition, morphology and As speciation in complex highly heterogeneous geological samples. Multivariate statistical analytical techniques, such as principal component analysis and clustering were used for data interpretation. These measurements revealed the quantitative and valance state inhomogeneity of As and its relation to the total compositional and morphological variation of the sample at sub-μm scales.

Near infrared spectroscopy and chemometrics analysis of complex traits in animal physiology

USDA-ARS?s Scientific Manuscript database

Near infrared reflectance (NIR) applications have been expanding from the traditional framework of small molecule chemical purity and composition (as defined by spectral libraries) to complex system analysis and holistic exploratory approaches to questions in biochemistry, biophysics and environment...

Calculation of point defect concentration in Cu2ZnSnS4: Insights into the high-temperature equilibrium and quenching

NASA Astrophysics Data System (ADS)

Kosyak, V.; Postnikov, A. V.; Scragg, J.; Scarpulla, M. A.; Platzer-Björkman, C.

2017-07-01

Herein, we study the native point defect equilibrium in Cu2ZnSnS4 (CZTS) by applying a statistical thermodynamic model. The stable chemical-potential space (SCPS) of CZTS at an elevated temperature was estimated directly, on the basis of deviations from stoichiometry calculated for the different combinations of chemical potential of the components. We show that the SCPS is narrow due to high concentration of (" separators="|VCu --ZnC u + ) complex which is dominant over other complexes and isolated defects. The CZTS was found to have p-type conductivity for both stoichiometric and Cu-poor/Zn-rich composition. It is established that the reason for this is that the majority of donor-like ZnC u + antisites are involved in the formation of (" separators="|VCu --ZnC u + ) complex making CuZ n - dominant and providing p-type conductivity even for Cu-poor/Zn-rich composition. However, our calculation reveals that the hole concentration is almost insensitive to the variation of the chemical composition within the composition region of the single-phase CZTS due to nearly constant concentration of dominant charged defects. The calculations for the full equilibrium and quenching indicate that hole concentration is strongly dependent on the annealing temperature and decreases substantially after the drastic cooling. This means that the precise control of annealing temperature and post-annealing cooling rate are critical for tuning the electrical properties of CZTS.

Characterisation of metals in the electronic waste of complex mixtures of end-of-life ICT products for development of cleaner recovery technology

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

Sun, Z.H.I.; Xiao, Y.; Sietsma, J.

2015-01-15

Highlights: • New characterisation methodology has been established to understand an industrially processed ICT waste. • Particle size distribution, composition, thermal–chemical behaviour and occurrence of metals were considered. • The characterisation provides direct guidelines for values recovery from the waste. - Abstract: Recycling of valuable metals from electronic waste, especially complex mixtures of end-of-life information and communication technology (ICT) products, is of great difficulty due to their complexity and heterogeneity. One of the important reasons is the lack of comprehensive characterisation on such materials, i.e. accurate compositions, physical/chemical properties. In the present research, we focus on developing methodologies for themore » characterisation of metals in an industrially processed ICT waste. The morphology, particle size distribution, compositional distribution, occurrence, liberation as well as the thermo-chemical properties of the ICT waste were investigated with various characterisation techniques, including X-ray Fluorescence Spectrometry (XRF), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) with energy dispersed spectroscopy (EDS). Due to the high heterogeneity of the material, special sample preparation procedures were introduced to minimise the discrepancies during compositional analyses. As a result, a clearer overview of the ICT waste has been reached. This research provides better understanding of the extractability of each metal and improves the awareness of potential obstacles for extraction. It will lead to smarter decisions during further development of a clean and effective recovery process.« less

Influence of feedstock chemical composition on product formation and characteristics derived from the hydrothermal carbonization of mixed feedstocks.

PubMed

Lu, Xiaowei; Berge, Nicole D

2014-08-01

As the exploration of the carbonization of mixed feedstocks continues, there is a distinct need to understand how feedstock chemical composition and structural complexity influence the composition of generated products. Laboratory experiments were conducted to evaluate the carbonization of pure compounds, mixtures of the pure compounds, and complex feedstocks comprised of the pure compounds (e.g., paper, wood). Results indicate that feedstock properties do influence carbonization product properties. Carbonization product characteristics were predicted using results from the carbonization of the pure compounds and indicate that recovered solids energy contents are more accurately predicted than solid yields and the carbon mass in each phase, while predictions associated with solids surface functional groups are more difficult to predict using this linear approach. To more accurately predict carbonization products, it may be necessary to account for feedstock structure and/or additional feedstock properties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzmán, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2009-02-01

Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzman, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2008-02-01

Variations on chemical composition in fossil biogenic carbonates, and in particular of mollusk shells, have been used in a range of palaeoenvironmental reconstructions. Therefore, it is of primary importance to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Pleistocene and Holocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusk shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to attest shell sample conservation state should not be considered as sufficient.

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements

DOE PAGES

Bonamici, Chloë E.; Hervig, Richard L.; Kinman, William S.

2017-08-25

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. By using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclidesmore » generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Moreover, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.« less

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements

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

Bonamici, Chloë E.; Hervig, Richard L.; Kinman, William S.

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. By using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclidesmore » generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Moreover, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.« less

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements.

PubMed

Bonamici, Chloë E; Hervig, Richard L; Kinman, William S

2017-09-19

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. Using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclides generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Furthermore, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.

Dye sensitized solar cell applications of CdTiO3-TiO2 composite thin films deposited from single molecular complex

NASA Astrophysics Data System (ADS)

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy; Huang, Nay Ming; Arifin, Zainudin; Mazhar, Muhammad

2015-10-01

A heterobimetallic complex [Cd2Ti4(μ-O)6(TFA)8(THF)6]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO3-TiO2 composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity, phase identification and chemical composition of microspherical architectured CdTiO3-TiO2 composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application.

[Advances in studies on bear bile powder].

PubMed

Zhou, Chao-fan; Gao, Guo-jian; Liu, Ying

2015-04-01

In this paper, a detailed analysis was made on relevant literatures about bear bile powder in terms of chemical component, pharmacological effect and clinical efficacy, indicating bear bile powder's significant pharmacological effects and clinical application in treating various diseases. Due to the complex composition, bear bile powder is relatively toxic. Therefore, efforts shall be made to study bear bile powder's pharmacological effects, clinical application, chemical composition and toxic side-effects, with the aim to provide a scientific basis for widespread reasonable clinical application of bear bile powder.

Proteomics-based compositional analysis of complex cellulase-hemicellulase mixtures.

PubMed

Chundawat, Shishir P S; Lipton, Mary S; Purvine, Samuel O; Uppugundla, Nirmal; Gao, Dahai; Balan, Venkatesh; Dale, Bruce E

2011-10-07

Efficient deconstruction of cellulosic biomass to fermentable sugars for fuel and chemical production is accomplished by a complex mixture of cellulases, hemicellulases, and accessory enzymes (e.g., >50 extracellular proteins). Cellulolytic enzyme mixtures, produced industrially mostly using fungi like Trichoderma reesei, are poorly characterized in terms of their protein composition and its correlation to hydrolytic activity on cellulosic biomass. The secretomes of commercial glycosyl hydrolase-producing microbes was explored using a proteomics approach with high-throughput quantification using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Here, we show that proteomics-based spectral counting approach is a reasonably accurate and rapid analytical technique that can be used to determine protein composition of complex glycosyl hydrolase mixtures that also correlates with the specific activity of individual enzymes present within the mixture. For example, a strong linear correlation was seen between Avicelase activity and total cellobiohydrolase content. Reliable, quantitative and cheaper analytical methods that provide insight into the cellulosic biomass degrading fungal and bacterial secretomes would lead to further improvements toward commercialization of plant biomass-derived fuels and chemicals.

Inhalation Exposure and Lung Dose Analysis of Multi-mode Complex Ambient Aerosols

EPA Science Inventory

Rationale: Ambient aerosols are complex mixture of particles with different size, shape and chemical composition. Although they are known to cause health hazard, it is not fully understood about causal mechanisms and specific attributes of particles causing the effects. Internal ...

Dye sensitized solar cell applications of CdTiO{sub 3}–TiO{sub 2} composite thin films deposited from single molecular complex

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

Ehsan, Muhammad Ali; Khaledi, Hamid; Pandikumar, Alagarsamy

2015-10-15

A heterobimetallic complex [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF (1) (TFA=trifluoroacetato, THF=tetrahydrofuran) comprising of Cd:Ti (1:2) ratio was synthesized by a chemical reaction of cadmium (II) acetate with titanium (IV) isopropoxide and triflouroacetic acid in THF. The stoichiometry of (1) was recognized by single crystal X-ray diffraction, spectroscopic and elemental analyses. Thermal studies revealed that (1) neatly decomposes at 450 °C to furnish 1:1 ratio of cadmium titanate:titania composite oxides material. The thin films of CdTiO{sub 3}–TiO{sub 2} composite oxides were deposited at 550 °C on fluorine doped tin oxide coated conducting glass substrate in air ambient. The micro-structure, crystallinity,more » phase identification and chemical composition of microspherical architectured CdTiO{sub 3}–TiO{sub 2} composite thin film have been determined by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The scope of composite thin film having band gap of 3.1 eV was explored as photoanode for dye-sensitized solar cell application. - Graphical abstarct: Microspherical designed CdTiO{sub 3}–TiO{sub 2} composite oxides photoanode film has been fabricated from single source precursor [Cd{sub 2}Ti{sub 4}(μ-O){sub 6}(TFA){sub 8}(THF){sub 6}]·1.5THF via aerosol assisted chemical vapor deposition technique for dye sensitized solar cell application. - Highlights: • Synthesis and characterization of a heterobimetallic Cd–Ti complex. • Fabrication of CdTiO{sub 3}–TiO{sub 2} thin film photoelectrode. • Application as dye sensitized photoanode for solar application.« less

Elemental Analysis of Soils by Laser Induced Breakdown Spectroscopy

NASA Astrophysics Data System (ADS)

Gondal, Mohammed Ashraf; Dastageer, Mohamed A.

The chemical and elemental composition of soil is very complex as it contains many constituents like minerals, organic matters, living organisms, fossils, air and water. Considering the diversity of soil contents, quality and usability, a systematic scientific study on the elemental and chemical composition of soil is very important. In order to study the chemical composition of soil, Laser induced breakdown spectroscopy (LIBS) has been applied recently. The important features of LIBS system and its applications for the measurement of nutrients in green house soil, on-line monitoring of remediation process of chromium polluted soil, determination of trace elements in volcanic erupted soil samples collected from ancient cenozoic lava eruption sites and detection of toxic metals in Gulf war oil spill contaminated soil using LIBS are described in this chapter.

The Brittleness and Chemical Stability of Optimized Geopolymer Composites

PubMed Central

Steinerova, Michaela; Matulova, Lenka; Vermach, Pavel; Kotas, Jindrich

2017-01-01

Geopolymers are known as high strength and durable construction materials but have a brittle fracture. In practice, this results in a sudden collapse at ultimate load, without any chance of preventing the breakdown of parts or of withstanding the stress for some time. Glass fiber usage as a total anisotropic shape acting as a compact structure component should hinder the fracture mechanism. The optimized compositions in this study led to a significant reinforcement, especially in the case of flexural strength, but also in terms of the compressive strength and notch toughness. The positive and negative influence of the fibers on the complex composite properties provided chemical stability. PMID:28772756

The Brittleness and Chemical Stability of Optimized Geopolymer Composites.

PubMed

Steinerova, Michaela; Matulova, Lenka; Vermach, Pavel; Kotas, Jindrich

2017-04-09

Geopolymers are known as high strength and durable construction materials but have a brittle fracture. In practice, this results in a sudden collapse at ultimate load, without any chance of preventing the breakdown of parts or of withstanding the stress for some time. Glass fiber usage as a total anisotropic shape acting as a compact structure component should hinder the fracture mechanism. The optimized compositions in this study led to a significant reinforcement, especially in the case of flexural strength, but also in terms of the compressive strength and notch toughness. The positive and negative influence of the fibers on the complex composite properties provided chemical stability.

The Impact of Aerosol Particle Mixing State on the Hygroscopicity of Sea Spray Aerosol.

PubMed

Schill, Steven R; Collins, Douglas B; Lee, Christopher; Morris, Holly S; Novak, Gordon A; Prather, Kimberly A; Quinn, Patricia K; Sultana, Camille M; Tivanski, Alexei V; Zimmermann, Kathryn; Cappa, Christopher D; Bertram, Timothy H

2015-06-24

Aerosol particles influence global climate by determining cloud droplet number concentrations, brightness, and lifetime. Primary aerosol particles, such as those produced from breaking waves in the ocean, display large particle-particle variability in chemical composition, morphology, and physical phase state, all of which affect the ability of individual particles to accommodate water and grow into cloud droplets. Despite such diversity in molecular composition, there is a paucity of methods available to assess how particle-particle variability in chemistry translates to corresponding differences in aerosol hygroscopicity. Here, an approach has been developed that allows for characterization of the distribution of aerosol hygroscopicity within a chemically complex population of atmospheric particles. This methodology, when applied to the interpretation of nascent sea spray aerosol, provides a quantitative framework for connecting results obtained using molecular mimics generated in the laboratory with chemically complex ambient aerosol. We show that nascent sea spray aerosol, generated in situ in the Atlantic Ocean, displays a broad distribution of particle hygroscopicities, indicative of a correspondingly broad distribution of particle chemical compositions. Molecular mimics of sea spray aerosol organic material were used in the laboratory to assess the volume fractions and molecular functionality required to suppress sea spray aerosol hygroscopicity to the extent indicated by field observations. We show that proper accounting for the distribution and diversity in particle hygroscopicity and composition are important to the assessment of particle impacts on clouds and global climate.

Ellipsometric study of metal-organic chemically vapor deposited III-V semiconductor structures

NASA Technical Reports Server (NTRS)

Alterovitz, Samuel A.; Sekula-Moise, Patricia A.; Sieg, Robert M.; Drotos, Mark N.; Bogner, Nancy A.

1992-01-01

An ellipsometric study of MOCVD-grown layers of AlGaAs and InGaAs in thick films and strained layer complex structures is presented. It is concluded that the ternary composition of thick nonstrained layers can be accurately determined to within experimental errors using numerical algorithms. In the case of complex structures, thickness of all layers and the alloy composition of nonstrained layers can be determined simultaneously, provided that the correlations between parameters is no higher than 0.9.

Analysis of x-ray diffraction pattern and complex plane impedance plot of polypyrrole/titanium dioxide nanocomposite: A simulation study

NASA Astrophysics Data System (ADS)

Ravikiran, Y. T.; Vijaya Kumari, S. C.

2013-06-01

To innovate the properties of Polypyrrole/Titanium dioxide (PPy/TiO2) nanocomposite further, it has been synthesized by chemical polymerization technique. The nanostructure and monoclinic phase of the prepared composite have been confirmed by simulating the X-ray diffraction pattern (XRD). Also, complex plane impedance plot of the composite has been simulated to find equivalent resistance capacitance circuit (RC circuit) and numerical values of R and C have been predicted.

Demonstration of Laser Induced Acoustic Desoprtion - Chemical Ionization Mass Spectrometry (LIAD-CIMS) for Fragment-Free Measurements of Organic Aerosol Molecular Composition

NASA Astrophysics Data System (ADS)

Browne, E. C.; Abdelhamid, A.; Berry, J.; Alton, M.

2017-12-01

Organic compounds account for a significant portion of fine atmospheric aerosol. Current analytical techniques have provided insights on organic aerosol (OA) sources, composition, and chemical modification pathways. Despite this knowledge, large uncertainties remain and hinder our understanding of aerosol impacts on climate, air quality, and health. Measuring OA composition is challenging due to the complex chemical composition and the wide variation in the properties (e.g., vapor pressure, solubility, reactivity) of organic compounds. In many current measurement techniques, the ability to chemically resolve and quantify OA components is complicated by molecular decomposition, matrix effects, and/or preferential ionization mechanisms. Here, we utilize a novel desorption technique, laser induced acoustic desorption (LIAD), that generates fragment-free, neutral gas-phase molecules. We couple LIAD with a high-resolution chemical ionization mass spectrometer (CIMS) to provide molecular composition OA measurements. Through a series of laboratory experiments, we demonstrate the ability of this technique to measure large, thermally labile species without fragmentation/thermal decomposition. We discuss quantification and detection limits of this technique. We compare LIAD-CIMS measurements with thermal desorption-CIMS measurements using off-line measurements of ambient aerosol collected in Boulder, CO. Lastly, we discuss future development for on-line measurements of OA using LIAD-CIMS.

Relationships between botanical and chemical composition of forages: a multivariate approach to grasslands in the Western Italian Alps.

PubMed

Ravetto Enri, Simone; Renna, Manuela; Probo, Massimiliano; Lussiana, Carola; Battaglini, Luca M; Lonati, Michele; Lombardi, Giampiero

2017-03-01

Plant composition of species-rich mountain grasslands can affect the sensorial and chemical attributes of dairy and meat products, with implications for human health. A multivariate approach was used to analyse the complex relationships between vegetation characteristics (botanical composition and plant community variables) and chemical composition (proximate constituents and fatty acid profile) in mesophilic and dry vegetation ecological groups, comprising six different semi-natural grassland types in the Western Italian Alps. Mesophilic and dry grasslands were comparable in terms of phenology, biodiversity indices and proportion of botanical families. The content of total fatty acids and that of the most abundant fatty acids (alpha-linolenic, linoleic and palmitic acids) were mainly associated to nutrient-rich plant species, belonging to the mesophilic grassland ecological group. Mesophilic grasslands showed also higher values of crude protein, lower values of fibre content and they were related to higher pastoral values of vegetation compared to dry grasslands. The proximate composition and fatty acid profile appeared mainly single species dependent rather than botanical family dependent. These findings highlight that forage from mesophilic grasslands can provide higher nutritive value for ruminants and may be associated to ruminant-derived food products with a healthier fatty acid profile. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Systematic Relationships Between Lidar Observables and Sizes And Mineral Composition Of Dust Aerosols

NASA Technical Reports Server (NTRS)

Van Diedenhoven, Bastiaan; Stangl, Alexander; Perlwitz, Jan; Fridlind, Ann M.; Chowdhary, Jacek; Cairns, Brian

2015-01-01

The physical and chemical properties of soil dust aerosol particles fundamentally affect their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, heterogeneous formation of sulfates and nitrates on the surface of dust particles, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Lidar measurements, such as extinction-to-backscatter, color and depolarization ratios, are frequently used to distinguish between aerosol types with different physical and chemical properties. The chemical composition of aerosol particles determines their complex refractive index, hence affecting their backscattering properties. Here we present a study on how dust aerosol backscattering and depolarization properties at wavelengths of 355, 532 and 1064 nm are related to size and complex refractive index, which varies with the mineral composition of the dust. Dust aerosols are represented by collections of spheroids with a range of prolate and oblate aspect ratios and their optical properties are obtained using T-matrix calculations. We find simple, systematic relationships between lidar observables and the dust size and complex refractive index that may aid the use of space-based or airborne lidars for direct retrieval of dust properties or for the evaluation of chemical transport models using forward simulated lidar variables. In addition, we present first results on the spatial variation of forward-simulated lidar variables based on a dust model that accounts for the atmospheric cycle of eight different mineral types plus internal mixtures of seven mineral types with iron oxides, which was recently implemented in the NASA GISS Earth System ModelE2.

Detailed Chemical Characterization of Unresolved Complex Mixtures (UCM) inAtmospheric Organics: Insights into Emission Sources, Atmospheric Processing andSecondary Organic Aerosol Formation

EPA Science Inventory

Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...

Characteristics of biochar: Microchemical properties

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

Amonette, James E.; Joseph, Stephen

2009-03-13

Biochars, being derived from a variety of biological feedstocks that have been thermally degraded under a range of conditions, exhibit a correspondingly large range in composition and chemistry. Due in part to the somewhat chaotic nature of the thermal process itself, this chemical heterogeneity extends to the microscopic scale even within a single biochar. Thus, in the strictest sense, each biochar made under a particular feedstock/process combination presents a unique mixture of phases and microenvironments that gives rise to a unique set of chemical properties. In some respects, the chemical complexity of biochars rivals that of incipient soils. In thismore » chapter we focus on the chemical complexity of biochar as manifested primarily at a microscopic and molecular scale. We start by describing the biochar-formation process and how this influences the composition and nature of the solid phases, entrained oils, and their organization at the microscopic level. We then proceed to discuss the range of surface chemistries exhibited by biochars in terms of functional groups and electrochemical properties. We conclude with a discussion of the influence of these properties on the sorption of aqueous species at biochar surfaces.« less

Interface Reactions and Synthetic Reaction of Composite Systems

PubMed Central

Park, Joon Sik; Kim, Jeong Min

2010-01-01

Interface reactions in composite systems often determine their overall properties, since product phases usually formed at interfaces during composite fabrication processing make up a large portion of the composites. Since most composite materials represent a ternary or higher order materials system, many studies have focused on analyses of diffusion phenomena and kinetics in multicomponent systems. However, the understanding of the kinetic behavior increases the complexity, since the kinetics of each component during interdiffusion reactions need to be defined for interpreting composite behaviors. From this standpoint, it is important to clarify the interface reactions for producing compatible interfaces with desired product phases. A thermodynamic evaluation such as a chemical potential of involving components can provide an understanding of the diffusion reactions, which govern diffusion pathways and product phase formation. A strategic approach for designing compatible interfaces is discussed in terms of chemical potential diagrams and interface morphology, with some material examples.

Method for Hot Real-Time Analysis of Pyrolysis Vapors at Pilot Scale

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

Pomeroy, Marc D

Pyrolysis oils contain more than 400 compounds, up to 60% of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during quenching and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition before condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors at the pilot scale, many challenges must be overcome.

IR spectroscopic study of the chemical composition of epiphytic lichens

NASA Astrophysics Data System (ADS)

Meysurova, A. F.; Khizhnyak, S. D.; Pakhomov, P. M.

2011-11-01

Changes in the chemical composition of lichens exposed to pollutants are investigated by means of FTIR spectroscopy. According to model experiments, alkyl nitrates, ammonium salts, amines, and sulfones develop in the lichen thallus through the action of ammonia and nitric and sulfuric acids. Spectroscopic data of modeling experiments enabled nitrogen- and sulfur-containing substances to be identified as the main air pollutants in the vicinity of a pig-breeding complex and information to be obtained on the content of the pollutants and their impact on the lichens.

Geochemistry and tectonic setting of the Golabad granitoid complex (SW Nain, Iran)

NASA Astrophysics Data System (ADS)

Mansouri Esfahani, Mahin; Khalili, Mahmoud; Alaminia, Zahra

2018-03-01

The Oligo-Miocene Golabad granitoid complex intrusive into the Eocene volcanic rocks occurs in the Urumieh-Dokhtar Magmatic Arc (UDMA) in Iran. According to microscopic and chemical studies, the granitoid complex consists of three different rock types: 1) plutonic rocks comprising diorite, quartz diorite, granodiorite and granite; 2) volcanic rocks composed of basalt, andesite basalt, ± pyroxene bearing andesite and rhyolite, and 3) pyroclastic rocks. The main mineral constituents of these rocks are mostly plagioclase (oligoclase and andesine), quartz, K-feldspar, amphibole (magnesio-hornblende and actinolite-hornblende) and Mg-biotite. In addition, apatite, titanite, zircon, and opaque minerals are common accessory minerals. The studied enclaves are classified as mafic micro-granular enclaves (MME) with monzodiorite compositions. Geochemically, the rocks in this study represent medium to high-K calc-alkaline series, metaluminous and I-type nature. Plotting, the chemical composition of plagioclase on the An-Ab-Or ternary diagram, the temperature of crystallization is estimated to range from 700 to 900 °C at a pressure of 4.5 Kbar. High TiO2 values of biotites from the Golabad granitoid complex suggest magmatic origin and the crystallization temperature is estimated to range from 700 to 750 °C. The amphiboles according to their chemical analysis, are classified as igneous amphiboles generated in high oxygen fugacity conditions. The chemical data of the amphiboles and biotites pointed out to the I- type nature of the Golabad granitoid complex emplaced in an active continental margin subduction setting. The amphibole crystallization pressure was estimated by Al in amphibole varies from 1.09 to 2.28 Kbar. Using the calculated pressure the depth of the formation of the Golabad granitoid complex estimated from 4 to 9 Km.

Chemical characterization, antioxidant and antimicrobial activity of propolis obtained from Melipona quadrifasciata quadrifasciata and Tetragonisca angustula stingless bees.

PubMed

Torres, A R; Sandjo, L P; Friedemann, M T; Tomazzoli, M M; Maraschin, M; Mello, C F; Santos, A R S

2018-01-01

In this study, we investigated the chemical composition, and antioxidant and antibacterial properties of ethanolic extracts of propolis (EEP) from Melipona quadrifasciata quadrifasciata and Tetragonisca angustula. Chemical composition of EEP was determined by colorimetry and chromatographic (HPLC-DAD and UPLC-Q/TOF-MS/MS) analysis. Antimicrobial activity of EEP was evaluated against gram-positive (S. aureus, methicillin-resistant S. aureus, E. faecalis) and gram-negative (E. coli and K. pneumoniae) bacteria by the minimal inhibitory concentration (MIC) test using the microdilution method. Furthermore, the growth curve and integrity of cell membrane of S. aureus and E. coli were investigated using standard microbiological methods. HPLC-DAD analysis showed that the EEP of M. quadrifasciata quadrifasciata has a more complex chemical composition than the EEP of T. angustula. Moreover, UPLC-MS analyses of M. quadrifasciata quadrifascita indicated flavonoids and terpenes as major constituents. The bactericidal activity of both EEPs was higher against gram-positive bacteria than for gram-negative bacteria. The EEP from M. quadrifasciata quadrifasciata presented MIC values lower than the EEP from T. angustula for all tested bacteria. The EEP from M. quadrifasciata quadrifasciata caused lysis of the bacterial wall and release of intracellular components from both E. coli and S. aureus. Our findings indicate that the chemical composition of propolis from stingless bees is complex and depends on the species. The extract from M. quadrifasciata quadrifascita was more effective against gram-positive than gram-negative strains, especially against S. aureus and methicillin-resistant S. aureus compared to T. angustula extract, by a mechanism that involves disturbance of the bacterial cell membrane integrity.

Surfactant-free electrodeposition of reduced graphene oxide/copper composite coatings with enhanced wear resistance

NASA Astrophysics Data System (ADS)

Mai, Y. J.; Zhou, M. P.; Ling, H. J.; Chen, F. X.; Lian, W. Q.; Jie, X. H.

2018-03-01

How to uniformly disperse graphene sheets into the electrolyte is one of the main challenges to synthesize graphene enhanced nanocomposites by electrodeposition. A surfactant-free colloidal solution comprised of copper (II)-ethylene diamine tetra acetic acid ([CuIIEDTA]2-) complexes and graphene oxide (GO) sheets is proposed to electrodeposit reduced graphene oxide/copper (RGO/Cu) composite coatings. Anionic [CuIIEDTA]2- complexes stably coexist with negatively charged GO sheets due to the electrostatic repulsion between them, facilitating the electrochemical reduction and uniform dispersion of GO sheets into the copper matrix. The RGO/Cu composite coatings are well characterized by XRD, Raman, SEM and XPS. Their tribological behavior as a function of RGO content in composite coatings and normal loads are investigated. Also the chemical composition and topography of the wear tracks for the composite coatings are analyzed to deduce the lubricating and anti-wear mechanism of RGO/Cu composite coatings.

The Lewis Chemical Equilibrium Program with parametric study capability

NASA Technical Reports Server (NTRS)

Sevigny, R.

1981-01-01

The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

The Ackley City Batholith, southeastern Newfoundland: Evidence for crystal versus liquid-state fractionation

NASA Astrophysics Data System (ADS)

Whalen, J. B.

1983-08-01

The 345 ± 10 Ma old composite Ackley City Batholith of southeastern Newfoundland, consists largely of very felsic K-feldspar megacrystic granite and alaskite. Spatially related to the southeast contact of the alaskite are younger aplites and pegmatite, intrusive phases which are interpreted to be pan of a tilted, high level roof zone complex to the batholith. The compositions of the alaskite and roof zone complex define major and trace element gradients similar to those in voluminous high-silica eruptive suites; i.e., the alaskite is more chemically evolved (higher in Rb, lower in Ca, Fe, Mn, Ti, P, Sr, Ba and LREE) toward the roof. Apparently these chemical gradients in the batholith are restricted to the top 2 to 3 kms of the former magma chamber. Fractional crystallization is a plausible process for generating the chemical dispersion in the granites, although very high feldspar partition coefficients for Ba, Sr and Eu are required to generate the observed chemical gradients by a reasonable degree of fractional crystallization. Restriction of crystal fractionation to near the roof of the batholith may reflect a decreased viscosity which would facilitate crystal-liquid separation by processes such as filter pressing, flow differentiation or convective fractionation. The chemical gradients in these granites closely resemble those attributed in high-silica volcanics to the process of thermogravitational diffusion (TGD). Compositional gradients in the upper portion of a magma chamber are consistent with the TGD model. This model, although still poorly understood, is, like fractional crystallization, a plausible mechanism to generate the chemical features of the Ackley City granites.

Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis

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

Kehimkar, Benjamin; Hoggard, Jamin C.; Marney, Luke C.

There is an increased need to more fully assess and control the composition of kerosene based rocket propulsion fuels, namely RP-1 and RP-2. In particular, it is crucial to be able to make better quantitative connections between the following three attributes: (a) fuel performance, (b) fuel properties (flash point, density, kinematic viscosity, net heat of combustion, hydrogen content, etc) and (c) the chemical composition of a given fuel (i.e., specific chemical compounds and compound classes present as a result of feedstock blending and processing). Indeed, recent efforts in predicting fuel performance through modeling put greater emphasis on detailed and accuratemore » fuel properties and fuel compositional information. In this regard, advanced distillation curve (ADC) metrology provides improved data relative to classical boiling point and volatility curve techniques. Using ADC metrology, data obtained from RP-1 and RP-2 fuels provides compositional variation information that is directly relevant to predictive modeling of fuel performance. Often, in such studies, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is typically employed to provide chemical composition information. Building on approaches using GC-MS, but to glean substantially more chemical composition information from these complex fuels, we have recently studied the use of comprehensive two dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC - TOFMS) to provide chemical composition data that is significantly richer than that provided by GC-MS methods. In this report, by applying multivariate data analysis techniques, referred to as chemometrics, we are able to readily model (correlate) the chemical compositional information from RP-1 and RP-2 fuels provided using GC × GC - TOFMS, to the fuel property information such as that provided by the ADC method and other specification properties. We anticipate that this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an optimized approach to fuel formulation and specification for advanced engine cycles.« less

Correlation of ash-flow tuffs.

USGS Publications Warehouse

Hildreth, W.; Mahood, G.

1985-01-01

Discrimination and correlation of ash-flow sheets is important in structurally complex, long-lived volcanic fields where such sheets provide the best keys to the regional stratigraphic framework. Three-dimensional complexities resulting from pulsatory eruptions, sectorial emplacement, mechanical sorting during outflow, thermal and compositional zoning of magmas, the physical zoning of cooling units, and structural and erosional disruption can make such correlation and discrimination difficult. When lithologic, magnetic, petrographic, chemical, and isotopic criteria for correlating ash-flow sheets are critically evaluated, many problems and pitfalls can be identified. Distinctive phenocrysts, pumice clasts, and lithic fragments are among the more reliable criteria, as are high-precision K-Ar ages and thermal remanent magnetization (TRM) directions in unaltered welded tuff. Chemical correlation methods should rely principally upon welded or nonwelded pumice blocks, not upon the ash-flow matrix, which is subject to fractionation, mixing, and contamination during emplacement. Compositional zoning of most large sheets requires that many samples be analyzed before phenocryst, glass or whole-rock chemical trends can be used confidently as correlation criteria.-Authors

Effect of cationic lipid composition on properties of oligonucleotide/emulsion complexes: Physico-chemical and release studies.

PubMed

Martini, Erico; Fattal, Elias; de Oliveira, Mônica Cristina; Teixeira, Helder

2008-03-20

This paper describes the influence of cationic lipid composition on physico-chemical properties of complexes formed between oligonucleotides (ON) and cationic emulsions. Formulations containing medium chain triglycerides, egg lecithin, increasing amounts of either oleylamine (OA) or 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP), and water were prepared by a spontaneous emulsification procedure. ON adsorption on emulsions was evidenced by the inversion of the zeta-potential, the increase in droplet size, and the morphology of the oil droplet examined through transmission electron microscopy. Adsorption isotherms showed a higher amount of ON adsorbed on emulsions containing DOTAP when compared to emulsions containing OA. In a final step, the role of the main parameters, which may in fact influence the ON release rate from emulsions, was investigated. ON were progressively released from emulsions with an increase in dilution ratio and remained quite similar for both OA and DOTAP emulsions over time. Conversely, the effect of the cationic lipid composition was observed upon increasing the charge ratio of complexes. ON release at a same charge ratio was lower from emulsions containing DOTAP (bearing dioleyl chains) than from those containing OA (bearing monoleyl chain).

The Chemistry of Planet Formation

NASA Astrophysics Data System (ADS)

Oberg, Karin I.

2017-01-01

Exo-planets are common, and they span a large range of compositions. The origins of the observed diversity of planetary compositions is largely unconstrained, but must be linked to the planet formation physics and chemistry. Among planets that are Earth-like, a second question is how often such planets form hospitable to life. A fraction of exo-planets are observed to be ‘physically habitable’, i.e. of the right temperature and bulk composition to sustain a water-based prebiotic chemistry, but this does not automatically imply that they are rich in the building blocks of life, in organic molecules of different sizes and kinds, i.e. that they are chemically habitable. In this talk I will argue that characterizing the chemistry of protoplanetary disks, the formation sites of planets, is key to address both the origins of planetary bulk compositions and the likelihood of finding organic matter on planets. The most direct path to constrain the chemistry in disks is to directly observe it. In the age of ALMA it is for the first time possible to image the chemistry of planet formation, to determine locations of disk snowlines, and to map the distributions of different organic molecules. Recent ALMA highlights include constraints on CO snowline locations, the discovery of spectacular chemical ring systems, and first detections of more complex organic molecules. Observations can only provide chemical snapshots, however, and even ALMA is blind to the majority of the chemistry that shapes planet formation. To interpret observations and address the full chemical complexity in disks requires models, both toy models and astrochemical simulations. These models in turn must be informed by laboratory experiments, some of which will be shown in this talk. It is thus only when we combine observational, theoretical and experimental constraints that we can hope to characterize the chemistry of disks, and further, the chemical compositions of nascent planets.

Thermal Curing Process Monitoring of the Composite Material Using the FBG sensor

NASA Astrophysics Data System (ADS)

Zhang, Youhong; Chang, Xinlong; Zhang, Xiaojun; He, Xiangyong

2018-03-01

The raw composite material will suffer complex chemical and morphological changes during the thermal curing process, and it is difficult to monitor the curing process and curing effect. In this paper, the FBG sensor was embedded in the raw composite material to monitor the whole curing process. The experiment results showed that the FBG sensor can monitor the resin transformation and residual deformation of the composite material, and the FBG sensor can be applied to monitor the thermal curing process of the composite structure.

Chemical investigation of commercial grape seed derived products to assess quality and detect adulteration.

PubMed

Villani, Tom S; Reichert, William; Ferruzzi, Mario G; Pasinetti, Giulio M; Simon, James E; Wu, Qingli

2015-03-01

Fundamental concerns in quality control arise due to increasing use of grape seed extract (GSE) and the complex chemical composition of GSE. Proanthocyanidin monomers and oligomers are the major bioactive compounds in GSE. Given no standardized criteria for quality, large variation exists in the composition of commercial GSE supplements. Using HPLC/UV/MS, 21 commercial GSE containing products were purchased and chemically profiled, major compounds quantitated, and compared against authenticated grape seed extract, peanut skin extract, and pine bark extract. The antioxidant capacity and total polyphenol content for each sample was also determined and compared using standard techniques. Nine products were adulterated, found to contain peanut skin extract. A wide degree of variability in chemical composition was detected in commercial products, demonstrating the need for development of quality control standards for GSE. A TLC method was developed to allow for rapid and inexpensive detection of adulteration in GSE by peanut skin. Copyright © 2014 Elsevier Ltd. All rights reserved.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

NASA Technical Reports Server (NTRS)

Svehla, R. A.; Mcbride, B. J.

1973-01-01

A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.

Confocal Raman microspectroscopy reveals a convergence of the chemical composition in methanogenic archaea from a Siberian permafrost-affected soil.

PubMed

Serrano, Paloma; Hermelink, Antje; Lasch, Peter; de Vera, Jean-Pierre; König, Nicole; Burckhardt, Oliver; Wagner, Dirk

2015-12-01

Methanogenic archaea are widespread anaerobic microorganisms responsible for the production of biogenic methane. Several new species of psychrotolerant methanogenic archaea were recently isolated from a permafrost-affected soil in the Lena Delta (Siberia, Russia), showing an exceptional resistance against desiccation, osmotic stress, low temperatures, starvation, UV and ionizing radiation when compared to methanogens from non-permafrost environments. To gain a deeper insight into the differences observed in their resistance, we described the chemical composition of methanogenic strains from permafrost and non-permafrost environments using confocal Raman microspectroscopy (CRM). CRM is a powerful tool for microbial identification and provides fingerprint-like information about the chemical composition of the cells. Our results show that the chemical composition of methanogens from permafrost-affected soils presents a high homology and is remarkably different from strains inhabiting non-permafrost environments. In addition, we performed a phylogenetic reconstruction of the studied strains based on the functional gene mcrA to prove the different evolutionary relationship of the permafrost strains. We conclude that the permafrost methanogenic strains show a convergent chemical composition regardless of their genotype. This fact is likely to be the consequence of a complex adaptive process to the Siberian permafrost environment and might be the reason underlying their resistant nature. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Heterogeneous Oxidation of Laboratory-generated Mixed Composition and Biomass Burning Particles

NASA Astrophysics Data System (ADS)

Lim, C. Y.; Sugrue, R. A.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Browne, E. C.

2016-12-01

Heterogeneous oxidation of organic aerosol (OA) can significantly transform the chemical and physical properties of particulate matter in the atmosphere, leading to changes to the chemical composition of OA and potential volatilization of organic compounds. It has become increasingly apparent that the heterogeneous oxidation kinetics of OA depend on the phase and morphology of the particles. However, most laboratory experiments to date have been performed on single-component, purely organic precursors, which may exhibit fundamentally different behavior than more complex particles in the atmosphere. Here we present laboratory studies of the heterogeneous oxidation of two more complex chemical systems: thin, organic coatings on inorganic seed particles and biomass burning OA. In the first system, squalane (C30H62), a model compound for reduced OA, is coated onto dry ammonium sulfate particles at various thicknesses (10-20 nm) and exposed to hydroxyl radical (OH) in a flow tube reactor. In the second, we use a semi-batch reactor to study the heterogeneous OH-initiated oxidation of biomass burning particles as a part of the 2016 FIREX campaign in Missoula, MT. The resulting changes in chemical composition are monitored with an Aerodyne High Resolution Time-of-flight Aerosol Mass Spectrometer (AMS) and a soot-particle AMS for the non-refractory and refractory systems, respectively. We show that the heterogeneous oxidation kinetics of these multicomponent particles are substantially different than that of the single-component particles. The oxidation of organic coatings is rapid, undergoing dramatic changes to carbon oxidation state and losing a significant amount of organic mass after relatively low OH exposures (equivalent to several days of atmospheric processing). In the case of biomass burning particles, the kinetics are complex, with different components (inferred by aerosol mass spectrometry) undergoing oxidation at different rates.

Application of surface complexation models to anion adsorption by natural materials.

PubMed

Goldberg, Sabine

2014-10-01

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the in the United States of America.

[The concept of the development of the state of chemical-analytical environmental monitoring].

PubMed

Rakhmanin, Iu A; Malysheva, A G

2013-01-01

Chemical and analytical monitoring of the quality of environment is based on the accounting of the trace amount of substances. Considering the multicomponent composition of the environment and running processes of transformation of substances in it, in determination of the danger of the exposure to the chemical pollution of environment on population health there is necessary evaluation based on the simultaneous account of complex of substances really contained in the environment and supplying from different sources. Therefore, in the analytical monitoring of the quality and safety of the environment there is a necessary conversion from the orientation, based on the investigation of specific target substances, to estimation of real complex of compounds.

Submillimeter-wave Observations of Complex Organic Molecules in Southern Massive Star Forming Regions

NASA Astrophysics Data System (ADS)

Kamegai, Kazuhisa; Sakai, Takeshi; Sakai, Nami; Hirota, Tomoya; Yamamoto, Satoshi

2013-03-01

Submillimeter-wave observations of complex organic molecules toward southern massive star forming regions were carried out with ASTE 10m telescope. Methyl formate (HCOOCH3) and dimethyl ether (CH3OCH3) were detected in some molecular cloud cores with young protostars. Differences in chemical composition among neighboring cores were also found.

It's a Sooty Problem: Black Carbon and Aerosols from Space

NASA Technical Reports Server (NTRS)

Kaufman, Yoram J.

2005-01-01

Our knowledge of atmospheric aerosols (smoke, pollution, dust or sea salt particles, small enough to be suspended in the air), their evolution, composition, variability in space and time and interaction with solar radiation, clouds and precipitation is lacking despite decades of research. Just recently we recognized that understanding the global aerosol system is fundamental for progress in climate change and hydrological cycle research. While a single instrument was used to demonstrate 50 yrs ago that the global CO2 levels are rising, posing thread to our climate, we need an may of satellites, surface networks of radiometers, elaborated laboratory and field experiments coupled with chemical transport models to understand the global aerosol system. This complexity of the aerosol problem results from their short lifetime (1 week), variability of the chemical composition and complex chemical and physical processes in the atmosphere. The result is a heterogeneous distribution of aerosol and their properties. The new generation of satellites and surface networks of radiometers provides exciting opportunities to measure the aerosol properties and their interaction with clouds and climate. However farther development in the satellite capability, aerosol chemical models and climate models is needed to fully decipher the aerosol secrets with accuracy required to predict future climates.

Recrystallized Impact Glasses of the Onaping Formation and the Sudbury Igneous Complex, Sudbury Structure, Ontario, Canada

NASA Technical Reports Server (NTRS)

Dressler, B. O.; Weiser, T.; Brockmeyer, P.

1996-01-01

The origin of the Sudbury Structure and of the associated heterolithic breccias of the Onaping Formation and the Sudbury Igneous Complex have been controversial. While an impact origin of the structure has gained wide acceptance over the last 15 years, the origin of the recrystallized Onaping Formation glasses and of the igneous complex is still being debated. Recently the interpretation of the breccias of the Onaping Formation as suevitic fall-back impact breccias has been challenged. The igneous complex is interpreted either as a differentiated impact melt sheet or as a combination of an upper impact melt represented by the granophyre, and a lower, impact-triggered magmatic body consisting of the norite-sublayer formations. The Onaping Formation contains glasses as fluidal and nonfluidal fragments of various shapes and sizes. They are recrystallized, and our research indicates that they are petrographically heterogeneous and span a wide range of chemical compositions. These characteristics are not known from glasses of volcanic deposits. This suggests an origin by shock vitrification, an interpretation consistent with their association with numerous and varied country rock clasts that exhibit microscopic shock metamorphic features. The recrystallized glass fragments represent individual solid-state and liquid-state vitrified rocks or relatively small melt pods. The basal member lies beneath the Gray and Black members of the Onaping Formation and, where not metamorphic, has an igneous matrix. Igneous-textured melt bodies occur in the upper two members and above the Basal Member. A comparison of the chemical compositions of recrystallized glasses and of the matrices of the Basal Member and the melt bodies with the components and the bulk composition of the igneous complex is inconclusive as to the origin of the igneous complex. Basal Member matrix and Melt Bodies, on average, are chemically similar to the granophyre of the Sudbury Igneous Complex, suggesting that they are genetically related. Our chemical results allow interpretation of the entire igneous complex as a differentiated impact melt. However, they are also consistent with the granophyre alone being the impact melt and the nofite and quartz gabbro beneath it representing an impact-triggered magmatic body. This interpretation is preferred, as it is consistent with a number of field observations. A re-evaluation and extension of structural field studies and of geochemical data, as well as a systematic study of the contact relationships of the various igneous phases of the igneous complex, are needed to establish a Sudbury impact model consistent with all data and observations

Analysis of elemental maps from glaze to body of ancient Chinese Jun and Ru porcelain by micro-X-ray fluorescence

NASA Astrophysics Data System (ADS)

Cheng, Lin; Li, Rongwu; Pan, Qiuli; Li, Guoxia; Zhao, Weijuan; Liu, Zhiguo

2009-01-01

The reasons how the middle layer of Ru and Jun porcelain between the glaze and body came into being are still not completely understood. Here, elemental maps from the glaze to the body of pieces of ancient Chinese Ru and Jun porcelain were analyzed by micro-X-ray fluorescence. The results show the middle layer was probably formed by the chemical composition of the glaze turning into glassy states and undergoing complex physical-chemical reactions with the body. However, the middle layer of Jun porcelain was formed by the chemical composition of the glaze turning into glassy states and then infiltrating the body at high temperatures during the firing process.

Analytical methods to characterize heterogeneous raw material for thermal spray process: cored wire Inconel 625

NASA Astrophysics Data System (ADS)

Lindner, T.; Bonebeau, S.; Drehmann, R.; Grund, T.; Pawlowski, L.; Lampke, T.

2016-03-01

In wire arc spraying, the raw material needs to exhibit sufficient formability and ductility in order to be processed. By using an electrically conductive, metallic sheath, it is also possible to handle non-conductive and/or brittle materials such as ceramics. In comparison to massive wire, a cored wire has a heterogeneous material distribution. Due to this fact and the complex thermodynamic processes during wire arc spraying, it is very difficult to predict the resulting chemical composition in the coating with sufficient accuracy. An Inconel 625 cored wire was used to investigate this issue. In a comparative study, the analytical results of the raw material were compared to arc sprayed coatings and droplets, which were remelted in an arc furnace under argon atmosphere. Energy-dispersive X-ray spectroscopy (EDX) and X-ray fluorescence (XRF) analysis were used to determine the chemical composition. The phase determination was performed by X-ray diffraction (XRD). The results were related to the manufacturer specifications and evaluated in respect to differences in the chemical composition. The comparison between the feedstock powder, the remelted droplets and the thermally sprayed coatings allows to evaluate the influence of the processing methods on the resulting chemical and phase composition.

Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion.

PubMed

Guan, Bu Yuan; Yu, Xin Yao; Wu, Hao Bin; Lou, Xiong Wen David

2017-12-01

Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

NASA Technical Reports Server (NTRS)

Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

2006-01-01

A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides; synthesis of hydrogen terminated carbon chains as precursors to complex PAHs and to carbonaceous dust grains in general; nitriles as precursor to amino acids).

Application of Biologically-Based Lumping To Investigate the ...

EPA Pesticide Factsheets

People are often exposed to complex mixtures of environmental chemicals such as gasoline, tobacco smoke, water contaminants, or food additives. However, investigators have often considered complex mixtures as one lumped entity. Valuable information can be obtained from these experiments, though this simplification provides little insight into the impact of a mixture's chemical composition on toxicologically-relevant metabolic interactions that may occur among its constituents. We developed an approach that applies chemical lumping methods to complex mixtures, in this case gasoline, based on biologically relevant parameters used in physiologically-based pharmacokinetic (PBPK) modeling. Inhalation exposures were performed with rats to evaluate performance of our PBPK model. There were 109 chemicals identified and quantified in the vapor in the chamber. The time-course kinetic profiles of 10 target chemicals were also determined from blood samples collected during and following the in vivo experiments. A general PBPK model was used to compare the experimental data to the simulated values of blood concentration for the 10 target chemicals with various numbers of lumps, iteratively increasing from 0 to 99. Large reductions in simulation error were gained by incorporating enzymatic chemical interactions, in comparison to simulating the individual chemicals separately. The error was further reduced by lumping the 99 non-target chemicals. Application of this biologic

The Chemical Structure of the Hawaiian Mantle Plume

NASA Astrophysics Data System (ADS)

Ren, Z.; Hirano, N.; Hirata, T.; Takahashi, E.; Ingle, S.

2004-12-01

Numerous geochemical studies of Hawaiian basaltic lavas have shown that the Hawaiian mantle plume is isotopically heterogeneous. However, the distribution and scale of these heterogeneities remain unknown. This is essentially due to the complex interactions created by melting a heterogeneous source, subsequent aggregation of the melts on their way to the surface, and mixing that takes place in shallow magma chambers prior to eruption. In sum, the measured compositions of bulk lavas may represent only _eaverage_f compositions that do not fully reflect the complexity of either the mantle source heterogeneity and/or chemical structure. Melt inclusions, or samples of the local magma frozen in olivine phenocrysts during their formation, are better at recording the complex magmatic history than are the bulk samples. Here, we report major and trace element compositions of olivine-hosted melt inclusions from submarine Haleakala lavas that were collected by 2001-2002 JAMSTEC cruises measured by EPMA and LA-ICP-MS after homogenization at 1250° C, QFM for 20min. Melt inclusions from the submarine Hana Ridge (Haleakala volcano) show large ranges in CaO/Al2O3 (0.92-1.50), TiO2/Na2O (0.79-1.60) and Sr/Nb (14.56-36.60), Zr/Nb (6.48-16.95), ranging from Kilauea-like to Mauna Loa-like compositions within separately-sampled lavas as well as in a single host lava sample. Bulk rocks geochemistry shows that major element composition and trace element ratios such as Zr/Nb, Sr/Nb (Ren et al., 2004a, in press, J. Petrol.) together with Pb, Nd and Sr isotopic ratios (Ren et al., 2004b, submitted to J. Petrol.) of Haleakala shield volcano also display systematic compositional variation changing from a Kilauea-like in the submarine Hana Ridge (main shield stage) to Kilauea-Mauna Loa-like in the subaerial Honomanu stage (late shield stage, data from Chen and Frey, 1991). Some of the compositional variations in melt inclusions in single rocks are wider range than over-all variation observed in bulk rocks. It is important that both Kilauea-like and Mauna Loa-like compositions co-exist in melt inclusions in single submarine Hana Ridge rocks which are identified as Kilauea-like based on bulk geochemistry. These observations are inconsistent with the current interpretation that magma compositions are controlled by concentric zonation of the Hawaiian mantle plume (e.g. Kea component and Loa component), manifested as the Kea trend and the Loa trend volcanoes (e.g. Hauri, 1996; Lassiter et al., 1996). Our new data from olivine-hosted melt inclusions imply that the chemical structure of the Hawaiian mantle plume is significantly more complicated than previously modeled and the length-scale of chemical heterogeneity must be remarkably smaller than estimated based on bulk rock geochemistry.

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios.

PubMed

Nazmutdinov, Renat R; Zinkicheva, Tamara T; Vassiliev, Sergey Yu; Glukhov, Dmitri V; Tsirlina, Galina A; Probst, Michael

2010-04-01

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms ("dimers") was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition. Copyright 2010. Published by Elsevier B.V.

Generalised syntheses of ordered mesoporous oxides: the atrane route

NASA Astrophysics Data System (ADS)

Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

2000-06-01

A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

Composition analysis by scanning femtosecond laser ultraprobing (CASFLU).

DOEpatents

Ishikawa, Muriel Y.; Wood, Lowell L.; Campbell, E. Michael; Stuart, Brent C.; Perry, Michael D.

2002-01-01

The composition analysis by scanning femtosecond ultraprobing (CASFLU) technology scans a focused train of extremely short-duration, very intense laser pulses across a sample. The partially-ionized plasma ablated by each pulse is spectrometrically analyzed in real time, determining the ablated material's composition. The steering of the scanned beam thus is computer directed to either continue ablative material-removal at the same site or to successively remove nearby material for the same type of composition analysis. This invention has utility in high-speed chemical-elemental, molecular-fragment and isotopic analyses of the microstructure composition of complex objects, e.g., the oxygen isotopic compositions of large populations of single osteons in bone.

Characterisation of metals in the electronic waste of complex mixtures of end-of-life ICT products for development of cleaner recovery technology.

PubMed

Sun, Z H I; Xiao, Y; Sietsma, J; Agterhuis, H; Visser, G; Yang, Y

2015-01-01

Recycling of valuable metals from electronic waste, especially complex mixtures of end-of-life information and communication technology (ICT) products, is of great difficulty due to their complexity and heterogeneity. One of the important reasons is the lack of comprehensive characterisation on such materials, i.e. accurate compositions, physical/chemical properties. In the present research, we focus on developing methodologies for the characterisation of metals in an industrially processed ICT waste. The morphology, particle size distribution, compositional distribution, occurrence, liberation as well as the thermo-chemical properties of the ICT waste were investigated with various characterisation techniques, including X-ray Fluorescence Spectrometry (XRF), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) with energy dispersed spectroscopy (EDS). Due to the high heterogeneity of the material, special sample preparation procedures were introduced to minimise the discrepancies during compositional analyses. As a result, a clearer overview of the ICT waste has been reached. This research provides better understanding of the extractability of each metal and improves the awareness of potential obstacles for extraction. It will lead to smarter decisions during further development of a clean and effective recovery process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Plasma filtering techniques for nuclear waste remediation

DOE PAGES

Gueroult, Renaud; Hobbs, David T.; Fisch, Nathaniel J.

2015-04-24

Nuclear waste cleanup is challenged by the handling of feed stocks that are both unknown and complex. Plasma filtering, operating on dissociated elements, offers advantages over chemical methods in processing such wastes. The costs incurred by plasma mass filtering for nuclear waste pretreatment, before ultimate disposal, are similar to those for chemical pretreatment. However, significant savings might be achieved in minimizing the waste mass. As a result, this advantage may be realized over a large range of chemical waste compositions, thereby addressing the heterogeneity of legacy nuclear waste.

The parent magma of the Nakhla (SNC) meteorite: Reconciliation of composition estimates from magmatic inclusions and element partitioning

NASA Technical Reports Server (NTRS)

Treiman, A. H.

1993-01-01

The composition of the parent magma of the Nakhla meteorite was difficult to determine, because it is accumulate rock, enriched in olivine and augite relative to a basalt magma. A parent magma composition is estimated from electron microprobe area analyses of magmatic inclusions in olivine. This composition is consistent with an independent estimate based on the same inclusions, and with chemical equilibria with the cores of Nakhla's augites. This composition reconciles most of the previous estimates of Nakhla's magma composition, and obviates the need for complex magmatic processes. Inconsistency between this composition and those calculated previously suggests that magma flowed through and crystallized into Nakhla as it cooled.

Mathematical Description of Complex Chemical Kinetics and Application to CFD Modeling Codes

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1993-01-01

A major effort in combustion research at the present time is devoted to the theoretical modeling of practical combustion systems. These include turbojet and ramjet air-breathing engines as well as ground-based gas-turbine power generating systems. The ability to use computational modeling extensively in designing these products not only saves time and money, but also helps designers meet the quite rigorous environmental standards that have been imposed on all combustion devices. The goal is to combine the very complex solution of the Navier-Stokes flow equations with realistic turbulence and heat-release models into a single computer code. Such a computational fluid-dynamic (CFD) code simulates the coupling of fluid mechanics with the chemistry of combustion to describe the practical devices. This paper will focus on the task of developing a simplified chemical model which can predict realistic heat-release rates as well as species composition profiles, and is also computationally rapid. We first discuss the mathematical techniques used to describe a complex, multistep fuel oxidation chemical reaction and develop a detailed mechanism for the process. We then show how this mechanism may be reduced and simplified to give an approximate model which adequately predicts heat release rates and a limited number of species composition profiles, but is computationally much faster than the original one. Only such a model can be incorporated into a CFD code without adding significantly to long computation times. Finally, we present some of the recent advances in the development of these simplified chemical mechanisms.

Mathematical description of complex chemical kinetics and application to CFD modeling codes

NASA Technical Reports Server (NTRS)

Bittker, D. A.

1993-01-01

A major effort in combustion research at the present time is devoted to the theoretical modeling of practical combustion systems. These include turbojet and ramjet air-breathing engines as well as ground-based gas-turbine power generating systems. The ability to use computational modeling extensively in designing these products not only saves time and money, but also helps designers meet the quite rigorous environmental standards that have been imposed on all combustion devices. The goal is to combine the very complex solution of the Navier-Stokes flow equations with realistic turbulence and heat-release models into a single computer code. Such a computational fluid-dynamic (CFD) code simulates the coupling of fluid mechanics with the chemistry of combustion to describe the practical devices. This paper will focus on the task of developing a simplified chemical model which can predict realistic heat-release rates as well as species composition profiles, and is also computationally rapid. We first discuss the mathematical techniques used to describe a complex, multistep fuel oxidation chemical reaction and develop a detailed mechanism for the process. We then show how this mechanism may be reduced and simplified to give an approximate model which adequately predicts heat release rates and a limited number of species composition profiles, but is computationally much faster than the original one. Only such a model can be incorporated into a CFD code without adding significantly to long computation times. Finally, we present some of the recent advances in the development of these simplified chemical mechanisms.

Digitally tunable physicochemical coding of material composition and topography in continuous microfibres.

PubMed

Kang, Edward; Jeong, Gi Seok; Choi, Yoon Young; Lee, Kwang Ho; Khademhosseini, Ali; Lee, Sang-Hoon

2011-09-04

Heterotypic functional materials with compositional and topographical properties that vary spatiotemporally on the micro- or nanoscale are common in nature. However, fabricating such complex materials in the laboratory remains challenging. Here we describe a method to continuously create microfibres with tunable morphological, structural and chemical features using a microfluidic system consisting of a digital, programmable flow control that mimics the silk-spinning process of spiders. With this method we fabricated hydrogel microfibres coded with varying chemical composition and topography along the fibre, including gas micro-bubbles as well as nanoporous spindle-knots and joints that enabled directional water collection. We also explored the potential use of the coded microfibres for tissue engineering applications by creating multifunctional microfibres with a spatially controlled co-culture of encapsulated cells.

A Novel Wearable Electronic Nose for Healthcare Based on Flexible Printed Chemical Sensor Array

PubMed Central

Lorwongtragool, Panida; Sowade, Enrico; Watthanawisuth, Natthapol; Baumann, Reinhard R.; Kerdcharoen, Teerakiat

2014-01-01

A novel wearable electronic nose for armpit odor analysis is proposed by using a low-cost chemical sensor array integrated in a ZigBee wireless communication system. We report the development of a carbon nanotubes (CNTs)/polymer sensor array based on inkjet printing technology. With this technique both composite-like layer and actual composite film of CNTs/polymer were prepared as sensing layers for the chemical sensor array. The sensor array can response to a variety of complex odors and is installed in a prototype of wearable e-nose for monitoring the axillary odor released from human body. The wearable e-nose allows the classification of different armpit odors and the amount of the volatiles released as a function of level of skin hygiene upon different activities. PMID:25340447

Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis.

PubMed

Kehimkar, Benjamin; Hoggard, Jamin C; Marney, Luke C; Billingsley, Matthew C; Fraga, Carlos G; Bruno, Thomas J; Synovec, Robert E

2014-01-31

There is an increased need to more fully assess and control the composition of kerosene-based rocket propulsion fuels such as RP-1. In particular, it is critical to make better quantitative connections among the following three attributes: fuel performance (thermal stability, sooting propensity, engine specific impulse, etc.), fuel properties (such as flash point, density, kinematic viscosity, net heat of combustion, and hydrogen content), and the chemical composition of a given fuel, i.e., amounts of specific chemical compounds and compound classes present in a fuel as a result of feedstock blending and/or processing. Recent efforts in predicting fuel chemical and physical behavior through modeling put greater emphasis on attaining detailed and accurate fuel properties and fuel composition information. Often, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is employed to provide chemical composition information. Building on approaches that used GC-MS, but to glean substantially more chemical information from these complex fuels, we recently studied the use of comprehensive two dimensional (2D) gas chromatography combined with time-of-flight mass spectrometry (GC×GC-TOFMS) using a "reversed column" format: RTX-wax column for the first dimension, and a RTX-1 column for the second dimension. In this report, by applying chemometric data analysis, specifically partial least-squares (PLS) regression analysis, we are able to readily model (and correlate) the chemical compositional information provided by use of GC×GC-TOFMS to RP-1 fuel property information such as density, kinematic viscosity, net heat of combustion, and so on. Furthermore, we readily identified compounds that contribute significantly to measured differences in fuel properties based on results from the PLS models. We anticipate this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an improved approach to fuel formulation and specification for advanced engine cycles. Copyright © 2014 Elsevier B.V. All rights reserved.

[Heterosis, macromolecular composition and several physico-chemical properties of the nucleolar-chromatic complex].

PubMed

Shereshevskaia, Ts M; Krasnopol'skiĭ, Iu M; Verkhovskiĭ, B A

1977-01-01

The nucleolar-chromatin complex of the hybrids liver cells is shown to contain a larger amount of RNA and phospholipids. When teeated with 1.0 M NaCl nucleoproteins of hybrid organisms display greater dissociation. A large number of free loci was determined in the matrix when titrating nucleolar chromatin complex with actinomycin "D". The effect of heterosis might be connected with a specific physiochemical state of chromosome in hybrid organisms.

Production of refractory chamotte particle-reinforced geopolymer composite

NASA Astrophysics Data System (ADS)

Kovářík, T.; Kullová, L.; Rieger, D.

2016-04-01

Geopolymer resins are obtained by alkaline activation of aluminosilicate sources where raw calcined clays are one of the suitable potentialities. Besides the fact that chemical composition has an essential effect on final properties of the geopolymer binder, the type of filler strongly affected resulting properties of such granular composite. However, very few comparative studies have been done on detail description of composite systems: binder - granular filler, in relation to aggregate gradation design and rheology properties of the mixture. The aim of this work is to develop and describe granular composite concerning workability of the mixture and kinetics of geopolymerization/polycondensation through flow behaviour. The rheological measurements indicated that initial viscosities of the mixtures and their evolution are different for various proportions of the filler. Moreover, it was demonstrated that increase in complex viscosity responds to the creation of chemical bonds and the formation of structural network. Finally, a correlation of the mechanism of geopolymer formation was carried out by differential scanning calorimetry (DSC).

Chemical composition of donor-acceptor complexes of hydroxyoxo(5,10,15,20-tetraphenylporphinato)molybdenum(V) with 3,5-dimethylpyrazole and equilibrium constants for their formation

NASA Astrophysics Data System (ADS)

Motorina, E. V.; Lomova, T. N.

2017-11-01

The results from a quantitative study of reactions between hydroxyoxo(5,10,15,20-tetraphenylporphinato)molybdenum(V) (O=Mo(OH)TPP) and 3,5-dimethylpyrazole, a biologically active base, in toluene are presented. The chemical structure and key parameters of intermediates and reaction products are determined by spectral means. The equilibrium constant ( K = 51.3 L/mol) is calculated and a full kinetic description of simple reactions that occur in this system during complex transformation is obtained. The prospect of using a mixed porphyrin-containing complex as a receptor for 3,5-dimethylpyrazole, a building block for alkaloids and pharmaceutical preparations, is substantiated.

In situ U-Th-Pb ages of the Miaoya carbonatite complex in the South Qinling orogenic belt, central China

NASA Astrophysics Data System (ADS)

Ying, Yuancan; Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Yang, Yueheng

2017-10-01

The Miaoya carbonatite complex in the South Qinling orogenic belt hosts one of the largest rare earth element (REE)-Nb deposits in China that is composed of carbonatite and syenite. The emplacement age of the complex and the geochronological relationship between the carbonatite and syenite have long been debated. In this study, in situ U-Th-Pb ages have been obtained for the constituent minerals zircon, monazite and columbite from carbonatite and syenite of the Miaoya complex, together with their chemical and isotopic compositions. In situ trace element compositions for zircon from carbonatite and syenite are highly variable. The zircon displays slightly heavy REE (HREE)-enriched chondrite-normalized patterns with no Eu anomaly and various light REE (LREE) contents. In situ Th-Pb dating for zircon from the Miaoya complex by laser ablation ICP-MS yields ages of 442.6 ± 4.0 Ma (n = 53) for syenite and 426.5 ± 8.0 Ma (n = 23) for carbonatite. Monazite from carbonatite and syenite shows similar chondrite-normalized REE patterns and yields a consistent Th-Pb age of 240 Ma. Based on petrographic and chemical composition, columbite from the carbonatite can be identified into two groups. The columbite dispersed within carbonatite is characterized by slightly LREE-enriched chondrite-normalized REE patterns, whereas columbite associated with apatite is characterized by LREE-depleted trends. Columbite has been further determined to have a weighted mean 206Pb/238U age of 232.8 ± 4.5 Ma (n = 9) using LA-ICP-MS. Detailed geochronological and chemical investigations suggest that there were two major episodes of magmatic/metasomatic activities in the formational history of the Miaoya carbonatite complex. The early alkaline magmatism emplaced in the Silurian was related to the opening of the Mianlue Ocean, whereas the late metasomatism or hydrothermal overprint occurred during the Triassic South Qinling orogeny. The latter serves as the major ore formation period for both REE (e.g., monazite) and Nb (e.g., columbite).

Natural organic matter and the event horizon of mass spectrometry.

PubMed

Hertkorn, N; Frommberger, M; Witt, M; Koch, B P; Schmitt-Kopplin, Ph; Perdue, E M

2008-12-01

Soils, sediments, freshwaters, and marine waters contain natural organic matter (NOM), an exceedingly complex mixture of organic compounds that collectively exhibit a nearly continuous range of properties (size-reactivity continuum). NOM is composed mainly of carbon, hydrogen, and oxygen, with minor contributions from heteroatoms such as nitrogen, sulfur, and phosphorus. Suwannee River fulvic acid (SuwFA) is a fraction of NOM that is relatively depleted in heteroatoms. Ultrahigh resolution Fourier transform ion cyclotron (FTICR) mass spectra of SuwFA reveal several thousand molecular formulas, corresponding in turn to several hundred thousand distinct chemical environments of carbon even without accountancy of isomers. The mass difference deltam among adjoining C,H,O-molecules between and within clusters of nominal mass is inversely related to molecular dissimilarity: any decrease of deltam imposes an ever growing mandatory difference in molecular composition. Molecular formulas that are expected for likely biochemical precursor molecules are notably absent from these spectra, indicating that SuwFA is the product of diagenetic reactions that have altered the major components of biomass beyond the point of recognition. The degree of complexity of SuwFA can be brought into sharp focus through comparison with the theoretical limits of chemical complexity, as constrained and quantized by the fundamentals of chemical binding. The theoretical C,H,O-compositional space denotes the isomer-filtered complement of the entire, very vast space of molecular structures composed solely of carbon, hydrogen, and oxygen. The molecular formulas within SuwFA occupy a sizable proportion of the theoretical C,H,O-compositional space. A 100 percent coverage of the theoretically feasible C,H,O-compositional space by SuwFA molecules is attained throughout a sizable range of mass and H/C and O/C elemental ratios. The substantial differences between (and complementarity of) the SuwFA molecular formulas that are observed using six different modes of ionization (APCI, APPI, and ESI in positive and negative modus) imply considerable selectivity of the ionization process and suggest that the observed mass spectra represent simplified projections of still more complex mixtures.

Characterizing cosmochemical materials with genetic affinities to the Earth: Genetic and chronological diversity within the IAB iron meteorite complex

NASA Astrophysics Data System (ADS)

Worsham, Emily A.; Bermingham, Katherine R.; Walker, Richard J.

2017-06-01

The IAB iron meteorite complex consists of a main group (MG) and five chemical subgroups (sLL, sLM, sLH, sHL, and sHH). Here, mass-independent Mo and radiogenic 182W isotope compositions are reported for IAB complex meteorites to evaluate the genetics and chronology, respectively, of the MG and subgroups. Osmium isotopes are used to correct for cosmic ray exposure effects on isotopes of Mo and W. The MG and three subgroups (i.e., sLL, sLM, and sLH), characterized by low Au abundances, have the same Mo isotopic compositions within analytical uncertainty, consistent with a common genetic origin. These meteorites, together with winonaites, are the only cosmochemical materials yet identified with Mo isotopic compositions that are identical to Earth. The Mo isotopic compositions of two subgroups characterized by higher Au abundances (sHL and sHH) are identical to one another within uncertainty, but differ from the low Au subgroups, indicating derivation from genetically distinct materials. The MG has a 182W, post calcium-aluminum inclusion (CAI) formation model age of 3.4 ± 0.7 Ma. One of the low Au subgroups (sLM) is ∼1.7 Ma younger, whereas the high Au subgroups are ∼1.5-3 Ma older. The new Mo-W data, coupled with chemical data, indicate that the MG and the low Au subgroups formed in different impact-generated melts, some of which evidently formed on a chemically disparate, but genetically identical parent body. The high Au subgroups likely formed via core-formation processes on separate, internally-heated parent bodies from other IAB subgroups. The IAB complex meteorites fall on a linear trend defined by 94Mo/96Mo vs. 95Mo/96Mo, along with most other iron meteorite groups. Variation along this line was caused by mixing between at least two nebular components. One component was likely a pure s-process enriched nucleosynthetic carrier, and the other a homogenized nebular component. Sombrerete, currently classified as an sHL iron, has a Mo isotopic composition that is distinct from all IAB complex meteorites analyzed here. Along with group IVB iron meteorites and some ungrouped iron meteorites, it falls on a separate line from other meteorites which may reflect addition of an r-process-enriched component, and it should no longer be classified as a IAB iron.

Structure and chemical composition of layers adsorbed at interfaces with champagne.

PubMed

Aguié-Béghin, V; Adriaensen, Y; Péron, N; Valade, M; Rouxhet, P; Douillard, R

2009-11-11

The structure and the chemical composition of the layer adsorbed at interfaces involving champagne have been investigated using native champagne, as well as ultrafiltrate (UFch) and ultraconcentrate (UCch) obtained by ultrafiltration with a 10(4) nominal molar mass cutoff. The layer adsorbed at the air/liquid interface was examined by surface tension and ellipsometry kinetic measurements. Brewster angle microscopy demonstrated that the layer formed on polystyrene by adsorption or drop evaporation was heterogeneous, with a domain structure presenting similarities with the layer adsorbed at the air/liquid interface. The surface chemical composition of polystyrene with the adlayer was determined by X-ray photoelectron spectroscopy (XPS). The contribution of champagne constituents varied according to the liquid (native, UFch, and UCch) and to the procedure of adlayer formation (evaporation, adsorption, and adsorption + rinsing). However, their chemical composition was not significantly influenced either by ultrafiltration or by the procedure of deposition on polystyrene. Modeling this composition in terms of classes of model compounds gave approximately 35% (w/w) of proteins and 65% (w/w) of polysaccharides. In the adlayer, the carboxyl groups or esters represent about 18% of carbon due to nonpolypeptidic compounds, indicating the presence of either uronic acids in the complex structure of pectic polysaccharides or of polyphenolic esters. This structural and chemical information and its relationship with the experimental procedures indicate that proteins alone cannot be used as a realistic model for the macromolecules forming the adsorption layer of champagne. Polysaccharides, the other major macromolecular components of champagne wine, are assembled with proteins at the interfaces, in agreement with the heterogeneous character of the adsorbed layer at interfaces.

Optical, thermal and morphological study of ZnS doped PVA polymer nano composites

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Sagar, Rohan N.; Hegde, Shreedatta

2018-05-01

The effect of ZnS nano particle doping on optical, thermal properties and morphological study of the PVA polymer has been investigated using FTIR, UV-Visible and TGA, FESEM techniques. Nano sized ZnS particles were synthesized by a simple wet chemical route. Pure and ZnS/PVA nano composites were prepared using solution casting technique. The FTIR study confirms that the ZnS nano particles interacts with the OH group of PVA polymer and forms the complex. The formation of these complexes affects the optical and thermal properties of the composite. The changes in optical properties were studied using UV-Vis absorption method. The variation in thermal property was analysed using TGA results. The modified surface morphology analysis was carried out using FESEM.

Precise Chemical Analyses of Planetary Surfaces

NASA Technical Reports Server (NTRS)

Kring, David; Schweitzer, Jeffrey; Meyer, Charles; Trombka, Jacob; Freund, Friedemann; Economou, Thanasis; Yen, Albert; Kim, Soon Sam; Treiman, Allan H.; Blake, David;

Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States

EPA Science Inventory

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results sug...

Transferring mixtures of chemicals from sediment to a bioassay using silicone-based passive sampling and dosing.

PubMed

Mustajärvi, Lukas; Eriksson-Wiklund, Ann-Kristin; Gorokhova, Elena; Jahnke, Annika; Sobek, Anna

2017-11-15

Environmental mixtures of chemicals consist of a countless number of compounds with unknown identity and quantity. Yet, chemical regulation is mainly built around the assessment of single chemicals. Existing frameworks for assessing the toxicity of mixtures require that both the chemical composition and quantity are known. Quantitative analyses of the chemical composition of environmental mixtures are however extremely challenging and resource-demanding. Bioassays may therefore serve as a useful approach for investigating the combined toxicity of environmental mixtures of chemicals in a cost-efficient and holistic manner. In this study, an unknown environmental mixture of bioavailable semi-hydrophobic to hydrophobic chemicals was sampled from a contaminated sediment in a coastal Baltic Sea area using silicone polydimethylsiloxane (PDMS) as an equilibrium passive sampler. The chemical mixture was transferred to a PDMS-based passive dosing system, and its applicability was demonstrated using green algae Tetraselmis suecica in a cell viability assay. The proportion of dead cells increased significantly with increasing exposure level and in a dose-response manner. At an ambient concentration, the proportion of dead cells in the population was nearly doubled compared to the control; however, the difference was non-significant due to high inter-replicate variability and a low number of replicates. The validation of the test system regarding equilibrium sampling, loading efficiency into the passive dosing polymer, stability of the mixture composition, and low algal mortality in control treatments demonstrates that combining equilibrium passive sampling and passive dosing is a promising tool for investigating the toxicity of bioavailable semi-hydrophobic and hydrophobic chemicals in complex environmental mixtures.

Plasma filtering techniques for nuclear waste remediation.

PubMed

Gueroult, Renaud; Hobbs, David T; Fisch, Nathaniel J

2015-10-30

Nuclear waste cleanup is challenged by the handling of feed stocks that are both unknown and complex. Plasma filtering, operating on dissociated elements, offers advantages over chemical methods in processing such wastes. The costs incurred by plasma mass filtering for nuclear waste pretreatment, before ultimate disposal, are similar to those for chemical pretreatment. However, significant savings might be achieved in minimizing the waste mass. This advantage may be realized over a large range of chemical waste compositions, thereby addressing the heterogeneity of legacy nuclear waste. Copyright © 2015 Elsevier B.V. All rights reserved.

Interstellar Ice and Dust: The Feedstock of the Solar System

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Morrison, David (Technical Monitor)

1994-01-01

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Mo(3)Sb(7-x)Te(x) for Thermoelectric Power Generation

NASA Technical Reports Server (NTRS)

Snyder, G. Jeffrey; Gascoin, Frank S.; Rasmussen, Julia

2009-01-01

Compounds having compositions of Mo(3)Sb(7-x)Te(x) (where x = 1.5 or 1.6) have been investigated as candidate thermoelectric materials. These compounds are members of a class of semiconductors that includes previously known thermoelectric materials. All of these compounds have complex crystalline and electronic structures. Through selection of chemical compositions and processing conditions, it may be possible to alter the structures to enhance or optimize thermoelectric properties.

Morphology-preserving chemical conversion of bioorganic and inorganic templates

NASA Astrophysics Data System (ADS)

Vernon, Jonathan Paul

The generation of nanostructured assemblies with complex (three-dimensional, 3D) self-assembled morphologies and with complex (multicomponent) tailorable inorganic compositions is of considerable technological and scientific interest. This dissertation demonstrates self-assembled 3D organic templates of biogenic origin can be converted into replicas comprised of numerous other functional nanocrystalline inorganic materials. Nature provides a spectacular variety of biologically-assembled 3D organic structures with intricate, hierarchical (macro-to-micro-to-nanoscale) morphologies. Such processing on readily-available structurally complex templates provides a framework for chemical conversion of synthetic organic templates and, potentially, production of organic/inorganic composites. Four specific research thrusts are detailed in this document. First, chemical conversion of a nanostructured bioorganic template into a multicomponent oxide compound (tetragonal BaTiO3) via SSG coating and subsequent morphology-preserving microwave hydrothermal processing is demonstrated. Second, morphology-preserving chemical conversion of bioorganic templates into hierarchical photoluminescent microparticles is demonstrated to reveal both the dramatic change in properties such processing can provide, and the potential utility of chemically transformed templates in anti-counterfeiting / authentication applications. Third, determination of the reaction mechanism(s) for morphology-preserving microwave hydrothermal conversion of TiO2 to BaTiO3, through Au inert markers on single crystal rutile titania, is detailed. Finally, utilization of constructive coating techniques (SSG) and moderate temperature (< 500°C) heat treatments to modify and replicate structural color is coupled with deconstructive focused ion beam microsurgery to prepare samples for microscale structure interrogation. Specifically, the effects of coating thickness and composition on reflection spectra of structurally colored templates are examined. Also, the effects of the replacement of natural material with higher index of refraction inorganic materials on optical properties are discussed. The three processing research thrusts constituting chapters 1, 2 and 4 take advantage of moderate temperature processing to ensure nanocrystalline materials, either for shape preservation or to prevent scattering in optical applications. The research thrust detailed in chapter 3 examines hydrothermal conversion of TiO2 to BaTiO3, not only to identify the reaction mechanism(s) involved in hydrothermal conversion under morphology-preserving conditions, but also to introduce inert marker experiments to the field of microwave hydrothermal processing.

Chemical weathering from the CoDA (Compositional Data Analysis) point of view: new insights for the Alpine rivers geochemistry

NASA Astrophysics Data System (ADS)

Gozzi, Caterina; Buccianti, Antonella; Frondini, Francesco

2017-04-01

The aim of this contribution is to explore the relationship among weathering reactions, the sample space of compositional data and fractals by means of distributional analysis. Weathering reactions represent the transfer of heat and entropy to the environment in geochemical cycles. Chemical weathering is a key process for understanding the global cycle of elements, both on long and short-terms and chemical weathering rates are complex functions of many factors including dissolution kinetics of minerals, mechanical erosion, lithology. Compositional data express the relative (proportional) abundance of chemical elements/species in a given total (i.e. volume or weight) so that compositions pertaining to the peculiar geometry of the simplex sample space. Fractals are temporal or spatial objects with self-similarity and scale invariance, so that internal structures repeat themselves over multiple levels of magnification or scales of measurement. Gibbs's free energy and the application of the Law Mass Action can be used to model weathering reactions, under the hypothesis of chemical equilibrium. Compositional data are obtained in the analytical phase after the determination of the concentrations of chemicals in sampled solid, liquid or gaseous materials. Fractals can be measured by using their fractal dimensions. The presence of fractal structures can be observed when the frequency distribution of isometric log-ratio coordinates is investigated, showing the logarithm of the cumulative number of samples exceeding a certain coordinate value plotted against the coordinate value itself. Isometric log-ratio coordinates (or balances) can be constructed by using the sequential binary partition (SBP) method. The balances can be identified to maintain, as far as possible, the similarity with a corresponding weathering reaction (Buccianti & Zuo, 2016). As an alternative, balances can be derived after the multivariate investigation of the variance-covariance structure of the compositional matrix. In both cases the idea is to probe the behaviour of geochemical processes to be analysed in time or space. An application example is presented for the chemistry of the surficial waters of the Alpine region (Donnini et al., 2016). The emergence of fractal structures indicates the presence of dissipative systems, which require complexity, large numbers of inter-connected elements and stochasticity requiring caution in the use of classical spatial methods to represent geochemical phenomena. Buccianti A. & Zuo R., 2016. Weathering reactions and isometric log-ratio coordinates: Do they speak to each other? Applied Geochemistry, 75, 189-199. Donnini M., Frondini F., Probst J.L., Probst A., Cardellini C., Marchesini I., Guzzetti F., 2016. Chemical weathering and consumption of atmospheric carbon dioxide in the Alpine region. Global and Planetary Change, 136 (2016) 65-81.

Disentangling oil weathering using GC x GC. 1. chromatogram analysis.

PubMed

Arey, J Samuel; Nelson, Robert K; Reddy, Christopher M

2007-08-15

Historically, the thousands of compounds found in oils constituted an "unresolved complex mixture" that frustrated efforts to analyze oil weathering. Moreover, different weathering processes inflict rich and diverse signatures of compositional change in oil, and conventional methods do not effectively decode this elaborate record. Using comprehensive two-dimensional gas chromatography (GC x GC), we can separate thousands of hydrocarbon components and simultaneously estimate their chemical properties. We investigated 13 weathered field samples collected from the Bouchard 120 heavy fuel oil spill in Buzzards Bay, Massachusetts in 2003. We first mapped hydrocarbon vapor pressures and aqueous solubilities onto the compositional space explored by GC x GC chromatograms of weathered samples. Then we developed methods to quantitatively decouple mass loss patterns associated with evaporation and dissolution. The compositional complexity of oil, traditionally considered an obstacle, was now an advantage. We exploited the large inventory of chemical information encoded in oil to robustly differentiate signatures of mass transfer to air and water. With this new approach, we can evaluate mass transfer models (the Part 2 companion to this paper) and more properly account for evaporation, dissolution, and degradation of oil in the environment.

Scanning and transmission electron microscope of suspended lead-rich particles in the air of San Luis Potosi, Mexico

NASA Astrophysics Data System (ADS)

Piña, A. Aragón; Villaseñor, G. Torres; Jacinto, P. Santiago; Fernández, M. Monroy

In the city of San Luis Potosi exists an important metallurgical plant and is known that in the adjacent urban zone, there is a high concentration of lead in the air, it is also supposed that most of the particles with lead have an anthropogenic origin because these particles show morphological characteristics and chemical composition very different in comparison with common lead minerals. In this work it was proved that most of the airborne particles with lead present in this urban zone, effectively came from the copper smelter. The airborne particles with lead were compared with particles with lead obtained starting from samples of slag and lead calcine of the copper smelter. To perform the comparative study, these particles were studied with energy dispersive X-ray microanalysis (EDS) in conjunction with scanning electron microscope to obtain chemical composition and associated morphological characteristics. Results suggest that these particles, composed of only one phase, are chemically distinct from any crustal lead mineral. Because of the complexity of the chemical composition of these particles (Pb, S, Cu, As, Fe, Zn, Cd, Sb, O), some of the airborne particles were analyzed by transmission microscopy in order to associate crystalline structure with any particular chemical phase.

An analytical platform for mass spectrometry-based identification and chemical analysis of RNA in ribonucleoprotein complexes.

PubMed

Taoka, Masato; Yamauchi, Yoshio; Nobe, Yuko; Masaki, Shunpei; Nakayama, Hiroshi; Ishikawa, Hideaki; Takahashi, Nobuhiro; Isobe, Toshiaki

2009-11-01

We describe here a mass spectrometry (MS)-based analytical platform of RNA, which combines direct nano-flow reversed-phase liquid chromatography (RPLC) on a spray tip column and a high-resolution LTQ-Orbitrap mass spectrometer. Operating RPLC under a very low flow rate with volatile solvents and MS in the negative mode, we could estimate highly accurate mass values sufficient to predict the nucleotide composition of a approximately 21-nucleotide small interfering RNA, detect post-transcriptional modifications in yeast tRNA, and perform collision-induced dissociation/tandem MS-based structural analysis of nucleolytic fragments of RNA at a sub-femtomole level. Importantly, the method allowed the identification and chemical analysis of small RNAs in ribonucleoprotein (RNP) complex, such as the pre-spliceosomal RNP complex, which was pulled down from cultured cells with a tagged protein cofactor as bait. We have recently developed a unique genome-oriented database search engine, Ariadne, which allows tandem MS-based identification of RNAs in biological samples. Thus, the method presented here has broad potential for automated analysis of RNA; it complements conventional molecular biology-based techniques and is particularly suited for simultaneous analysis of the composition, structure, interaction, and dynamics of RNA and protein components in various cellular RNP complexes.

Towards a nondestructive chemical characterization of biofilm matrix by Raman microscopy.

PubMed

Ivleva, Natalia P; Wagner, Michael; Horn, Harald; Niessner, Reinhard; Haisch, Christoph

2009-01-01

In this study, the applicability of Raman microscopy (RM) for nondestructive chemical analysis of biofilm matrix, including microbial constituents and extracellular polymeric substances (EPS), has been assessed. The examination of a wide range of reference samples such as biofilm-specific polysaccharides, proteins, microorganisms, and encapsulated bacteria revealed characteristic frequency regions and specific marker bands for different biofilm constituents. Based on received data, the assignment of Raman bands in spectra of multispecies biofilms was performed. The study of different multispecies biofilms showed that RM can correlate various structural appearances within the biofilm to variations in their chemical composition and provide chemical information about a complex biofilm matrix. The results of RM analysis of biofilms are in good agreement with data obtained by confocal laser scanning microscopy (CLSM). Thus, RM is a promising tool for a label-free chemical characterization of different biofilm constituents. Moreover, the combination of RM with CLSM analysis for the study of biofilms grown under different environmental conditions can provide new insights into the complex structure/function correlations in biofilms.

Respiratory dose analysis for components of ambient particulate matter

EPA Science Inventory

Particulate matter (PM) in the atmosphere is a complex mixture of particles with different sizes and chemical compositions. Although PM is known to induce health effects, specific attributes of PM that may cause health effects are somewhat ambiguous. Dose of each specific compone...

THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

EPA Science Inventory

Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

The key properties of solu...

Respiratory dose analysis for components of ambient particulate matter#

EPA Science Inventory

Particulate matter (PM) in the atmosphere is a complex mixture of particles with different sizes and chemical compositions. Although PM is known to cause health hazard, specific attributes of PM that may cause health effects are somewhat ambiguous. The dose of each specific compo...

Propolis: A Complex Natural Product with a Plethora of Biological Activities That Can Be Explored for Drug Development

PubMed Central

Silva-Carvalho, Ricardo; Baltazar, Fátima; Almeida-Aguiar, Cristina

2015-01-01

The health industry has always used natural products as a rich, promising, and alternative source of drugs that are used in the health system. Propolis, a natural resinous product known for centuries, is a complex product obtained by honey bees from substances collected from parts of different plants, buds, and exudates in different geographic areas. Propolis has been attracting scientific attention since it has many biological and pharmacological properties, which are related to its chemical composition. Several in vitro and in vivo studies have been performed to characterize and understand the diverse bioactivities of propolis and its isolated compounds, as well as to evaluate and validate its potential. Yet, there is a lack of information concerning clinical effectiveness. The goal of this review is to discuss the potential of propolis for the development of new drugs by presenting published data concerning the chemical composition and the biological properties of this natural compound from different geographic origins. PMID:26106433

Use of tourmaline as a potential petrogenetic indicator in the determination of host magma: CRS, XRD and PED-XRF methods

NASA Astrophysics Data System (ADS)

Gullu, Bahattin; Kadioglu, Yusuf Kagan

2017-08-01

Tourmaline defines a group of complex borosilicate forms as accessory mineral in igneous and metamorphic rocks and they act an important role in the interpretation of the chemical composition changes of the composition of the host fluid of the magma. The variety of tourmaline can be identified by using optical microscopy, X-Ray Diffraction (XRD) and by determining its chemical composition through Polarized Energy Dispersive X-Ray Fluorescence (PED-XRF) methods. However, microscopic investigations and XRD analyses are not quite adequate for detailed determination of tourmaline sub-groups. In addition, the use of chemical composition of tourmaline as a strict indicator of geochemical processes might be a misleading method. In this study, variable tourmaline crystals were collected from three different pegmatitic occurrences in Behrekdag, Yozgat and Karakaya granitic bodies of Central Anatolia to identify their chemical properties through Confocal Raman Spectroscopy (CRS), PED-XRF and XRD analyses. The confocal Raman spectrometry of collected tourmalines from the Behrekdag, Yozgat and Karakaya granites are in the compositions of schorl, schorl and elbaite respectively. The dominant compositional groups of these tourmalines are in the form of schorl. Raman shift values of tourmalines revealed four bands centered at almost 1050, 750, 400 and 300 cm- 1. The first group of the band arises from SiO stretching, the second from Bsbnd O stretching and the other two belong to bending modes of Osbnd Bsbnd O and Bsbnd Osbnd Al with symmetrical deformation of Sisbnd Osbnd Si. The strongest spectra near 360 cm- 1 should belong to the bonding of Alsbnd O. As a result, the confocal Raman studies are more sensitive for identification of tourmaline subgroup compositions and have a quite important in the explaining source of the magma.

Use of tourmaline as a potential petrogenetic indicator in the determination of host magma: CRS, XRD and PED-XRF methods.

PubMed

Gullu, Bahattin; Kadioglu, Yusuf Kagan

2017-08-05

Tourmaline defines a group of complex borosilicate forms as accessory mineral in igneous and metamorphic rocks and they act an important role in the interpretation of the chemical composition changes of the composition of the host fluid of the magma. The variety of tourmaline can be identified by using optical microscopy, X-Ray Diffraction (XRD) and by determining its chemical composition through Polarized Energy Dispersive X-Ray Fluorescence (PED-XRF) methods. However, microscopic investigations and XRD analyses are not quite adequate for detailed determination of tourmaline sub-groups. In addition, the use of chemical composition of tourmaline as a strict indicator of geochemical processes might be a misleading method. In this study, variable tourmaline crystals were collected from three different pegmatitic occurrences in Behrekdag, Yozgat and Karakaya granitic bodies of Central Anatolia to identify their chemical properties through Confocal Raman Spectroscopy (CRS), PED-XRF and XRD analyses. The confocal Raman spectrometry of collected tourmalines from the Behrekdag, Yozgat and Karakaya granites are in the compositions of schorl, schorl and elbaite respectively. The dominant compositional groups of these tourmalines are in the form of schorl. Raman shift values of tourmalines revealed four bands centered at almost 1050, 750, 400 and 300cm -1 . The first group of the band arises from SiO stretching, the second from BO stretching and the other two belong to bending modes of OBO and BOAl with symmetrical deformation of SiOSi. The strongest spectra near 360cm -1 should belong to the bonding of AlO. As a result, the confocal Raman studies are more sensitive for identification of tourmaline subgroup compositions and have a quite important in the explaining source of the magma. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of Fecal Near-infrared Spectroscopy to Predict Feces Chemical Composition and Apparent Total Tract Digestibility of Nutrients in Pigs.

PubMed

Nirea, K G; Pérez de Nanclares, M; Skugor, A; Afseth, N K; Meuwissen, T H E; Hansen, J Ø; Mydland, L T; Øverland, M

2018-05-08

Apparent total tract digestibility (ATTD) of nutrients could be an alternative measure of feed efficiency when breeding for robust animals that are fed fiber-rich diets. Apparent total tract digestibility of nutrients requires measuring individual feed intake of a large number of animals which is expensive and complex. Alternatively, ATTD of nutrients and feces chemical composition can be predicted using fecal near-infrared spectroscopy (FNIRS). The objective of this study was to assess if the feces chemical composition and ATTD of nutrients can be predicted using FNIRS that originate from various pig experimental datasets. Fecal samples together with detailed information on the feces chemical composition and ATTD of nutrients were obtained from four different pig experiments. Feces near-infrared spectroscopy were analyzed from fecal samples of a complete dataset. The model was calibrated using the FNIRS and reference samples of feces chemical composition and ATTD of nutrients. The robustness and predictability of the model was evaluated by the r2 and the closeness between SE of calibration (SEC) and SE of cross-validation (SECV). Prediction of the feces chemical components and ATTD of nutrients was successful as SEC and SECV were equivalent. Calibration model was developed to estimate the ATTD of nutrients and fecal chemical composition from the FNIRS and worked well for OM (r2 = 0.94; SEC = 48.5; SECV = 56.6), CP ( r2 = 0.89; SEC = 18.1; SECV = 18.8), GE ( r2 = 0.92; SEC = 1.2; SECV = 1.4), NDF (r2 = 0.94 ; SEC = 55; SECV = 60.2), OM digestibility (r2 = 0.94; SEC = 5.5; SECV = 6.7), GE digestibility (r2 = 0.88; SEC = 2.3; SECV = 2.6) and fat digestibility (r2 = 0.79 ; SEC = 6, SECV = 6.8). However, the SE of prediction was slightly higher than what has been reported in another study. The prediction of feces chemical composition for fat (r2 = 0.69; SEC = 11.7, SECV = 12.3), CP digestibility (r2 = 0.63; SEC = 2.3; SECV = 2.7) and NDF digestibility (r2 = 0.64, SEC = 7.7, SECV = 8.8) was moderate. We conclude that the FNIRS accurately predicts the chemical composition of feces and ATTD of nutrients for OM, CP and GE. The approach of FNIRS is a cost-effective method for measuring digestibility and feed efficiency in a large-scale pig breeding programs.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

PubMed

Haikal, Rana R; Wang, Xia; Hassan, Youssef S; Parida, Manas R; Murali, Banavoth; Mohammed, Omar F; Pellechia, Perry J; Fontecave, Marc; Alkordi, Mohamed H

2016-08-10

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

Effects of nucleoside analog incorporation on DNA binding to the DNA binding domain of the GATA-1 erythroid transcription factor.

PubMed

Foti, M; Omichinski, J G; Stahl, S; Maloney, D; West, J; Schweitzer, B I

1999-02-05

We investigate here the effects of the incorporation of the nucleoside analogs araC (1-beta-D-arabinofuranosylcytosine) and ganciclovir (9-[(1,3-dihydroxy-2-propoxy)methyl] guanine) into the DNA binding recognition sequence for the GATA-1 erythroid transcription factor. A 10-fold decrease in binding affinity was observed for the ganciclovir-substituted DNA complex in comparison to an unmodified DNA of the same sequence composition. AraC substitution did not result in any changes in binding affinity. 1H-15N HSQC and NOESY NMR experiments revealed a number of chemical shift changes in both DNA and protein in the ganciclovir-modified DNA-protein complex when compared to the unmodified DNA-protein complex. These changes in chemical shift and binding affinity suggest a change in the binding mode of the complex when ganciclovir is incorporated into the GATA DNA binding site.

Rapid production of hollow SS316 profiles by extrusion based additive manufacturing

NASA Astrophysics Data System (ADS)

Rane, Kedarnath; Cataldo, Salvatore; Parenti, Paolo; Sbaglia, Luca; Mussi, Valerio; Annoni, Massimiliano; Giberti, Hermes; Strano, Matteo

2018-05-01

Complex shaped stainless steel tubes are often required for special purpose biomedical equipment. Nevertheless, traditional manufacturing technologies, such as extrusion, lack the ability to compete in a market of customized complex components because of associated expenses towards tooling and extrusion presses. To rapid manufacture few of such components with low cost and high precision, a new Extrusion based Additive Manufacturing (EAM) process, is proposed in this paper, and as an example, short stainless steel 316L complex shaped and sectioned tubes were prepared by EAM. Several sample parts were produced using this process; the dimensional stability, surface roughness and chemical composition of sintered samples were investigated to prove process competence. The results indicate that feedstock with a 316L particle content of 92.5 wt. % can be prepared with a sigma blade mixing, whose rheological behavior is fit for EAM. The green samples have sufficient strength to handle them for subsequent treatments. The sintered samples considerably shrunk to designed dimensions and have a homogeneous microstructure to impart mechanical strength. Whereas, maintaining comparable dimensional accuracy and chemical composition which are required for biomedical equipment still need iterations, a kinematic correction and modification in debinding cycle was proposed.

Nanoscale Charge Balancing Mechanism in Calcium-Silicate-Hydrate Gels: Novel Complex Disordered Materials from First-principles

NASA Astrophysics Data System (ADS)

Ozcelik, Ongun; White, Claire

Alkali-activated materials which have augmented chemical compositions as compared to ordinary Portland cement are sustainable technologies that have the potential to lower CO2 emissions associated with the construction industry. In particular, calcium-silicate-hydrate (C-S-H) gel is altered at the atomic scale due to changes in its chemical composition. Here, based on first-principles calculations, we predict a charge balancing mechanism at the molecular level in C-S-H gels when alkali atoms are introduced into their structure. This charge balancing process is responsible for the formation of novel structures which possess superior mechanical properties compared to their charge unbalanced counterparts. Different structural representations are obtained depending on the level of substitution and the degree of charge balancing incorporated in the structures. The impact of these charge balancing effects on the structures is assessed by analyzing their formation energies, local bonding environments, diffusion barriers and mechanical properties. These results provide information on the phase stability of alkali/aluminum containing C-S-H gels, shedding light on the fundamental mechanisms that play a crucial role in these complex disordered materials. We acknowledge funding from the Princeton Center for Complex Materials, a MRSEC supported by NSF.

Optical and scintillation properties of Nd-doped complex garnet

NASA Astrophysics Data System (ADS)

Yanagida, Takayuki; Sato, Hiroki

2014-12-01

Nd 1% doped complex garnet scintillators were prepared by Furukawa and their optical and scintillation properties were investigated on a comparison with previously reported Nd-doped YAG. Chemical compositions of newly developed complex garnets were Lu2Y1Al5O12, Lu2Y1Ga3Al2O12, Lu2Gd1Al5O12, Lu2Gd1Ga3Al2O12, Gd1Y2Al5O12, Gd1Y2Ga3Al2O12, and Gd3Ga3Al2O12. They all showed 50-80% transmittance from ultraviolet to near infrared wavelengths with several absorption bands due to Gd3+ or Nd3+ 4f-4f transition. In X-ray induced radioluminescence spectra, all samples exhibited intense lines at 310 nm due to Gd3+ or 400 nm due to Nd3+ depending on their chemical composition. Among them, the highest scintillation light yield was achieved by Lu2Y1Al5O12. Typical scintillation decay times of them resulted 1.5-3 μs. Thermally stimulated glow curve after 1 Gy exposure and X-ray induced afterglow were also investigated.

Chemical mixing model studies of lunar orbital geochemical data - Apollo 16 and 17 highlands compositions

NASA Technical Reports Server (NTRS)

Spudis, P. D.; Hawke, B. R.

1982-01-01

Chemical mixing model studies of lunar geochemical data for the central and Taurus-Littrow lunar highlands were performed utilizing pristine highland rock types as end member compositions. The central highlands show considerable diversity in composition; anorthosite is the principal rock type in the Apollo 16/Descartes region, while norite predominates in the highlands west of the landing site. This change in crustal composition is coincident with a major color boundary seen in earth-based multispectral data and probably represents the presence of distinct geochemical provinces within the central highlands. The Taurus-Littrow highlands are dominated by norite; anorthosite is far less abundant than in the central highlands. This suggests that the impact target for the Serenitatis basin was different than that of the Nectaris basin and further strengthens the hypothesis that the lunar highlands are petrologically heterogeneous on a regional basis. It is suggested that the lunar highlands should be viewed in terms of geochemical provinces that have undergone distinct and complex igneous and impact histories.

Variation in chemical composition and acaricidal activity against Dermanyssus gallinae of four eucalyptus essential oils.

PubMed

George, David R; Masic, Dino; Sparagano, Olivier A E; Guy, Jonathan H

2009-06-01

The results of this study suggest that certain eucalyptus essential oils may be of use as an alternative to synthetic acaricides in the management of the poultry red mite, Dermanyssus gallinae. At a level of 0.21 mg/cm(2), the essential oil from Eucalyptus citriodora achieved 85% mortality in D. gallinae over a 24 h exposure period in contact toxicity tests. A further two essential oils from different eucalyptus species, namely E. globulus and E. radiata, provided significantly (P < 0.05) lower mite mortality (11 and 19%, respectively). Notable differences were found between the eucalyptus essential oils regarding their chemical compositions. There appeared to be a trend whereby the essential oils that were composed of the fewer chemical components were the least lethal to D. gallinae. It may therefore be the case that the complexity of an essential oil's chemical make up plays an important role in dictating the toxicity of that oil to pests such as D. gallinae.

Chemical Composition and Source Apportionment of Size Fractionated Particulate Matter in Cleveland, Ohio, USA

EPA Science Inventory

The Cleveland airshed comprises a complex mixture of industrial source emissions that contribute to periods of non-attainment for fine particulate matter (PM 2.5 ) and are associated with increased adverse health outcomes in the exposed population. Specific PM sources responsible...

Linking Different Exposure Patterns to Internal Lung Dose for Heterogeneous Ambient Aerosols

EPA Science Inventory

Particulate matter (PM) in the ambient air is a complex mixture of particles with different sizes and chemical compositions. Because potential health effects are known to be different for different size particles, specific dose of size-fractionated PM under realistic exposure con...

Polysaccharide-based hydrogels with tunable composition as 3D cell culture systems.

PubMed

Gentilini, Roberta; Munarin, Fabiola; Bloise, Nora; Secchi, Eleonora; Visai, Livia; Tanzi, Maria Cristina; Petrini, Paola

2018-04-01

To date, cell cultures have been created either on 2-dimensional (2D) polystyrene surfaces or in 3-dimensional (3D) systems, which do not offer a controlled chemical composition, and which lack the soft environment encountered in vivo and the chemical stimuli that promote cell proliferation and allow complex cellular behavior. In this study, pectin-based hydrogels were developed and are proposed as versatile cell culture systems. Pectin-based hydrogels were produced by internally crosslinking pectin with calcium carbonate at different initial pH, aiming to control crosslinking kinetics and degree. Additionally, glucose and glutamine were added as additives, and their effects on the viscoelastic properties of the hydrogels and on cell viability were investigated. Pectin hydrogels showed in high cell viability and shear-thinning behavior. Independently of hydrogel composition, an initial swelling was observed, followed by a low percentage of weight variation and a steady-state stage. The addition of glucose and glutamine to pectin-based hydrogels rendered higher cell viability up to 90%-98% after 1 hour of incubation, and these hydrogels were maintained for up to 7 days of culture, yet no effect on viscoelastic properties was detected. Pectin-based hydrogels that offer tunable composition were developed successfully. They are envisioned as synthetic extracellular matrix (ECM) either to study complex cellular behaviors or to be applied as tissue engineering substitutes.

Online-LASIL: Laser Ablation of Solid Samples in Liquid with online-coupled ICP-OES detection for direct determination of the stoichiometry of complex metal oxide thin layers.

PubMed

Bonta, Maximilian; Frank, Johannes; Taibl, Stefanie; Fleig, Jürgen; Limbeck, Andreas

2018-02-13

Advanced materials such as complex metal oxides are used in a wide range of applications and have further promising perspectives in the form of thin films. The exact chemical composition essentially influences the electronic properties of these materials which makes correct assessment of their composition necessary. However, due to high chemical resistance and in the case of thin films low absolute analyte amounts, this procedure is in most cases not straightforward and extremely time-demanding. Commonly applied techniques either lack in ease of use (i.e., solution-based analysis with preceding sample dissolution), or adequately accurate quantification (i.e., solid sampling techniques). An analysis approach which combines the beneficial aspects of solution-based analysis as well as direct solid sampling is Laser Ablation of a Sample in Liquid (LASIL). In this work, it is shown that the analysis of major as well as minor sample constituents is possible using a novel online-LASIL setup, allowing sample analysis without manual sample handling after placing it in an ablation chamber. Strontium titanate (STO) thin layers with different compositions were analyzed in the course of this study. Precision of the newly developed online-LASIL method is comparable to conventional wet chemical approaches. With only about 15-20 min required for the analysis per sample, time demand is significantly reduced compared to often necessary fusion procedures lasting multiple hours. Copyright © 2017 Elsevier B.V. All rights reserved.

Tying Biological Activity to Changes in Sea Spray Aerosol Chemical Composition via Single Particle Analyses

NASA Astrophysics Data System (ADS)

Sultana, C. M.; Lee, C.; Collins, D. B.; Axson, J. L.; Laskina, O.; Grandquist, J. R.; Grassian, V. H.; Prather, K. A.

2014-12-01

In remote marine environments, sea spray aerosols (SSA) often represent the greatest aerosol burden, thus having significant impacts on direct radiative interactions and cloud processes. Previous studies have shown that SSA is a complex mixture of inorganic salts and an array of dissolved and particulate organic components. Enrichment of SSA organic content is often correlated to seawater chlorophyll concentrations, a measure of oceanic biological activity. As the physical and chemical properties of aerosols control their radiative effects, recent studies conducted by the Center for Aerosol Impacts on Climate and the Environment have endeavored to further elucidate the ties between marine biological activity and primary SSA chemical composition using highly time resolved single particle analyses. A series of experiments performed in the recently developed Marine Aerosol Reference Tank evaluated the effect of changing marine microbial populations on SSA chemical composition, which was monitored via an aerosol time-of-flight mass spectrometer and a variety of offline spectroscopic and microscopic techniques. Each experiment was initiated using unfiltered and untreated seawater, thus maintaining a high level of biogeochemical complexity. This study is the first of its kind to capture daily changes in the primary SSA mixing state over the growth and death of a natural phytoplankton bloom. Increases in organic aerosol types (0.4-3 μm), internally and externally mixed with sea salt, could not be correlated to chlorophyll concentrations. Maximum production of these populations occurred two to four days after the in vivo chlorophyll fluorescence peaked in intensity. This work is in contrast to the current paradigm of correlating SSA organic content to seawater chlorophyll concentration.

Premixed autoignition in compressible turbulence

NASA Astrophysics Data System (ADS)

Konduri, Aditya; Kolla, Hemanth; Krisman, Alexander; Chen, Jacqueline

2016-11-01

Prediction of chemical ignition delay in an autoignition process is critical in combustion systems like compression ignition engines and gas turbines. Often, ignition delay times measured in simple homogeneous experiments or homogeneous calculations are not representative of actual autoignition processes in complex turbulent flows. This is due the presence of turbulent mixing which results in fluctuations in thermodynamic properties as well as chemical composition. In the present study the effect of fluctuations of thermodynamic variables on the ignition delay is quantified with direct numerical simulations of compressible isotropic turbulence. A premixed syngas-air mixture is used to remove the effects of inhomogeneity in the chemical composition. Preliminary results show a significant spatial variation in the ignition delay time. We analyze the topology of autoignition kernels and identify the influence of extreme events resulting from compressibility and intermittency. The dependence of ignition delay time on Reynolds and turbulent Mach numbers is also quantified. Supported by Basic Energy Sciences, Dept of Energy, United States.

Prediction of aged red wine aroma properties from aroma chemical composition. Partial least squares regression models.

PubMed

Aznar, Margarita; López, Ricardo; Cacho, Juan; Ferreira, Vicente

2003-04-23

Partial least squares regression (PLSR) models able to predict some of the wine aroma nuances from its chemical composition have been developed. The aromatic sensory characteristics of 57 Spanish aged red wines were determined by 51 experts from the wine industry. The individual descriptions given by the experts were recorded, and the frequency with which a sensory term was used to define a given wine was taken as a measurement of its intensity. The aromatic chemical composition of the wines was determined by already published gas chromatography (GC)-flame ionization detector and GC-mass spectrometry methods. In the whole, 69 odorants were analyzed. Both matrixes, the sensory and chemical data, were simplified by grouping and rearranging correlated sensory terms or chemical compounds and by the exclusion of secondary aroma terms or of weak aroma chemicals. Finally, models were developed for 18 sensory terms and 27 chemicals or groups of chemicals. Satisfactory models, explaining more than 45% of the original variance, could be found for nine of the most important sensory terms (wood-vanillin-cinnamon, animal-leather-phenolic, toasted-coffee, old wood-reduction, vegetal-pepper, raisin-flowery, sweet-candy-cacao, fruity, and berry fruit). For this set of terms, the correlation coefficients between the measured and predicted Y (determined by cross-validation) ranged from 0.62 to 0.81. Models confirmed the existence of complex multivariate relationships between chemicals and odors. In general, pleasant descriptors were positively correlated to chemicals with pleasant aroma, such as vanillin, beta damascenone, or (E)-beta-methyl-gamma-octalactone, and negatively correlated to compounds showing less favorable odor properties, such as 4-ethyl and vinyl phenols, 3-(methylthio)-1-propanol, or phenylacetaldehyde.

Spectroscopic Case-Based Studies in a Flipped Quantum Mechanics Course

NASA Astrophysics Data System (ADS)

Shipman, Steven

2015-06-01

Students in a flipped Quantum Mechanics course were expected to apply their knowledge of spectroscopy to a variety of case studies involving complex mixtures of chemicals. They used simulated data, prepared in advance by the instructor, to determine the major chemical constituents of complex mixtures. Students were required to request the appropriate data in order to ultimately make plausible guesses about the composition of the mixtures, allowing them ownership over the discovery process. This talk will describe how these activities worked in practice, give caveats for instructors who wish to adopt them in the future, and discuss how the results of these exercises can be used for both formative and summative assessment.

SUPRAMOLECULAR COMPOSITE MATERIALS FROM CELLULOSE, CHITOSAN AND CYCLODEXTRIN: FACILE PREPARATION AND THEIR SELECTIVE INCLUSION COMPLEX FORMATION WITH ENDOCRINE DISRUPTORS

PubMed Central

Duri, Simon; Tran, Chieu D.

2013-01-01

We have successfully developed a simple and one step method to prepare high performance supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and (2,3,6-tri-O-acetyl)-α-, β- and γ-cyclodextrin (α-, β- and γ-TCD). In this method, [BMIm+Cl−], an ionic liquid (IL), was used as a solvent to dissolve and prepare the composites. Since majority (>88%) of the IL used was recovered for reuse, the method is recyclable. XRD, FT-IR, NIR and SEM were used to monitor the dissolution process and to confirm that the polysaccharides were regenerated without any chemical modifications. It was found that unique properties of each component including superior mechanical properties (from CEL), excellent adsorbent for pollutants and toxins (from CS) and size/structure selectivity through inclusion complex formation (from TCDs) remain intact in the composites. Specifically, results from kinetics and adsorption isotherms show that while CS-based composites can effectively adsorb the endocrine disruptors (polychlrophenols, bisphenol-A), its adsorption is independent on the size and structure of the analytes. Conversely, the adsorption by γ-TCD-based composites exhibits strong dependency on size and structure of the analytes. For example, while all three TCD-based composites (i.e., α-, β- and γ-TCD) can effectively adsorb 2-, 3- and 4-chlorophenol, only γ-TCD-based composite can adsorb analytes with bulky groups including 3,4-dichloro- and 2,4,5-trichlorophenol. Furthermore, equilibrium sorption capacities for the analytes with bulky groups by γ-TCD-based composite are much higher than those by CS-based composites. Together, these results indicate that γ-TCD-based composite with its relatively larger cavity size can readily form inclusion complexes with analytes with bulky groups, and through inclusion complex formation, it can strongly adsorb much more analytes and with size/structure selectivity compared to CS-based composites which can adsorb the analyte only by surface adsorption. PMID:23517477

Environmental hazard and risk characterisation of petroleum substances: a guided "walking tour" of petroleum hydrocarbons.

PubMed

Bierkens, Johan; Geerts, Lieve

2014-05-01

Petroleum substances are used in large quantities, primarily as fuels. They are complex mixtures whose major constituents are hydrocarbons derived from crude oil by distillation and fractionation. Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the huge number of molecular components. This complex nature of petroleum products, with their varied number of constituents, all of them exhibiting different fate and effect characteristics, merits a dedicated hazard and risk assessment approach. From a regulatory perspective they pose a great challenge in a number of REACH processes, in particular in the context of dossier and substance evaluation but also for priority setting activities. In order to facilitate the performance of hazard and risk assessment for petroleum substances the European oil company association, CONCAWE, has developed the PETROTOX and PETRORISK spreadsheet models. Since the exact composition of many petroleum products is not known, an underlying assumption of the PETROTOX and PETRORISK tools is that the behaviour and fate of a total petroleum substance can be simulated based on the physical-chemical properties of representative structures mapped to hydrocarbon blocks (HBs) and on the relative share of each HB in the total mass of the product. To assess how differing chemical compositions affect the simulated chemical fate and toxicity of hydrocarbon mixtures, a series of model simulations were run using an artificial petroleum substance, containing 386 (PETROTOX) or 160 (PETRORISK) HBs belonging to different chemical classes and molecular weight ranges, but with equal mass assigned to each of them. To this artificial petroleum substance a guided series of subsequent modifications in mass allocation to a delineated number of HBs belonging to different chemical classes and carbon ranges was performed, in what we perceived as a guided "walking tour" through the chemical space of petroleum substances. We show that the PETROTOX and PETRORISK predictions reflect changes in mass distribution introduced to selected HBs by affecting hazard and risk estimates in correspondence with what is expected based on physical-chemical properties of individual constituents in the corresponding HBs. Copyright © 2014 Elsevier Ltd. All rights reserved.

A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

USGS Publications Warehouse

Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

1996-01-01

A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

Zebrafish Locomotor Responses Demonstrate Irritant Effects of Fine Particulate Matter Sources and a Role for TRPA1

EPA Science Inventory

Fine particulate matter (PM) air pollution is a complex mixture of chemicals, the composition of which is determined by contributing sources, and has been linked to cardiopulmonary dysfunction. These effects stem in part from the irritating properties of PM constituents, which ...

The chemical composition of aerosols from Wildland fires: Current state of the science and possible new directions.

EPA Science Inventory

Wildland fire emits a substantial quantity of aerosol to the atmosphere. These aerosols typically comprise a complex mixture of organic matter and refractory elemental or black carbon with a relatively minor contribution of inorganic matter from soils and plant micronutrients. Id...

Optical Basicity and Nepheline Crystallization in High Alumina Glasses

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

Rodriguez, Carmen P.; McCloy, John S.; Schweiger, M. J.

2011-02-25

The purpose of this study was to find compositions that increase waste loading of high-alumina wastes beyond what is currently acceptable while avoiding crystallization of nepheline (NaAlSiO4) on slow cooling. Nepheline crystallization has been shown to have a large impact on the chemical durability of high-level waste glasses. It was hypothesized that there would be some composition regions where high-alumina would not result in nepheline crystal production, compositions not currently allowed by the nepheline discriminator. Optical basicity (OB) and the nepheline discriminator (ND) are two ways of describing a given complex glass composition. This report presents the theoretical and experimentalmore » basis for these models. They are being studied together in a quadrant system as metrics to explore nepheline crystallization and chemical durability as a function of waste glass composition. These metrics were calculated for glasses with existing data and also for theoretical glasses to explore nepheline formation in Quadrant IV (passes OB metric but fails ND metric), where glasses are presumed to have good chemical durability. Several of these compositions were chosen, and glasses were made to fill poorly represented regions in Quadrant IV. To evaluate nepheline formation and chemical durability of these glasses, quantitative X-ray diffraction (XRD) analysis and the Product Consistency Test were conducted. A large amount of quantitative XRD data is collected here, both from new glasses and from glasses of previous studies that had not previously performed quantitative XRD on the phase assemblage. Appendix A critically discusses a large dataset to be considered for future quantitative studies on nepheline formation in glass. Appendix B provides a theoretical justification for choice of the oxide coefficients used to compute the OB criterion for nepheline formation.« less

Terahertz detection and identification of defects in layered polymer composites and composite coatings

NASA Astrophysics Data System (ADS)

Lopato, Przemyslaw; Chady, Tomasz

2013-03-01

Modern industry makes more and more extensive use of various composite materials. In this paper, for the purposes of various composite materials evaluation, the terahertz imaging method is presented. Basalt fibre-reinforced composites and polymeric anticorrosion coatings are considered. Basalt fibre composites are the innovative materials that are being increasingly used in modern industry. The paper also briefly introduces a specific type of complex coating of steel applied in the industry (e.g. oil or chemical). Two methods of defects detection in the mentioned structures are presented. The first method is based on a system identification, whereas the second one is on the estimation of time-domain signal parameters. Finally, the results achieved during terahertz inspection of coatings are compared with those obtained using active thermography.

The presence of cutan limits the interpretation of cuticular chemistry and structure: Ficus elastica leaf as an example.

PubMed

Guzmán-Delgado, Paula; Graça, José; Cabral, Vanessa; Gil, Luis; Fernández, Victoria

2016-06-01

Plant cuticles have been traditionally classified on the basis of their ultrastructure, with certain chemical composition assumptions. However, the nature of the plant cuticle may be misinterpreted in the prevailing model, which was established more than 150 years ago. Using the adaxial leaf cuticle of Ficus elastica, a study was conducted with the aim of analyzing cuticular ultrastructure, chemical composition and the potential relationship between structure and chemistry. Gradual chemical extractions and diverse analytical and microscopic techniques were performed on isolated leaf cuticles of two different stages of development (i.e. young and mature leaves). Evidence for the presence of cutan in F. elastica leaf cuticles has been gained after chemical treatments and tissue analysis by infrared spectroscopy and electron microscopy. Significant calcium, boron and silicon concentrations were also measured in the cuticle of this species. Such mineral elements which are often found in plant cell walls may play a structural role and their presence in isolated cuticles further supports the interpretation of the cuticle as the most external region of the epidermal cell wall. The complex and heterogeneous nature of the cuticle, and constraints associated with current analytical procedures may limit the chance for establishing a relationship between cuticle chemical composition and structure also in relation to organ ontogeny. © 2016 Scandinavian Plant Physiology Society.

Modeling the chemistry of complex petroleum mixtures.

PubMed Central

Quann, R J

1998-01-01

Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the astronomical number of molecular components. Modeling the composition and behavior of such complex mixtures in refinery processes has accordingly evolved along a simplifying concept called lumping. Lumping reduces the complexity of the problem to a manageable form by grouping the entire set of molecular components into a handful of lumps. This traditional approach does not have a molecular basis and therefore excludes important aspects of process chemistry and molecular property fundamentals from the model's formulation. A new approach called structure-oriented lumping has been developed to model the composition and chemistry of complex mixtures at a molecular level. The central concept is to represent an individual molecular or a set of closely related isomers as a mathematical construct of certain specific and repeating structural groups. A complex mixture such as petroleum can then be represented as thousands of distinct molecular components, each having a mathematical identity. This enables the automated construction of large complex reaction networks with tens of thousands of specific reactions for simulating the chemistry of complex mixtures. Further, the method provides a convenient framework for incorporating molecular physical property correlations, existing group contribution methods, molecular thermodynamic properties, and the structure--activity relationships of chemical kinetics in the development of models. PMID:9860903

Municipal solid waste landfills harbor distinct microbiomes

USGS Publications Warehouse

Stamps, Blake W.; Lyles, Christopher N.; Suflita, Joseph M.; Masoner, Jason R.; Cozzarelli, Isabelle M.; Kolpin, Dana W.; Stevenson, Bradley S.

2016-01-01

Landfills are the final repository for most of the discarded material from human society and its “built environments.” Microorganisms subsequently degrade this discarded material in the landfill, releasing gases (largely CH4 and CO2) and a complex mixture of soluble chemical compounds in leachate. Characterization of “landfill microbiomes” and their comparison across several landfills should allow the identification of environmental or operational properties that influence the composition of these microbiomes and potentially their biodegradation capabilities. To this end, the composition of landfill microbiomes was characterized as part of an ongoing USGS national survey studying the chemical composition of leachates from 19 non-hazardous landfills across 16 states in the continental U.S. The landfills varied in parameters such as size, waste composition, management strategy, geography, and climate zone. The diversity and composition of bacterial and archaeal populations in leachate samples were characterized by 16S rRNA gene sequence analysis, and compared against a variety of physical and chemical parameters in an attempt to identify their impact on selection. Members of the Epsilonproteobacteria, Gammaproteobacteria, Clostridia, and candidate division OP3 were the most abundant. The distribution of the observed phylogenetic diversity could best be explained by a combination of variables and was correlated most strongly with the concentrations of chloride and barium, rate of evapotranspiration, age of waste, and the number of detected household chemicals. This study illustrates how leachate microbiomes are distinct from those of other natural or built environments, and sheds light on the major selective forces responsible for this microbial diversity.

Municipal Solid Waste Landfills Harbor Distinct Microbiomes

PubMed Central

Stamps, Blake W.; Lyles, Christopher N.; Suflita, Joseph M.; Masoner, Jason R.; Cozzarelli, Isabelle M.; Kolpin, Dana W.; Stevenson, Bradley S.

2016-01-01

Landfills are the final repository for most of the discarded material from human society and its “built environments.” Microorganisms subsequently degrade this discarded material in the landfill, releasing gases (largely CH4 and CO2) and a complex mixture of soluble chemical compounds in leachate. Characterization of “landfill microbiomes” and their comparison across several landfills should allow the identification of environmental or operational properties that influence the composition of these microbiomes and potentially their biodegradation capabilities. To this end, the composition of landfill microbiomes was characterized as part of an ongoing USGS national survey studying the chemical composition of leachates from 19 non-hazardous landfills across 16 states in the continental U.S. The landfills varied in parameters such as size, waste composition, management strategy, geography, and climate zone. The diversity and composition of bacterial and archaeal populations in leachate samples were characterized by 16S rRNA gene sequence analysis, and compared against a variety of physical and chemical parameters in an attempt to identify their impact on selection. Members of the Epsilonproteobacteria, Gammaproteobacteria, Clostridia, and candidate division OP3 were the most abundant. The distribution of the observed phylogenetic diversity could best be explained by a combination of variables and was correlated most strongly with the concentrations of chloride and barium, rate of evapotranspiration, age of waste, and the number of detected household chemicals. This study illustrates how leachate microbiomes are distinct from those of other natural or built environments, and sheds light on the major selective forces responsible for this microbial diversity. PMID:27148222

Dependences of Ratio of the Luminosity to Ionization on Velocity and Chemical Composition of Meteors

NASA Technical Reports Server (NTRS)

Narziev, M.

2011-01-01

On the bases of results simultaneous photographic and radio echo observations, the results complex radar and television observations of meteors and also results of laboratory modeling of processes of a luminescence and ionization, correlation between of luminous intensity Ip to linear electronic density q from of velocities and chemical structure are investigated. It is received that by increasing value of velocities of meteors and decrease of nuclear weight of substance of particles, lg Ip/q decreased more than one order.

125Te NMR chemical-shift trends in PbTe–GeTe and PbTe–SnTe alloys

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

Njegic, Bosiljka; Levin, Evgenii M.; Schmidt-Rohr, Klaus

2013-10-08

Complex tellurides, such as doped PbTe, GeTe, and their alloys, are among the best thermoelectric materials. Knowledge of the change in 125Te NMR chemical shift due to bonding to dopant or “solute” atoms is useful for determination of phase composition, peak assignment, and analysis of local bonding. We have measured the 125Te NMR chemical shifts in PbTe-based alloys, Pb 1-xGe xTe and Pb 1-xSn xTe, which have a rocksalt-like structure, and analyzed their trends. For low x, several peaks are resolved in the 22-kHz MAS 125Te NMR spectra. A simple linear trend in chemical shifts with the number of Pbmore » neighbors is observed. No evidence of a proposed ferroelectric displacement of Ge atoms in a cubic PbTe matrix is detected at low Ge concentrations. The observed chemical shift trends are compared with the results of DFT calculations, which confirm the linear dependence on the composition of the first-neighbor shell. The data enable determination of the composition of various phases in multiphase telluride materials. They also provide estimates of the 125Te chemical shifts of GeTe and SnTe (+970 and +400±150 ppm, respectively, from PbTe), which are otherwise difficult to access due to Knight shifts of many hundreds of ppm in neat GeTe and SnTe.« less

Bulk measurements of messy chemistries are needed for a theory of the origins of life

NASA Astrophysics Data System (ADS)

Guttenberg, Nicholas; Virgo, Nathaniel; Chandru, Kuhan; Scharf, Caleb; Mamajanov, Irena

2017-11-01

A feature of many of the chemical systems plausibly involved in the origins of terrestrial life is that they are complex and messy-producing a wide range of compounds via a wide range of mechanisms. However, the fundamental behaviour of such systems is currently not well understood; we do not have the tools to make statistical predictions about such complex chemical networks. This is, in part, due to a lack of quantitative data from which such a theory could be built; specifically, functional measurements of messy chemical systems. Here, we propose that the pantheon of experimental approaches to the origins of life should be expanded to include the study of `functional measurements'-the direct study of bulk properties of chemical systems and their interactions with other compounds, the formation of structures and other behaviours, even in cases where the precise composition and mechanisms are unknown. This article is part of the themed issue 'Reconceptualizing the origins of life'.

Tuff of Bridge Spring: A mid-Miocene ash-flow tuff, northern Colorado River extensional corridor, Nevada and Arizona

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

Smith, E.I.; Morikawa, S.A.; Martin, M.W.

1993-04-01

The Tuff of Bridge Spring (TBS) (15.19[+-]0.02 Ma; Gans, 1991) is a compositionally variable dacite to rhyolite ash-flow tuff that crops out over 1800 sq. km in the northern Colorado River extensional corridor. The TBS varies in composition from 59.5 to 74 wt. % SiO[sub 2] and typically contains phenocrysts of sanidine, plagioclase, biotite, clinopyroxene, [+-] sphene, [+-] apatite, [+-] zircon, and [+-] hornblende. The TBS is thickest and displays its greatest compositional range in the center of its area of exposure. The McCullough Range section contains at least three chemically distinct flow units that vary in composition from dacitemore » to rhyolite. The basal and uppermost units are normally zoned and the middle unit is reversely zoned. The complex chemical zonation and zoning reversals in the TBS indicate that it erupted from a magma chamber that was periodically injected by both mafic and felsic magmas. Sections at the edge of the exposure area are thin, contain only one or two chemically definable flow units and have a limited compositional range. To the west at Sheep Mountain, TBS is 2.9 m thick and ranges from 70.2--71.7 wt % SiO[sub 2]. To the east in the White Hills, TBS is 14 m thick and ranges from 59.5--65.3 wt % SiO[sub 2]. This chemical and field data indicate that although the TBS is regionally extensive, individual flow units are not. Isotopic data and chemistry suggest that all sections of the TBS are cogenetic. Comparisons of chemical, geochronological and isotopic data between the TBS and nearby coeval plutons indicate that the Aztec Wash (Eldorado Mts., Nevada) and Mt. Perkins (Black Mountain, Arizona) plutons are possible source for the TBS. Both plutons exhibit ample evidence of magma mixing and commingling, processes that may produce compositional zonation such as that observed in the TBS.« less

A new look at sulphur chemistry in hot cores and corinos

NASA Astrophysics Data System (ADS)

Vidal, Thomas H. G.; Wakelam, Valentine

2018-03-01

Sulphur-bearing species are often used to probe the evolution of hot cores because their abundances are particularly sensitive to physical and chemical variations. However, the chemistry of sulphur is not well understood in these regions, notably because observations of several hot cores have displayed a large variety of sulphur compositions, and because the reservoir of sulphur in dense clouds, in which hot cores form, is still poorly constrained. In order to help disentangle its complexity, we present a fresh comprehensive review of sulphur chemistry in hot cores along with a study of sulphur's sensibility to temperature and pre-collapse chemical composition. In parallel, we analyse the discrepencies that result from the use of two different types of models (static and dynamic) in order to highlight the sensitivity to the choice of model to be used in astrochemical studies. Our results show that the pre-collapse chemical composition is a critical parameter for sulphur chemistry in hot cores and that it could explain the different sulphur compositions observed. We also report that differences in abundances for a given species between the static and dynamic models can reach six orders of magnitude in the hot core, which reveals the key role of the choice of model in astrochemical studies.

Chemically Active, Porous 3D-Printed Thermoplastic Composites.

PubMed

Evans, Kent A; Kennedy, Zachary C; Arey, Bruce W; Christ, Josef F; Schaef, Herbert T; Nune, Satish K; Erikson, Rebecca L

2018-05-02

Metal-organic frameworks (MOFs) exhibit exceptional properties and are widely investigated because of their structural and functional versatility relevant to catalysis, separations, and sensing applications. However, their commercial or large-scale application is often limited by their powder forms which make integration into devices challenging. Here, we report the production of MOF-thermoplastic polymer composites in well-defined and customizable forms and with complex internal structural features accessed via a standard three-dimensional (3D) printer. MOFs (zeolitic imidazolate framework; ZIF-8) were incorporated homogeneously into both poly(lactic acid) (PLA) and thermoplastic polyurethane (TPU) matrices at high loadings (up to 50% by mass), extruded into filaments, and utilized for on-demand access to 3D structures by fused deposition modeling. Printed, rigid PLA/MOF composites display a large surface area (SA avg = 531 m 2 g -1 ) and hierarchical pore features, whereas flexible TPU/MOF composites achieve a high surface area (SA avg = 706 m 2 g -1 ) by employing a simple method developed to expose obstructed micropores postprinting. Critically, embedded particles in the plastic matrices retain their ability to participate in chemical interactions characteristic of the parent framework. The fabrication strategies were extended to other MOFs and illustrate the potential of 3D printing to create unique porous and high surface area chemically active structures.

Physical characteristics and chemical quality of selected springs in parts of Juab, Millard, Tooele, and Utah counties, Utah

USGS Publications Warehouse

Wilberg, D.E.; Stolp, B.J.

1985-01-01

Hydrologic, geologic, and partial water quality data were collected at 90 selected springs in west-central Utah, and chemical analyses performed on water samples from 62 of the springs. Descriptions of the physiographic and geologic conditions, climate, and vegetation patterns for the study area are included. Allowable limits of certain chemical constituents in water for human and livestock consumption are included with the water quality data. Three classifications of springs were established based on physical characteristics of the springs, and chemical composition of the springflow: (1) mountain springs; (2) non-thermal valley springs, and (3) thermal valley springs. Mountain springs are in and near recharge areas, have seasonal variations of discharge and temperature, typically discharge from extrusive and metamorphic geohydrologic units, and generally discharge freshwater. Non-thermal valley springs are peripheral to recharge areas, have seasonal variations of discharge and temperature, typically discharge from a variety of geohydrologic units, and have variable water composition. Thermal valley springs are near topographic low areas of valleys , and have little seasonal variation of discharge or temperature. They typically discharge from unconsolidated deposits (but the discharge probably has flowed through buried carbonate geohydrologic units). They also have a considerable range of water composition that reflects the relative complexity of the groundwater system. (Author 's abstract)

Shocks and Molecules in Protostellar Outflows

NASA Astrophysics Data System (ADS)

Arce, Héctor

2014-06-01

As protostars form through the gravitational infall of material from their parent molecular cloud, they power energetic bipolar outflows that interact with the surrounding medium. Protostellar outflows are important to the chemical evolution of star forming regions, as the shocks produced by the interaction of the high-velocity protostellar wind and the ambient cloud can heat the surrounding medium and trigger chemical and physical processes that would otherwise not take place in a quiescent molecular cloud. Protostellar outflows, are therefore a great laboratory to study shock physics and shock-induced chemistry. I will present results from millimeter-wave observations of a small sample of outflow shocks. The spectra show clear evidence of the existence of complex organic molecules (e.g., methyl formate, ethanol, acetaldehyde) and high abundance of certain simple molecules (e.g., HCO^+, HCN, H_2O) in outflows. Results indicate that, most likely, the complex species formed on the surface of grains and were then ejected from the grain mantles by the shock. Spectral surveys of shocked regions using ALMA could therefore be used to probe the composition of dust in molecular clouds. Our results demonstrate that outflows modify the chemical composition of the surrounding gaseous environment and that this needs to be considered when using certain species to study active star forming regions.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications II. Users Manual and Program Description. 2; Users Manual and Program Description

NASA Technical Reports Server (NTRS)

McBride, Bonnie J.; Gordon, Sanford

1996-01-01

This users manual is the second part of a two-part report describing the NASA Lewis CEA (Chemical Equilibrium with Applications) program. The program obtains chemical equilibrium compositions of complex mixtures with applications to several types of problems. The topics presented in this manual are: (1) details for preparing input data sets; (2) a description of output tables for various types of problems; (3) the overall modular organization of the program with information on how to make modifications; (4) a description of the function of each subroutine; (5) error messages and their significance; and (6) a number of examples that illustrate various types of problems handled by CEA and that cover many of the options available in both input and output. Seven appendixes give information on the thermodynamic and thermal transport data used in CEA; some information on common variables used in or generated by the equilibrium module; and output tables for 14 example problems. The CEA program was written in ANSI standard FORTRAN 77. CEA should work on any system with sufficient storage. There are about 6300 lines in the source code, which uses about 225 kilobytes of memory. The compiled program takes about 975 kilobytes.

Layer-by-layer cell membrane assembly

NASA Astrophysics Data System (ADS)

Matosevic, Sandro; Paegel, Brian M.

2013-11-01

Eukaryotic subcellular membrane systems, such as the nuclear envelope or endoplasmic reticulum, present a rich array of architecturally and compositionally complex supramolecular targets that are as yet inaccessible. Here we describe layer-by-layer phospholipid membrane assembly on microfluidic droplets, a route to structures with defined compositional asymmetry and lamellarity. Starting with phospholipid-stabilized water-in-oil droplets trapped in a static droplet array, lipid monolayer deposition proceeds as oil/water-phase boundaries pass over the droplets. Unilamellar vesicles assembled layer-by-layer support functional insertion both of purified and of in situ expressed membrane proteins. Synthesis and chemical probing of asymmetric unilamellar and double-bilayer vesicles demonstrate the programmability of both membrane lamellarity and lipid-leaflet composition during assembly. The immobilized vesicle arrays are a pragmatic experimental platform for biophysical studies of membranes and their associated proteins, particularly complexes that assemble and function in multilamellar contexts in vivo.

Micropatterned stretchable circuit and strain sensor fabricated by lithography on an electrospun nanofiber mat.

PubMed

Park, Minwoo; Im, Jungkyun; Park, Jongjin; Jeong, Unyong

2013-09-11

This paper describes a novel approach for composite nanofiber mats and its application to fabricate a strain sensor. Electrospun poly(4-vinylpyridine) (P4VP) nanofiber mats are micropatterned by a lithographic approach that includes selective oxidation of the nanofibers and removal of unreacted fibers. The P4VP/HAuCl4 complex is converted to P4VP/Au composites by chemical reduction. We investigate the electrical resistivity of the composite mats according to the number of complexation-and-reduction cycles, the thickness of the fiber mats, and the annealing temperatures which control the percolation of the Au nanoparticles in the fiber mats. Nozzle printing of a polymeric solution on the patterned nanofiber mats simply produces an array of strain-sensitive and strain-invariant units. The patterns demonstrate high strain-sensing performance without any mechanical and electrical failure over 200 bending cycles in the strain range of ε<0.17.

Grain Surface Chemistry and the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.

2006-01-01

Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

Efficient analysis of complex natural materials using LA-ICP-MS

NASA Astrophysics Data System (ADS)

Kent, A. J.; Loewen, M. W.; Koleszar, A. M.; Miller, J.; Ungerer, C. "

2011-12-01

Many natural materials exhibit complex variations in chemical or isotopic composition over relatively short length scales, and these compositional variations often record important information about the environment or nature of the processes that lead to formation. Examples include complexly zoned crystals within volcanic rocks that record magmatic and volcanic signals, otoliths and other biominerals that record life history and environmental information, and speleothems that record climatic variables. Laser ablation ICP-MS analyses offer several advantages for quantifying compositional in chemically complex natural materials. These include the speed of analysis, the ability to sample at atmospheric pressures, the wide diversity of possible analytes, and the ability to make measurements in both spot and raster modes. The latter in particular offers advantages for analyses that require efficient acquisition of information over significant length scales, as in raster mode compositional data can be rapidly obtained by translating the laser laterally over a compositional variable material during a single analysis. In this fashion elemental or isotopic composition at a given analysis time corresponds to the lateral spatial dimension. This contrasts with a record obtained by a row of individual spots, which require a large number of discrete analyses, and requires significantly more analysis time. However there are also disadvantages to this style of analysis. Translation of the circular spots typically used for analysis results in significant signal attenuation and production of artifacts that may mirror natural diffusion profiles or other gradual changes. The ability to ablate using non-circular spots significantly reduces this effect, although the degree of attenuation is also increased by slower ablation cell response times. For single volume cells this may result in 50-100% additional attenuation than that produced by the translation of the spot alone, although two-volume and other rapid response cells significantly reduce this effect. Raster analyses are also highly sensitive to the presence of small contaminant phases along the raster trajectory, as the compositional signal from these can become attenuated and difficult to distinguish from natural compositional variations. It can also be difficult to establish exactly where compositional changes occur in materials that are visually homogenous. In this contribution we discuss these issues in more detail and present data acquisition and processing strategies that minimize these difficulties.

Bulk and surface properties of liquid Al-Cr and Cr-Ni alloys.

PubMed

Novakovic, R

2011-06-15

The energetics of mixing and structural arrangement in liquid Al-Cr and Cr-Ni alloys has been analysed through the study of surface properties (surface tension and surface segregation), dynamic properties (chemical diffusion) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of statistical mechanical theory in conjunction with quasi-lattice theory. The Al-Cr phase diagram exhibits the existence of different intermetallic compounds in the solid state, while that of Cr-Ni is a simple eutectic-type phase diagram at high temperatures and includes the low-temperature peritectoid reaction in the range near a CrNi(2) composition. Accordingly, the mixing behaviour in Al-Cr and Cr-Ni alloy melts was studied using the complex formation model in the weak interaction approximation and by postulating Al(8)Cr(5) and CrNi(2) chemical complexes, respectively, as energetically favoured.

An intermediate level of abstraction for computational systems chemistry.

PubMed

Andersen, Jakob L; Flamm, Christoph; Merkle, Daniel; Stadler, Peter F

2017-12-28

Computational techniques are required for narrowing down the vast space of possibilities to plausible prebiotic scenarios, because precise information on the molecular composition, the dominant reaction chemistry and the conditions for that era are scarce. The exploration of large chemical reaction networks is a central aspect in this endeavour. While quantum chemical methods can accurately predict the structures and reactivities of small molecules, they are not efficient enough to cope with large-scale reaction systems. The formalization of chemical reactions as graph grammars provides a generative system, well grounded in category theory, at the right level of abstraction for the analysis of large and complex reaction networks. An extension of the basic formalism into the realm of integer hyperflows allows for the identification of complex reaction patterns, such as autocatalysis, in large reaction networks using optimization techniques.This article is part of the themed issue 'Reconceptualizing the origins of life'. © 2017 The Author(s).

Chemical and physical characterization of the first stages of protoplanetary disk formation

NASA Astrophysics Data System (ADS)

Hincelin, Ugo

2012-12-01

Low mass stars, like our Sun, are born from the collapse of a molecular cloud. The matter falls in the center of the cloud, creating a protoplanetary disk surrounding a protostar. Planets and other Solar System bodies will be formed in the disk. The chemical composition of the interstellar matter and its evolution during the formation of the disk are important to better understand the formation process of these objects. I studied the chemical and physical evolution of this matter, from the cloud to the disk, using the chemical gas-grain code Nautilus. A sensitivity study to some parameters of the code (such as elemental abundances and parameters of grain surface chemistry) has been done. More particularly, the updates of rate coefficients and branching ratios of the reactions of our chemical network showed their importance, such as on the abundances of some chemical species, and on the code sensitivity to others parameters. Several physical models of collapsing dense core have also been considered. The more complex and solid approach has been to interface our chemical code with the radiation-magneto-hydrodynamic model of stellar formation RAMSES, in order to model in three dimensions the physical and chemical evolution of a young disk formation. Our study showed that the disk keeps imprints of the past history of the matter, and so its chemical composition is sensitive to the initial conditions.

Infrared nanospectroscopy reveals the chemical nature of pit membranes in water-conducting cells of the plant xylem.

PubMed

Pereira, Luciano; Flores-Borges, Denisele; Bittencourt, Paulo; Mayer, Juliana; Kiyota, Eduardo; Araújo, Pedro; Jansen, Steven; Freitas, Raul; Oliveira, Rafael; Mazzafera, Paulo

2018-06-05

In the xylem of angiosperm plants, microscopic pits through the secondary cell walls connect the water-conducting vessels. Cellulosic meshes originated from primary walls and middle lamella between adjacent vessels, called pit membrane, separates one conduit from another. The intricate structure of the nano-sized pores in pit membranes enables the passage of water under negative pressure without hydraulic failure due to obstruction by gas bubbles (i.e., embolism) under normal conditions or mild drought stress. Since the chemical composition of pit membranes affects embolism formation and bubble behavior, we directly measured pit membrane composition in Populus nigra wood. Here, we characterized the chemical composition of cell wall structures by synchrotron infrared nanospectroscopy and atomic force microscopy-infrared nanospectroscopy with high spatial resolution. Characteristic peaks of cellulose, phenolic compounds, and proteins were found in the intervessel pit membrane of P. nigra wood. In addition, vessel to parenchyma pit membranes and developing cell walls of the vascular cambium showed clear signals of cellulose, proteins, and pectin. We did not find a distinct peak of lignin and other compounds in these structures. Our investigation of the complex chemical composition of intervessel pit membranes furthers our understanding of the flow of water and bubbles between neighboring conduits. The advances presented here pave the way for further label-free studies related to the nano-chemistry of plant cell components. {copyright, serif} 2018 American Society of Plant Biologists. All rights reserved.

SUMMARY OF 2010 DOE EM INTERNATIONAL PROGRAM STUDIES OF WASTE GLASS STRUCTURE AND PROPERTIES

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

Fox, K.; Choi, A.; Marra, J.

2011-02-07

Collaborative work between the Savannah River National Laboratory (SRNL) and SIA Radon in Russia was divided among three tasks for calendar year 2010. The first task focused on the study of simplified high level waste glass compositions with the objective of identifying the compositional drivers that lead to crystallization and poor chemical durability. The second task focused on detailed characterization of more complex waste glass compositions with unexpectedly poor chemical durabilities. The third task focused on determining the structure of select high level waste glasses made with varying frit compositions in order to improve models under development for predicting themore » melt rate of the Defense Waste Processing Facility (DWPF) glasses. The majority of these tasks were carried out at SIA Radon. Selection and fabrication of the glass compositions, along with chemical composition measurements and evaluations of durability were carried out at SRNL and are described in this report. SIA Radon provided three summary reports based on the outcome of the three tasks. These reports are included as appendices to this document. Briefly, the result of characterization of the Task 1 glasses may indicate that glass compositions where iron is predominantly tetrahedrally coordinated have more of a tendency to crystallize nepheline or nepheline-like phases. For the Task 2 glasses, the results suggested that the relatively low fraction of tetrahedrally coordinated boron and the relatively low concentrations of Al{sub 2}O{sub 3} available to form [BO{sub 4/2}]{sup -}Me{sup +} and [AlO{sub 4/2}]{sup -}Me{sup +} tetrahedral units are not sufficient to consume all of the alkali ions, and thus these alkali ions are easily leached from the glasses. All of the twelve Task 3 glass compositions were determined to be mainly amorphous, with some minor spinel phases. Several key structural units such as metasilicate chains and rings were identified, which confirms the current modeling approach for the silicate phase. The coordination of aluminum and iron was found to be mainly tetrahedral, with some octahedral iron ions. In all samples, trigonally-coordinated boron was determined to dominate over tetrahedrally-coordinated boron. The results further suggested that BO{sub 4} tetrahedra and BO{sub 3} triangles form complex borate units and may be present as separate constituents. However, no quantification of tetrahedral-to-trigonal boron ratio was made.« less

Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Nickel and Copper Complexes of Bis(thiosemicrbazone)

PubMed Central

Chandra, Sulekh; Raizada, Smriti; Tyagi, Monika; Gautam, Archana

2007-01-01

A series of metal complexes of Cu(II) and Ni(II) having the general composition [M(L)X2] with benzil bis(thiosemicarbazone) has been prepared and characterized by element chemical analysis, molar conductance, magnetic susceptibility measurements, and spectral (electronic, IR, EPR, mass) studies. The IR spectral data suggest the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes but a tetragonal geometry for Cu(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties. PMID:18273385

Groundwater geochemistry of a Mio-Pliocene aquifer in the northeastern Algerian Sahara (Djamaa region)

NASA Astrophysics Data System (ADS)

Houari, Idir Menad; Nezli, Imed Eddine; Belksier, Mohamed Salah

2018-05-01

The groundwater resources in the Northern Sahara are represented by two superimposed major aquifer systems: the Intercalary Continental (CI) and the Terminal Complex (CT). The waters of these aquifers pose serious physical and chemical quality problems; they are highly mineralized and very hard. The present work aims to describe the water's geochemical evolution of sand groundwater (Mio-Pliocene) of the Terminal Complex in the area of Djamaa, by the research of the relationship between water's chemical composition and lithology of aquifer formations through. The results obtained show that the water's chemistry is essentially governed by the dissolution of evaporate formations, which gives to, waters an excessive mineralization expressed by high concentrations of sulfates, chlorides and sodium.

Protection of trabecular bone in ovariectomized rats by turmeric (Curcuma longa L.) is dependent on extract composition.

PubMed

Wright, Laura E; Frye, Jennifer B; Timmermann, Barbara N; Funk, Janet L

2010-09-08

Extracts prepared from turmeric (Curcuma longa L., [Zingiberaceae]) containing bioactive phenolic curcuminoids were evaluated for bone-protective effects in a hypogonadal rat model of postmenopausal osteoporosis. Three-month female Sprague-Dawley rats were ovariectomized (OVX) and treated with a chemically complex turmeric fraction (41% curcuminoids by weight) or a curcuminoid-enriched turmeric fraction (94% curcuminoids by weight), both dosed at 60 mg/kg 3x per week, or vehicle alone. Effects of two months of treatment on OVX-induced bone loss were followed prospectively by serial assessment of bone mineral density (BMD) of the distal femur using dual-energy X-ray absorptiometry (DXA), while treatment effects on trabecular bone microarchitecture were assessed at two months by microcomputerized tomography (microCT). Chemically complex turmeric did not prevent bone loss, however, the curcuminoid-enriched turmeric prevented up to 50% of OVX-induced loss of trabecular bone and also preserved the number and connectedness of the strut-like trabeculae. These results suggest that turmeric may have bone-protective effects but that extract composition is a critical factor.

Protection of Trabecular Bone in Ovariectomized Rats by Turmeric (Curcuma longa L.) is Dependent on Extract Composition

PubMed Central

Wright, Laura E.; Frye, Jennifer B.; Timmermann, Barbara N.; Funk, Janet L.

2010-01-01

Extracts prepared from turmeric (Curcuma longa L., [Zingiberaceae]) containing bioactive phenolic curcuminoids were evaluated for bone-protective effects in a hypogonadal rat model of postmenopausal osteoporosis. Three-month female Sprague Dawley rats were ovariectomized (OVX) and treated with a chemically complex turmeric fraction (41% curcuminoids by weight) or a curcuminoid-enriched turmeric fraction (94% curcuminoids by weight), both dosed at 60mg/kg 3x per week, or vehicle alone. Effects of two months of treatment on OVX-induced bone loss were followed prospectively by serial assessment of bone mineral density (BMD) of the distal femur using dual-energy x-ray absorptiometry (DXA), while treatment effects on trabecular bone microarchitecture were assessed at two months by micro-computerized tomography (μCT). Chemically complex turmeric did not prevent bone loss, however, the curcuminoid-enriched turmeric prevented up to 50% of OVX-induced loss of trabecular bone and also preserved the number and connectedness of the strut-like trabeculae. These results suggest that turmeric may have bone-protective effects but that extract composition is a critical factor. PMID:20695490

Structural building principles of complex face-centered cubic intermetallics.

PubMed

Dshemuchadse, Julia; Jung, Daniel Y; Steurer, Walter

2011-08-01

Fundamental structural building principles are discussed for all 56 known intermetallic phases with approximately 400 or more atoms per unit cell and space-group symmetry F43m, Fd3m, Fd3, Fm3m or Fm3c. Despite fundamental differences in chemical composition, bonding and electronic band structure, their complex crystal structures show striking similarities indicating common building principles. We demonstrate that the structure-determining elements are flat and puckered atomic {110} layers stacked with periodicities 2p. The atoms on this set of layers, which intersect each other, form pentagon face-sharing endohedral fullerene-like clusters arranged in a face-centered cubic packing (f.c.c.). Due to their topological layer structure, all these crystal structures can be described as (p × p × p) = p(3)-fold superstructures of a common basic structure of the double-diamond type. The parameter p, with p = 3, 4, 7 or 11, is determined by the number of layers per repeat unit and the type of cluster packing, which in turn are controlled by chemical composition.

Dynamically reconfigurable complex emulsions via tunable interfacial tensions

PubMed Central

Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

2015-01-01

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including multiple emulsions and Janus droplets which contain hemispheres of differing material, are of increasing importance1 in pharmaceuticals and medical diagnostics2, in the fabrication of microparticles and capsules3–5 for food6, in chemical separations7, in cosmetics8, and in dynamic optics9. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets’ physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes10, to small-volume but more precise microfluidic methods11,12. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have greatly increased utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials. PMID:25719669

Dynamically reconfigurable complex emulsions via tunable interfacial tensions.

PubMed

Zarzar, Lauren D; Sresht, Vishnu; Sletten, Ellen M; Kalow, Julia A; Blankschtein, Daniel; Swager, Timothy M

2015-02-26

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials.

Dynamically reconfigurable complex emulsions via tunable interfacial tensions

NASA Astrophysics Data System (ADS)

Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

2015-02-01

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials.

A multi-species exchange model for fully fluctuating polymer field theory simulations.

PubMed

Düchs, Dominik; Delaney, Kris T; Fredrickson, Glenn H

2014-11-07

Field-theoretic models have been used extensively to study the phase behavior of inhomogeneous polymer melts and solutions, both in self-consistent mean-field calculations and in numerical simulations of the full theory capturing composition fluctuations. The models commonly used can be grouped into two categories, namely, species models and exchange models. Species models involve integrations of functionals that explicitly depend on fields originating both from species density operators and their conjugate chemical potential fields. In contrast, exchange models retain only linear combinations of the chemical potential fields. In the two-component case, development of exchange models has been instrumental in enabling stable complex Langevin (CL) simulations of the full complex-valued theory. No comparable stable CL approach has yet been established for field theories of the species type. Here, we introduce an extension of the exchange model to an arbitrary number of components, namely, the multi-species exchange (MSE) model, which greatly expands the classes of soft material systems that can be accessed by the complex Langevin simulation technique. We demonstrate the stability and accuracy of the MSE-CL sampling approach using numerical simulations of triblock and tetrablock terpolymer melts, and tetrablock quaterpolymer melts. This method should enable studies of a wide range of fluctuation phenomena in multiblock/multi-species polymer blends and composites.

Method of forming a chemical composition

DOEpatents

Bingham, Dennis N.; Wilding, Bruce M.; Klingler, Kerry M.; Zollinger, William T.; Wendt, Kraig M.

2007-10-09

A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

Astrochemical evolution along star formation: Overview of the IRAM Large Program ASAI

NASA Astrophysics Data System (ADS)

Lefloch, Bertrand; Bachiller, R.; Ceccarelli, C.; Cernicharo, J.; Codella, C.; Fuente, A.; Kahane, C.; López-Sepulcre, A.; Tafalla, M.; Vastel, C.; Caux, E.; González-García, M.; Bianchi, E.; Gómez-Ruiz, A.; Holdship, J.; Mendoza, E.; Ospina-Zamudio, J.; Podio, L.; Quénard, D.; Roueff, E.; Sakai, N.; Viti, S.; Yamamoto, S.; Yoshida, K.; Favre, C.; Monfredini, T.; Quitián-Lara, H. M.; Marcelino, N.; Roberty, H. Boechat; Cabrit, S.

2018-04-01

Evidence is mounting that the small bodies of our Solar System, such as comets and asteroids, have at least partially inherited their chemical composition from the first phases of the Solar System formation. It then appears that the molecular complexity of these small bodies is most likely related to the earliest stages of star formation. It is therefore important to characterize and to understand how the chemical evolution changes with solar-type protostellar evolution. We present here the Large Program "Astrochemical Surveys At IRAM" (ASAI). Its goal is to carry out unbiased millimeter line surveys between 80 and 272 GHz of a sample of ten template sources, which fully cover the first stages of the formation process of solar-type stars, from prestellar cores to the late protostellar phase. In this article, we present an overview of the surveys and results obtained from the analysis of the 3 mm band observations. The number of detected main isotopic species barely varies with the evolutionary stage and is found to be very similar to that of massive star-forming regions. The molecular content in O- and C- bearing species allows us to define two chemical classes of envelopes, whose composition is dominated by either a) a rich content in O-rich complex organic molecules, associated with hot corino sources, or b) a rich content in hydrocarbons, typical of Warm Carbon Chain Chemistry sources. Overall, a high chemical richness is found to be present already in the initial phases of solar-type star formation.

Fatty acid and sterol composition of three phytomonas species.

PubMed

Nakamura, C V; Waldow, L; Pelegrinello, S R; Ueda-Nakamura, T; Filho, B A; Filho, B P

1999-01-01

Fatty acid and sterol analysis were performed on Phytomonas serpens and Phytomonas sp. grown in chemically defined and complex medium, and P. françai cultivated in complex medium. The three species of the genus Phytomonas had qualitatively identical fatty acid patterns. Oleic, linoleic, and linolenic were the major unsaturated fatty acids. Miristic and stearic were the major saturated fatty acids. Ergosterol was the only sterol isolated from Phytmonas sp. and P. serpens grown in a sterol-free medium, indicating that it was synthesized de novo. When P. françai that does not grow in defined medium was cultivated in a complex medium, cholesterol was the only sterol detected. The fatty acids and sterol isolated from Phytomonas sp. and P. serpens grown in a chemically defined lipid-free medium indicated that they were able to biosynthesize fatty acids and ergosterol from acetate or from acetate precursors such as glucose or threonine.

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

Stair, Peter C.

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supportedmore » metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.« less

Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains

PubMed Central

Pollard, Benjamin

2016-01-01

Summary Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force–distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

From Astrochemistry to prebiotic chemistry? An hypothetical approach toward Astrobiology

NASA Astrophysics Data System (ADS)

Le Sergeant d'Hendecourt, L.; Danger, G.

2012-12-01

We present in this paper a general perspective about the evolution of molecular complexity, as observed from an astrophysicist point of view and its possible relation to the problem of the origin of life on Earth. Based on the cosmic abundances of the elements and the molecular composition of our life, we propose that life cannot really be based on other elements. We discuss where the necessary molecular complexity is built-up in astrophysical environments, actually within inter/circumstellar solid state materials known as ``grains''. Considerations based on non-directed laboratory experiments, that must be further extended in the prebiotic domain, lead to the hypothesis that if the chemistry at the origin of life may indeed be a rather universal and deterministic phenomenon, once molecular complexity is installed, the chemical evolution that generated the first prebiotic reactions that involve autoreplication must be treated in a systemic approach because of the strong contingency imposed by the complex local environment(s) and associated processes in which these chemical systems have evolved.

Synthesis of Hierarchical Nanoporous Microstructures via the Kirkendall Effect in Chemical Reduction Process

NASA Astrophysics Data System (ADS)

Gao, Ling; Pang, Chao; He, Dafang; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

2015-11-01

A series of novel hierarchical nanoporous microstructures have been synthesized through one-step chemical reduction of micron size Cu2O and Co3O4 particles. By controlling the reduction time, non-porous Cu2O microcubes sequentially transform to nanoporous Cu/Cu2O/Cu dented cubic composites and hollow eightling-like Cu microparticles. The mechanism involved in the complex structural evolution is explained based on oxygen diffusion and Kirkendall effect. The nanoporous Cu/Cu2O/Cu dented cubic composites exhibit superior electrochemical performance as compared to solid Cu2O microcubes. The reduction of nonporous Co3O4 also exhibits a uniform sequential reduction process from nonporous Co3O4 to porous Co3O4/CoO composites, porous CoO, porous CoO/Co composites, and porous foam-like Co particles. Nanoscale channels originate from the particle surface and eventually develop inside the entire product, resulting in porous foam-like Co microparticles. The Kirkendall effect is believed to facilitate the formation of porous structures in both processes.

Modern views on the composition of anionic oxy-fluoride complexes of aluminium and their rearrangement during the electrolysis of cryolite-alumina melts

NASA Astrophysics Data System (ADS)

Khramov, A. P.; Shurov, N. I.

2014-08-01

Some consequences of the hypothesis of the absence of free F- ions in cryolite-alumina melts are observed. The melt at 1 < CR < 3 is assumed to consist of the complexes AlF{6/3-}, AlF{5/2-}, AlF{4/-}, Al2OF{6/2-}, and Al2O2F{4/2-}, and alkali metal cations. A formal-stoichiometric study of the processes occurring during electrolysis is performed on the basis of the accepted hypothesis. Judgments about some of the features of the electrode reactions and chemical reactions in the electrolyte volume are presented. The reaction schemes for the instances with and without the subsequent/preceding chemical reaction near the electrode or in the molten salt volume are given. The mass flows of various forms of ionic complexes through the electrolyte volume are given for these schemes. Definitive conclusions are not made in the study, but the range of possible variants for the electrochemical routes of the overall chemical reaction in the cell is limited.

High-Speed, Three Dimensional Object Composition Mapping Technology

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

Ishikawa, M Y

2001-02-14

This document overviews an entirely new approach to determining the composition--the chemical-elemental, isotopic and molecular make-up--of complex, highly structured objects, moreover with microscopic spatial resolution in all 3 dimensions. The front cover depicts the new type of pulsed laser system at the heart of this novel technology under adjustment by Alexis Wynne, and schematically indicates two of its early uses: swiftly analyzing the 3-D composition governed structure of a transistor circuit with both optical and mass-spectrometric detectors, and of fossilized dinosaur and turtle bones high-speed probed by optical detection means. Studying the composition-cued 3-D micro-structures of advanced composite materials andmore » the microscopic scale composition-texture of biological tissues are two near-term examples of the rich spectrum of novel applications enabled by this field-opening analytic tool-set.« less

On the competition among aerosol number, size and composition in predicting CCN variability: a multi-annual field study in an urbanized desert.

PubMed

Crosbie, E; Youn, J-S; Balch, B; Wonaschütz, A; Shingler, T; Wang, Z; Conant, W C; Betterton, E A; Sorooshian, A

2015-02-10

A 2-year data set of measured CCN (cloud condensation nuclei) concentrations at 0.2 % supersaturation is combined with aerosol size distribution and aerosol composition data to probe the effects of aerosol number concentrations, size distribution and composition on CCN patterns. Data were collected over a period of 2 years (2012-2014) in central Tucson, Arizona: a significant urban area surrounded by a sparsely populated desert. Average CCN concentrations are typically lowest in spring (233 cm -3 ), highest in winter (430 cm -3 ) and have a secondary peak during the North American monsoon season (July to September; 372 cm -3 ). There is significant variability outside of seasonal patterns, with extreme concentrations (1 and 99 % levels) ranging from 56 to 1945 cm -3 as measured during the winter, the season with highest variability. Modeled CCN concentrations based on fixed chemical composition achieve better closure in winter, with size and number alone able to predict 82% of the variance in CCN concentration. Changes in aerosol chemical composition are typically aligned with changes in size and aerosol number, such that hygroscopicity can be parameterized even though it is still variable. In summer, models based on fixed chemical composition explain at best only 41% (pre-monsoon) and 36% (monsoon) of the variance. This is attributed to the effects of secondary organic aerosol (SOA) production, the competition between new particle formation and condensational growth, the complex interaction of meteorology, regional and local emissions and multi-phase chemistry during the North American monsoon. Chemical composition is found to be an important factor for improving predictability in spring and on longer timescales in winter. Parameterized models typically exhibit improved predictive skill when there are strong relationships between CCN concentrations and the prevailing meteorology and dominant aerosol physicochemical processes, suggesting that similar findings could be possible in other locations with comparable climates and geography.

Presence of chemical additives and microbial inhibition capacity in grapefruit seed extracts used in apiculture.

PubMed

Spinosi, Valerio; Semprini, Primula; Langella, Vincenzo; Scortichini, Giampiero; Calvarese, Silvano

2007-01-01

American foulbrood, caused by Paenibacillus larvae subsp. larvae (White 1906) is one of the most serious diseases of honey bees, causing beekeepers and health workers to make difficult, complex decisions and leading to the development of 'organic' treatments, such as grapefruit seed extract, with minor residue problems in the end product. This study evaluates the chemical composition of grapefruit seed extracts using gas chromatography/mass spectrometry for the detection of benzethonium chloride, cetrimonium bromide and decyltrimethylammonium chloride. The results obtained suggest a close correlation between the microbial effect and the presence of chemical additives in the samples analysed.

A chemical-biological similarity-based grouping of complex substances as a prototype approach for evaluating chemical alternatives.

PubMed

Grimm, Fabian A; Iwata, Yasuhiro; Sirenko, Oksana; Chappell, Grace A; Wright, Fred A; Reif, David M; Braisted, John; Gerhold, David L; Yeakley, Joanne M; Shepard, Peter; Seligmann, Bruce; Roy, Tim; Boogaard, Peter J; Ketelslegers, Hans B; Rohde, Arlean M; Rusyn, Ivan

2016-08-21

Comparative assessment of potential human health impacts is a critical step in evaluating both chemical alternatives and existing products on the market. Most alternatives assessments are conducted on a chemical-by-chemical basis and it is seldom acknowledged that humans are exposed to complex products, not individual substances. Indeed, substances of U nknown or V ariable composition, C omplex reaction products, and B iological materials (UVCBs) are ubiquitous in commerce yet they present a major challenge for registration and health assessments. Here, we present a comprehensive experimental and computational approach to categorize UVCBs according to global similarities in their bioactivity using a suite of in vitro models. We used petroleum substances, an important group of UVCBs which are grouped for regulatory approval and read-across primarily on physico-chemical properties and the manufacturing process, and only partially based on toxicity data, as a case study. We exposed induced pluripotent stem cell-derived cardiomyocytes and hepatocytes to DMSO-soluble extracts of 21 petroleum substances from five product groups. Concentration-response data from high-content imaging in cardiomyocytes and hepatocytes, as well as targeted high-throughput transcriptomic analysis of the hepatocytes, revealed distinct groups of petroleum substances. Data integration showed that bioactivity profiling affords clustering of petroleum substances in a manner similar to the manufacturing process-based categories. Moreover, we observed a high degree of correlation between bioactivity profiles and physico-chemical properties, as well as improved groupings when chemical and biological data were combined. Altogether, we demonstrate how novel in vitro screening approaches can be effectively utilized in combination with physico-chemical characteristics to group complex substances and enable read-across. This approach allows for rapid and scientifically-informed evaluation of health impacts of both existing substances and their chemical alternatives.

Relationship between Composition and Toxicity of Motor Vehicle Emission Samples

PubMed Central

McDonald, Jacob D.; Eide, Ingvar; Seagrave, JeanClare; Zielinska, Barbara; Whitney, Kevin; Lawson, Douglas R.; Mauderly, Joe L.

2004-01-01

In this study we investigated the statistical relationship between particle and semivolatile organic chemical constituents in gasoline and diesel vehicle exhaust samples, and toxicity as measured by inflammation and tissue damage in rat lungs and mutagenicity in bacteria. Exhaust samples were collected from “normal” and “high-emitting” gasoline and diesel light-duty vehicles. We employed a combination of principal component analysis (PCA) and partial least-squares regression (PLS; also known as projection to latent structures) to evaluate the relationships between chemical composition of vehicle exhaust and toxicity. The PLS analysis revealed the chemical constituents covarying most strongly with toxicity and produced models predicting the relative toxicity of the samples with good accuracy. The specific nitro-polycyclic aromatic hydrocarbons important for mutagenicity were the same chemicals that have been implicated by decades of bioassay-directed fractionation. These chemicals were not related to lung toxicity, which was associated with organic carbon and select organic compounds that are present in lubricating oil. The results demonstrate the utility of the PCA/PLS approach for evaluating composition–response relationships in complex mixture exposures and also provide a starting point for confirming causality and determining the mechanisms of the lung effects. PMID:15531438

Understanding the human health effects of chemical mixtures.

PubMed Central

Carpenter, David O; Arcaro, Kathleen; Spink, David C

2002-01-01

Most research on the effects of chemicals on biologic systems is conducted on one chemical at a time. However, in the real world people are exposed to mixtures, not single chemicals. Although various substances may have totally independent actions, in many cases two substances may act at the same site in ways that can be either additive or nonadditive. Many even more complex interactions may occur if two chemicals act at different but related targets. In the extreme case there may be synergistic effects, in which case the effects of two substances together are greater than the sum of either effect alone. In reality, most persons are exposed to many chemicals, not just one or two, and therefore the effects of a chemical mixture are extremely complex and may differ for each mixture depending on the chemical composition. This complexity is a major reason why mixtures have not been well studied. In this review we attempt to illustrate some of the principles and approaches that can be used to study effects of mixtures. By the nature of the state of the science, this discussion is more a presentation of what we do not know than of what we do know about mixtures. We approach the study of mixtures at three levels, using specific examples. First, we discuss several human diseases in relation to a variety of environmental agents believed to influence the development and progression of the disease. We present results of selected cellular and animal studies in which simple mixtures have been investigated. Finally, we discuss some of the effects of mixtures at a molecular level. PMID:11834461

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

NASA Astrophysics Data System (ADS)

Barmina, I.; Kolmickovs, A.; Valdmanis, R.; Vostrikovs, S.; Zake, M.

2018-05-01

Thermo-chemical conversion of microwave activated wheat straw mixtures with wood or peat pellets is studied experimentally with the aim to provide more effective application of wheat straw for heat energy production. Microwave pre-processing of straw pellets is used to provide a partial decomposition of the main constituents of straw and to activate the thermo-chemical conversion of wheat straw mixtures with wood or peat pellets. The experimental study includes complex measurements of the elemental composition of biomass pellets (wheat straw, wood, peat), DTG analysis of their thermal degradation, FTIR analysis of the composition of combustible volatiles entering the combustor, the flame temperature, the heat output of the device and composition of the products by comparing these characteristics for mixtures with unprocessed and mw pre-treated straw pellets. The results of experimental study confirm that mw pre-processing of straw activates the thermal decomposition of mixtures providing enhanced formation of combustible volatiles. This leads to improvement of the combustion conditions in the flame reaction zone, completing thus the combustion of volatiles, increasing the flame temperature, the heat output from the device, the produced heat energy per mass of burned mixture and decreasing at the same time the mass fraction of unburned volatiles in the products.

Variations in Depth and Chemical Composition of Groundwater During an Interval in Intermittent Water Delivery.

PubMed

Yongjin, Chen; Weihong, Li; Jiazhen, Liu; Ming, Lu; Mengchen, Xu; Shengliang, Liu

2015-08-01

Based on monitoring data collected from 2006 to 2009 at the lower reaches of the Tarim River, tempo-spatial variations in groundwater depth and chemistry during an approximately 3-year interval of intermittent water delivery were studied. Results indicate that as the groundwater depth increased at the upper sector of the river's lower reaches from March 2007 to September 2009, so too did the main chemical composition of groundwater. Groundwater depth at the intermediate sector also increased, but major ions in groundwater declined. The groundwater depth at the lower sector started to decrease in August 2008, and the concentrations of main ions in the groundwater generally rose and fell along with the variations in groundwater depth. The groundwater depth and chemistry in the monitoring wells located at a distance from the aqueduct expressed complex changes at different sections. For instance, at the section near the Daxihaizi Reservoir Section B, groundwater depth increased gradually, but chemical composition changed little. In contrast, the groundwater depth of monitoring wells far from the Daxihaizi Reservoir (Section I) decreased and salt content in the groundwater increased. In sectors at a moderate distance from the reservoir, groundwater depth decreased and concentrations of main ions significantly increased.

Immobilization of long-lived radionuclides in carbon matrices produced with the use of polyimide binders

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

Abdulakhatov, Murat; Bartenev, Sergey; Firsin, Nikolai

Available in abstract form only. Full text of publication follows: Conditions for immobilization of long-lived radionuclides {sup 99}Tc, {sup 129}I and {sup 241}Am in carbon matrices were investigated by using their chemical analogs. Stable isotopes of rhenium, iodine and europium were used as chemical analogs of {sup 99}Tc, {sup 129}I and {sup 241}Am, respectively. It is shown that the carbon matrices incorporating the above elements can be produced by carbonization of composites with ITA-31 polyimide binder of the following composition: equal molar ratio between dianhydride of 3,3/,4,4/-benzophenone-tetracarboxylic acid and tetraacetyl derivative of 4,4/-diaminodiphenyl ester, radionuclide being investigated or its chemicalmore » analog and carbon fabric as reinforcing component. The elements under investigation were used both in the form of salts or oxides and in the form of their complexes with ion-exchange resins. The produced composites were carbonized in inert gas (argon) or in vacuum. The physical-chemical properties of the samples were studied. It was revealed that the resultant matrices meet the requirements imposed on waste storage and final disposal. (authors)« less

Recent progress to understand stress corrosion cracking in sodium borosilicate glasses: linking the chemical composition to structural, physical and fracture properties

NASA Astrophysics Data System (ADS)

Rountree, Cindy L.

2017-08-01

This topical review is dedicated to understanding stress corrosion cracking in oxide glasses and specifically the SiO_2{\\text-B_2O_3{\\text-}Na_2O} (SBN) ternary glass systems. Many review papers already exist on the topic of stress corrosion cracking in complex oxide glasses or overly simplified glasses (pure silica). These papers look at how systematically controlling environmental factors (pH, temperature...) alter stress corrosion cracking, while maintaining the same type of glass sample. Many questions still exist, including: What sets the environmental limit? What sets the velocity versus stress intensity factor in the slow stress corrosion regime (Region I)? Can researchers optimize these two effects to enhance a glass’ resistance to failure? To help answer these questions, this review takes a different approach. It looks at how systemically controlling the glass’ chemical composition alters the structure and physical properties. These changes are then compared and contrasted to the fracture toughness and the stress corrosion cracking properties. By taking this holistic approach, researchers can begin to understand the controlling factors in stress corrosion cracking and how to optimize glasses via the initial chemical composition.

Interactive effects of chemical and biological controls on food-web composition in saline prairie lakes.

PubMed

Cooper, Ryan N; Wissel, Björn

2012-11-27

Salinity is restricting habitatability for many biota in prairie lakes due to limited physiological abilities to cope with increasing osmotic stress. Yet, it remains unclear how salinity effects vary among major taxonomic groups and what role other environmental parameters play in shaping food-web composition. To answer these questions, we sampled fish, zooplankton and littoral macroinvertebrates in 20 prairie lakes (Saskatchewan, Canada) characterized by large gradients in water chemistry and lake morphometry. We showed that salinity thresholds differed among major taxonomic groups, as most fishes were absent above salinities of 2 g L-1, while littoral macroinvertebrates were ubiquitous. Zooplankton occurred over the whole salinity range, but changed taxonomic composition as salinity increased. Subsequently, the complexity of fish community (diversity) was associated with large changes in invertebrate communities. The directional changes in invertebrate communities to smaller taxa indicated that complex fish assemblages resulted in higher predation pressure. Most likely, as the complexity of fish community decreased, controls of invertebrate assemblages shifted from predation to competition and ultimately to productivity in hypersaline lakes. Surprisingly, invertebrate predators did not thrive in the absence of fishes in these systems. Furthermore, the here identified salinity threshold for fishes was too low to be a result of osmotic stress. Hence, winterkill was likely an important factor eliminating fishes in low salinity lakes that had high productivity and shallow water depth. Ultimately, while salinity was crucial, intricate combinations of chemical and biological mechanisms also played a major role in controlling the assemblages of major taxonomic groups in prairie lakes.

Interactive effects of chemical and biological controls on food-web composition in saline prairie lakes

PubMed Central

2012-01-01

Salinity is restricting habitatability for many biota in prairie lakes due to limited physiological abilities to cope with increasing osmotic stress. Yet, it remains unclear how salinity effects vary among major taxonomic groups and what role other environmental parameters play in shaping food-web composition. To answer these questions, we sampled fish, zooplankton and littoral macroinvertebrates in 20 prairie lakes (Saskatchewan, Canada) characterized by large gradients in water chemistry and lake morphometry. We showed that salinity thresholds differed among major taxonomic groups, as most fishes were absent above salinities of 2 g L-1, while littoral macroinvertebrates were ubiquitous. Zooplankton occurred over the whole salinity range, but changed taxonomic composition as salinity increased. Subsequently, the complexity of fish community (diversity) was associated with large changes in invertebrate communities. The directional changes in invertebrate communities to smaller taxa indicated that complex fish assemblages resulted in higher predation pressure. Most likely, as the complexity of fish community decreased, controls of invertebrate assemblages shifted from predation to competition and ultimately to productivity in hypersaline lakes. Surprisingly, invertebrate predators did not thrive in the absence of fishes in these systems. Furthermore, the here identified salinity threshold for fishes was too low to be a result of osmotic stress. Hence, winterkill was likely an important factor eliminating fishes in low salinity lakes that had high productivity and shallow water depth. Ultimately, while salinity was crucial, intricate combinations of chemical and biological mechanisms also played a major role in controlling the assemblages of major taxonomic groups in prairie lakes. PMID:23186395

Low temperature hall effect investigation of conducting polymer-carbon nanotubes composite network.

PubMed

Bahrami, Afarin; Talib, Zainal Abidin; Yunus, Wan Mahmood Mat; Behzad, Kasra; M Abdi, Mahnaz; Din, Fasih Ud

2012-11-14

Polypyrrole (PPy) and polypyrrole-carboxylic functionalized multi wall carbon nanotube composites (PPy/f-MWCNT) were synthesized by in situ chemical oxidative polymerization of pyrrole on the carbon nanotubes (CNTs). The structure of the resulting complex nanotubes was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The effects of f-MWCNT concentration on the electrical properties of the resulting composites were studied at temperatures between 100 K and 300 K. The Hall mobility and Hall coefficient of PPy and PPy/f-MWCNT composite samples with different concentrations of f-MWCNT were measured using the van der Pauw technique. The mobility decreased slightly with increasing temperature, while the conductivity was dominated by the gradually increasing carrier density.

Dragonfly: Investigating the Surface Composition of Titan

NASA Technical Reports Server (NTRS)

Brinckerhoff, W. B.; Lawrence, D. J.; Barnes, J. W.; Lorenz, R. D.; Horst, S. M.; Zacny, K.; Freissinet, C.; Parsons, A. M.; Turtle, E. P.; Trainer, M. G.;

Chemically designed Pt/PPy nano-composite for effective LPG gas sensor.

PubMed

Gaikwad, Namrata; Bhanoth, Sreenu; More, Priyesh V; Jain, G H; Khanna, P K

2014-03-07

Simultaneous in situ reduction of hexachloroplatinic acid by the amine group in the pyrrole monomer and oxidation of pyrrole to form polypyrrole (PPy) was examined. The reactions were performed at various temperatures to understand the degree of reduction of platinum precursor as well as doping of polypyrrole with Pt(II) chloro-complex. Spectroscopic images revealed different morphologies for the Pt/PPy nano-composite prepared at various temperatures. The as-prepared Pt/PPy nano-composite samples were tested for their ability to sense liquefied petroleum gas (LPG) which resulted in excellent sensing at relatively low temperature. The porous nature and ohmic contact between the PPy and platinum nanoparticles makes the as-prepared Pt/PPy nano-composite highly useful for sensors as well as electronic applications.

The contribution of vapor deposition to amorphous rims on lunar soil grains. [Abstract only

NASA Technical Reports Server (NTRS)

Keller, L. P.; Mckay, D. S.

1994-01-01

Recent analysis analytical electron microscope study of lunar soils showed that the approximately 60-nm-wide amorphous rims surrounding many lunar soils grains exhibit distinct compositional differences from their hosts. On average, the amorphous rim compositions reflect the local bulk soil composition with the exceptions of Si and S, which are enriched relative to the bulk soil. These chemical trends led us to propose that the amorphous rims were in fact deposits of impact-generated vapors produced during regolith gardening, a hypothesis that runs contrary to the generally accepted view that the rims are produced through amorphization of the outer parts of mineral grains by interaction with the solar wind. Analytical data are reported for amorphous rims on individual minerals in lunar soils in order to show that the magnitude of the chemical differences between rim and host are so great that they require a major addition of foreign elements to the grain surfaces. The average composition of amorphous rims is listed as a function of host mineralogy as determined in microtone thin sections using energy-dispersive X-ray spectrometry in the transmission electron microscope. As the host mineral becomes chemically more complex, the chemical differences are not as clear. The average rim compositions are remarkably similar and are independent of the host grain mineralogy. Whether there are 'sputtering' or radiation effects superimposed on the vapor-deposited material can be debated. We do not explicitly exclude the effects of radiation damage as a contributing factor to the formation of amorphous rims; we are merely emphasizing the major role played by condensed vapors in the formation of amorphous rims on lunar soil grains.

Magnetic and electromagnetic properties of composites of iron oxide and Co-B alloy prepared by chemical reduction

NASA Astrophysics Data System (ADS)

Li, XueAi; Han, XiJiang; Du, YunChen; Xu, Ping

2011-01-01

Magnetic and electromagnetic properties were investigated on the composites of iron oxide and Co-B alloy, which were prepared by a modified chemical reduction method. The composites are characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDXA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometry (VSM). The complex electromagnetic parameters (permittivity ɛr= ɛr'+j ɛr″ and permeability μr= μr'+j μr″) of paraffin mixed composite samples (paraffin:composites=1:1 in mass ratio) were measured in the frequency range 2-18 GHz by vector network analyzer. The measured real part ( ɛr') and imaginary part ( ɛr″) of the relative permittivity show two resonant peaks in the range of 2-18 GHz. The imaginary parts of relative permeability ( μr″) of all samples exhibited one broad resonant peak over the 2-8 GHz range. The μr″ of samples with higher molar ratio of Co to Fe (C and D) shows negative values within 13-18 GHz, which exhibit resonant and antiresonant permeabilities simultaneously. Calculation results indicated that the reflection loss values of the composites and paraffin wax mixtures are less than -10 dB with frequency width of about 6 GHz at the matching thickness.

A chemical–biological similarity-based grouping of complex substances as a prototype approach for evaluating chemical alternatives† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6gc01147k Click here for additional data file.

PubMed Central

Grimm, Fabian A.; Iwata, Yasuhiro; Sirenko, Oksana; Chappell, Grace A.; Wright, Fred A.; Reif, David M.; Braisted, John; Gerhold, David L.; Yeakley, Joanne M.; Shepard, Peter; Seligmann, Bruce; Roy, Tim; Boogaard, Peter J.; Ketelslegers, Hans B.; Rohde, Arlean M.

2016-01-01

Comparative assessment of potential human health impacts is a critical step in evaluating both chemical alternatives and existing products on the market. Most alternatives assessments are conducted on a chemical-by-chemical basis and it is seldom acknowledged that humans are exposed to complex products, not individual substances. Indeed, substances of Unknown or Variable composition, Complex reaction products, and Biological materials (UVCBs) are ubiquitous in commerce yet they present a major challenge for registration and health assessments. Here, we present a comprehensive experimental and computational approach to categorize UVCBs according to global similarities in their bioactivity using a suite of in vitro models. We used petroleum substances, an important group of UVCBs which are grouped for regulatory approval and read-across primarily on physico-chemical properties and the manufacturing process, and only partially based on toxicity data, as a case study. We exposed induced pluripotent stem cell-derived cardiomyocytes and hepatocytes to DMSO-soluble extracts of 21 petroleum substances from five product groups. Concentration-response data from high-content imaging in cardiomyocytes and hepatocytes, as well as targeted high-throughput transcriptomic analysis of the hepatocytes, revealed distinct groups of petroleum substances. Data integration showed that bioactivity profiling affords clustering of petroleum substances in a manner similar to the manufacturing process-based categories. Moreover, we observed a high degree of correlation between bioactivity profiles and physico-chemical properties, as well as improved groupings when chemical and biological data were combined. Altogether, we demonstrate how novel in vitro screening approaches can be effectively utilized in combination with physico-chemical characteristics to group complex substances and enable read-across. This approach allows for rapid and scientifically-informed evaluation of health impacts of both existing substances and their chemical alternatives. PMID:28035192

Metal nanoparticle-graphene oxide composites: Photophysical properties and sensing applications

NASA Astrophysics Data System (ADS)

Murphy, Sean J.

Composite nanomaterials allow for attractive properties of multiple functional components to be combined. Fundamental understanding of the interaction between different nanomaterials, their surroundings, and nearby molecular species is pertinent for implementation into devices. Metal nanoparticles have been used for their optical properties in many applications including stained glass, cancer therapy, solar steam generation, surface enhanced Raman spectroscopy (SERS), and catalysis. Carbon-based nanomaterials such as graphene and carbon nanotubes show potential for a wide variety of applications including solar energy harvesting, chemical sensors, and electronics. Combining useful and in some cases new properties of composite nanomaterials offers exciting opportunities in fundamental science and device development. In this dissertation, I aim to address understanding photoinduced interaction between porphyrin and silver nanoparticles, inter-sheet interaction between stacked graphene oxide (GO) sheets in thin films, complexation of reduced GO with Raman active target molecule in SERS applications, and efficacy of graphene-metal nanoparticle composites for sensing applications. Molecule-metal nanoparticle composite material made up of photoactive porphyrin and silver nanoparticles was studied using various spectroscopic tools. UV-visible absorption and surface enhanced Raman spectroscopic results suggest formation of a charge-transfer complex for porphyrin-silver nanoparticle composite. Ultrafast transient absorption and fluorescence upconversion spectroscopies further corroborate electronic interaction by providing evidence for excited state electron transfer between porphyrin and silver nanoparticles. Understanding electronic interaction between adsorbed photoactive molecules and metal nanoparticles may be of use for applications in photocatalysis or light-energy harvesting. Graphene oxide (GO) thin films have been prepared and studied using transient absorption microscopy (TAM). Transient absorption microscopy correlated with atomic force microscope allows for the morphological properties of GO thin film to be related to optical properties, namely dynamics of photoexcited carriers in GO. Results suggest short-timescale (ps -- ˜1 ns) dynamics of charge carriers in GO are affected very little by interaction with the glass substrate on which GO is placed. Also, the stack thickness or number of stacked GO sheets does not play a large role in the short-timescale dynamics of GO charge carriers. GO or reduced GO (RGO)-silver nanoparticles composites were produced using different methods: (1) chemical reduction of silver ion precursor and (2) photocatalytic reduction of GO and silver ion using TiO2 nanoparticles. Optical and morphological properties of composites were studied using spectroscopy and electron microscopy revealing a degree of control in metal nanoparticle growth and loading on the surface of RGO. Nanocomposites were shown to be capable of complexing with or adsorbing target molecular species. Complexation and adsorption are corroborated with demonstration that the composite nanomaterials act as effective SERRS sensors taking advantage of localized surface plasmon resonance of metal nanoparticles and the ability of RGO to interact with molecular and ionic species.

Atmospheric chemical and thermal structure evolution after one Titanian year

NASA Astrophysics Data System (ADS)

Coustenis, A.; Bampasidis, G.; Vinatier, S.; Achterberg, R.; Lavvas, P.; Nixon, C.; Jennings, D.; Teanby, N.; Flasar, F. M.; Carlson, R.; Orton, G.; Romani, P.; Guandique, E. A.

2012-09-01

We analyze Cassini Composite Infrared Spectrometer (CIRS) data taken during the numerous Titan flybys from 2004-2010 and compare them to the 1980 Voyager 1 flyby values inferred from the re-analysis of the Infrared Radiometer Spectrometer (IRIS) spectra. Seven years after Cassini's Saturn orbit insertion, we look at the evolution of the chemical composition by combining these recordings and the intervening ground- and space- based observations, we have in hand almost a complete picture of the stratospheric evolution within a Titan year. The fulfillment of one Titanian year of observations provides us for the first time with the opportunity to evaluate the relative role of different physical processes in the long-term evolution of this complex environment. By comparing V1 (1980), ISO (1997) and Cassini (2010) we find that a reversal of composition near the equator from autumnal equinox to vernal equinox (1996 min -2009 max, half a year), as well as some differences in polar enhancement at the same era as Voyager.

Laser-induced breakdown spectroscopy (LIBS) technique for the determination of the chemical composition of complex inorganic materials

NASA Astrophysics Data System (ADS)

Łazarek, Łukasz; Antończak, Arkadiusz J.; Wójcik, Michał R.; Kozioł, Paweł E.; Stepak, Bogusz; Abramski, Krzysztof M.

2014-08-01

Laser-induced breakdown spectroscopy (LIBS) is a fast, fully optical method, that needs little or no sample preparation. In this technique qualitative and quantitative analysis is based on comparison. The determination of composition is generally based on the construction of a calibration curve namely the LIBS signal versus the concentration of the analyte. Typically, to calibrate the system, certified reference materials with known elemental composition are used. Nevertheless, such samples due to differences in the overall composition with respect to the used complex inorganic materials can influence significantly on the accuracy. There are also some intermediate factors which can cause imprecision in measurements, such as optical absorption, surface structure, thermal conductivity etc. This paper presents the calibration procedure performed with especially prepared pellets from the tested materials, which composition was previously defined. We also proposed methods of post-processing which allowed for mitigation of the matrix effects and for a reliable and accurate analysis. This technique was implemented for determination of trace elements in industrial copper concentrates standardized by conventional atomic absorption spectroscopy with a flame atomizer. A series of copper flotation concentrate samples was analyzed for contents of three elements, that is silver, cobalt and vanadium. It has been shown that the described technique can be used to qualitative and quantitative analyses of complex inorganic materials, such as copper flotation concentrates.

Modeling of Fine-Particle Formation in Turbulent Flames

NASA Astrophysics Data System (ADS)

Raman, Venkat; Fox, Rodney O.

2016-01-01

The generation of nanostructured particles in high-temperature flames is important both for the control of emissions from combustion devices and for the synthesis of high-value chemicals for a variety of applications. The physiochemical processes that lead to the production of fine particles in turbulent flames are highly sensitive to the flow physics and, in particular, the history of thermochemical compositions and turbulent features they encounter. Consequently, it is possible to change the characteristic size, structure, composition, and yield of the fine particles by altering the flow configuration. This review describes the complex multiscale interactions among turbulent fluid flow, gas-phase chemical reactions, and solid-phase particle evolution. The focus is on modeling the generation of soot particles, an unwanted pollutant from automobile and aircraft engines, as well as metal oxides, a class of high-value chemicals sought for specialized applications, including emissions control. Issues arising due to the numerical methods used to approximate the particle number density function, the modeling of turbulence-chemistry interactions, and model validation are also discussed.

Usage of FT-ICR-MS Metabolomics for Characterizing the Chemical Signatures of Barrel-Aged Whisky

PubMed Central

Roullier-Gall, Chloé; Signoret, Julie; Hemmler, Daniel; Witting, Michael A.; Kanawati, Basem; Schäfer, Bernhard; Gougeon, Régis D.; Schmitt-Kopplin, Philippe

2018-01-01

Whisky can be described as a complex matrix integrating the chemical history from the fermented cereals, the wooden barrels, the specific distillery processes, aging, and environmental factors. In this study, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS), we analyzed 150 whisky samples from 49 different distilleries, 7 countries, and ranging from 1 day new make spirit to 43 years of maturation with different types of barrel. Chemometrics revealed the unexpected impact of the wood history on the distillate's composition during barrel aging, regardless of the whisky origin. Flavonols, oligolignols, and fatty acids are examples of important chemical signatures for Bourbon casks, whereas a high number of polyphenol glycosides, including for instance quercetin-glucuronide or myricetin-glucoside as potential candidates, and carbohydrates would discriminate Sherry casks. However, the comparison of barrel aged rums and whiskies revealed specific signatures, highlighting the importance of the initial composition of the distillate and the distillery processes. PMID:29520358

Usage of FT-ICR-MS Metabolomics for characterizing the chemical signatures of barrel-aged whisky

NASA Astrophysics Data System (ADS)

Roullier-Gall, Chloé; Signoret, Julie; Hemmler, Daniel; Witting, Michael A.; Kanawati, Basem; Schäfer, Bernhard; Gougeon, Régis D.; Schmitt-Kopplin, Philippe

2018-02-01

Whisky can be described as a complex matrix integrating the chemical history from the fermented cereals, the wooden barrels, the specific distillery processes, ageing and environmental factors. In this study, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS), we analysed 150 whisky samples from 49 different distilleries, 7 countries, and ranging from 1 day new make spirit to 43 years of maturation with different types of barrel. Chemometrics revealed the unexpected impact of the wood history on the distillatés composition during barrel ageing, regardless of the whisky origin. Flavonols, oligolignols and fatty acids are examples of important chemical signatures for Bourbon casks, whereas a high number of polyphenol glycosides, including for instance quercetin-glucuronide or myricetin-glucoside as potential candidates, and carbohydrates would discriminate Sherry casks. However, the comparison of barrel aged rums and whiskies revealed specific signatures, highlighting the importance of the initial composition of the distillate and the distillery processes.

Bottom-Up and Top-Down Solid-State NMR Approaches for Bacterial Biofilm Matrix Composition

PubMed Central

Cegelski, Lynette

2015-01-01

The genomics and proteomics revolutions have been enormously successful in providing crucial “parts lists” for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a non-crystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this Perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The “sum-of-theparts” bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by E. coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in V. cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture. PMID:25797008

Bottom-up and top-down solid-state NMR approaches for bacterial biofilm matrix composition.

PubMed

Cegelski, Lynette

2015-04-01

The genomics and proteomics revolutions have been enormously successful in providing crucial "parts lists" for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a non-crystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The "sum-of-the-parts" bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by Escherichia coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in Vibrio cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture. Copyright © 2015 Elsevier Inc. All rights reserved.

Bottom-up and top-down solid-state NMR approaches for bacterial biofilm matrix composition

NASA Astrophysics Data System (ADS)

Cegelski, Lynette

2015-04-01

The genomics and proteomics revolutions have been enormously successful in providing crucial "parts lists" for biological systems. Yet, formidable challenges exist in generating complete descriptions of how the parts function and assemble into macromolecular complexes and whole-cell assemblies. Bacterial biofilms are complex multicellular bacterial communities protected by a slime-like extracellular matrix that confers protection to environmental stress and enhances resistance to antibiotics and host defenses. As a non-crystalline, insoluble, heterogeneous assembly, the biofilm extracellular matrix poses a challenge to compositional analysis by conventional methods. In this perspective, bottom-up and top-down solid-state NMR approaches are described for defining chemical composition in complex macrosystems. The "sum-of-the-parts" bottom-up approach was introduced to examine the amyloid-integrated biofilms formed by Escherichia coli and permitted the first determination of the composition of the intact extracellular matrix from a bacterial biofilm. An alternative top-down approach was developed to define composition in Vibrio cholerae biofilms and relied on an extensive panel of NMR measurements to tease out specific carbon pools from a single sample of the intact extracellular matrix. These two approaches are widely applicable to other heterogeneous assemblies. For bacterial biofilms, quantitative parameters of matrix composition are needed to understand how biofilms are assembled, to improve the development of biofilm inhibitors, and to dissect inhibitor modes of action. Solid-state NMR approaches will also be invaluable in obtaining parameters of matrix architecture.

Elastic anomalies in Fe-Cr alloys

NASA Astrophysics Data System (ADS)

Zhang, Hualei; Wang, Guisheng; Punkkinen, Marko P. J.; Hertzman, Staffan; Johansson, Börje; Vitos, Levente

2013-05-01

Using ab initio alloy theory, we determine the elastic parameters of ferromagnetic and paramagnetic Fe1-cCrc (0 ≤ c ≤ 1) alloys in the body centered cubic crystallographic phase. Comparison with the experimental data demonstrates that the employed theoretical approach accurately describes the observed composition dependence of the polycrystalline elastic moduli. The predicted single-crystal elastic constants follow complex anomalous trends, which are shown to originate from the interplay between magnetic and chemical effects. The nonmonotonic composition dependence of the elastic parameters has marked implications on the micro-mechanical properties of ferrite stainless steels.

Coal Research

NASA Technical Reports Server (NTRS)

1986-01-01

Coal slurries are "clean" pulverized coal mixed with oil or water. Significant fuel savings can be realized when using coal slurries. Advanced Fuels Technology (AFT) utilized a COSMIC program, (Calculation of Complex Chemical Equilibrium Compositions), which provides specific capabilities for determining combustion products. The company has developed a cleaning process that removes much of the mineral sulphur and ash from the coals.

Compositional effects on the ignition of FACE gasolines [Compositional effects on the ignition of FACE gasoline fuels: experiments, surrogate fuel formulation, and chemical kinetic modeling

DOE PAGES

Sarathy, S. Mani; Kukkadapu, Goutham; Mehl, Marco; ...

2016-05-08

As regulatory measures for improved fuel economy and decreased emissions are pushing gasoline engine combustion technologies towards extreme conditions (i.e., boosted and intercooled intake with exhaust gas recirculation), fuel ignition characteristics become increasingly important for enabling stable operation. Here, this study explores the effects of chemical composition on the fundamental ignition behavior of gasoline fuels. Two well-characterized, high-octane, non-oxygenated FACE (Fuels for Advanced Combustion Engines) gasolines, FACE F and FACE G, having similar antiknock indices but different octane sensitivities and chemical compositions are studied. Ignition experiments were conducted in shock tubes and a rapid compression machine (RCM) at nominal pressuresmore » of 20 and 40 atm, equivalence ratios of 0.5 and 1.0, and temperatures ranging from 650 to 1270 K. Results at temperatures above 900 K indicate that ignition delay time is similar for these fuels. However, RCM measurements below 900 K demonstrate a stronger negative temperature coefficient behavior for FACE F gasoline having lower octane sensitivity. In addition, RCM pressure profiles under two-stage ignition conditions illustrate that the magnitude of low-temperature heat release (LTHR) increases with decreasing fuel octane sensitivity. However, intermediate-temperature heat release is shown to increase as fuel octane sensitivity increases. Various surrogate fuel mixtures were formulated to conduct chemical kinetic modeling, and complex multicomponent surrogate mixtures were shown to reproduce experimentally observed trends better than simpler two- and three-component mixtures composed of n-heptane, iso-octane, and toluene. Measurements in a Cooperative Fuels Research (CFR) engine demonstrated that the multicomponent surrogates accurately captured the antiknock quality of the FACE gasolines. Simulations were performed using multicomponent surrogates for FACE F and G to reveal the underlying chemical kinetics linking fuel composition with ignition characteristics. Finally, a key discovery of this work is the kinetic coupling between aromatics and naphthenes, which affects the radical pool population and thereby controls ignition.« less

Compositional effects on the ignition of FACE gasolines [Compositional effects on the ignition of FACE gasoline fuels: experiments, surrogate fuel formulation, and chemical kinetic modeling

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

Sarathy, S. Mani; Kukkadapu, Goutham; Mehl, Marco

As regulatory measures for improved fuel economy and decreased emissions are pushing gasoline engine combustion technologies towards extreme conditions (i.e., boosted and intercooled intake with exhaust gas recirculation), fuel ignition characteristics become increasingly important for enabling stable operation. Here, this study explores the effects of chemical composition on the fundamental ignition behavior of gasoline fuels. Two well-characterized, high-octane, non-oxygenated FACE (Fuels for Advanced Combustion Engines) gasolines, FACE F and FACE G, having similar antiknock indices but different octane sensitivities and chemical compositions are studied. Ignition experiments were conducted in shock tubes and a rapid compression machine (RCM) at nominal pressuresmore » of 20 and 40 atm, equivalence ratios of 0.5 and 1.0, and temperatures ranging from 650 to 1270 K. Results at temperatures above 900 K indicate that ignition delay time is similar for these fuels. However, RCM measurements below 900 K demonstrate a stronger negative temperature coefficient behavior for FACE F gasoline having lower octane sensitivity. In addition, RCM pressure profiles under two-stage ignition conditions illustrate that the magnitude of low-temperature heat release (LTHR) increases with decreasing fuel octane sensitivity. However, intermediate-temperature heat release is shown to increase as fuel octane sensitivity increases. Various surrogate fuel mixtures were formulated to conduct chemical kinetic modeling, and complex multicomponent surrogate mixtures were shown to reproduce experimentally observed trends better than simpler two- and three-component mixtures composed of n-heptane, iso-octane, and toluene. Measurements in a Cooperative Fuels Research (CFR) engine demonstrated that the multicomponent surrogates accurately captured the antiknock quality of the FACE gasolines. Simulations were performed using multicomponent surrogates for FACE F and G to reveal the underlying chemical kinetics linking fuel composition with ignition characteristics. Finally, a key discovery of this work is the kinetic coupling between aromatics and naphthenes, which affects the radical pool population and thereby controls ignition.« less

The composition-explicit distillation curve technique: Relating chemical analysis and physical properties of complex fluids.

PubMed

Bruno, Thomas J; Ott, Lisa S; Lovestead, Tara M; Huber, Marcia L

2010-04-16

The analysis of complex fluids such as crude oils, fuels, vegetable oils and mixed waste streams poses significant challenges arising primarily from the multiplicity of components, the different properties of the components (polarity, polarizability, etc.) and matrix properties. We have recently introduced an analytical strategy that simplifies many of these analyses, and provides the added potential of linking compositional information with physical property information. This aspect can be used to facilitate equation of state development for the complex fluids. In addition to chemical characterization, the approach provides the ability to calculate thermodynamic properties for such complex heterogeneous streams. The technique is based on the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. The analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin layer chromatography, FTIR, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. By far, the most widely used analytical technique we have used with the ADC is gas chromatography. This has enabled us to study finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oils streams (used automotive and transformer oils). In this special issue of the Journal of Chromatography, specifically dedicated to extraction technologies, we describe the essential features of the advanced distillation curve metrology as an analytical strategy for complex fluids. Published by Elsevier B.V.

Effect of graphene oxide on the structural and electrochemical behavior of polypyrrole deposited on cotton fabric

NASA Astrophysics Data System (ADS)

Yaghoubidoust, Fatemeh; Wicaksono, Dedy H. B.; Chandren, Sheela; Nur, Hadi

2014-10-01

Improving the electrical response of polypyrrole-cotton composite is the key issue in making flexible electrode with favorable mechanical strength and large capacitance. Flexible graphene oxide/cotton (GO/Cotton) composite has been prepared by dipping pristine cotton in GO ink. The composite‘s surface was further modified with polypyrrole (Ppy) via chemical polymerization to obtain Ppy/GO/Cotton composite. The composite was characterized using SEM, FTIR and XRD measurements, while the influence of GO in modifying the physicochemical properties of the composite was also examined using TG and cyclic voltammetry. The achieved mean particle size for Ppy/Cotton, Ppy/GO/Cotton and GO estimated using Scherrer formula are 58, 67 and 554 nm, respectively. FTIR spectra revealed prominent fundamental absorption bands in the range of 1400-1800 cm-1. The increased electrical conductivity as much as 2.2 × 10-1 S cm-1 for Ppy/GO/Cotton composite measured by complex impedance, is attributed to the formation of continuous conducting network. The partial reduction of GO on the surface of cotton (GO/Cotton) during chemical polymerization can also affect the conductivity. This simple, economic and environmental-friendly preparation method may contribute towards the controlled growth of quality and stable Ppy/GO/Cotton composites for potential applications in microwave attenuation, energy storage system, static electric charge dissipation and electrotherapy.

Structural characteristics of fulvic acids from Continental Shelf sediments

USGS Publications Warehouse

Hatcher, P.G.; Breger, I.A.; Mattingly, M.A.

1980-01-01

Fulvic acids are those components of soil organic matter that remain soluble after a dilute alkaline extract of the soil is acidified to pH 2 (refs 1, 2). This extraction procedure has been applied to marine sediments, and the organic compounds so recovered have been called marine sedimentary fulvic acids. These fulvic acids are thought to form more complex humic substances in marine sediments by condensation reactions3. However, the chemical structural compositions of marine fulvic acids have not been defined sufficiently to allow this precursor relationship to be made. Here NMR spectroscopy is used to identify more clearly the chemical structural components of some marine sedimentary fulvic acids, thus enabling a more useful examination of their relationship to more complex humic substances. ?? 1980 Nature Publishing Group.

Monitoring cell culture media degradation using surface enhanced Raman scattering (SERS) spectroscopy.

PubMed

Calvet, Amandine; Ryder, Alan G

2014-08-20

The quality of the cell culture media used in biopharmaceutical manufacturing is a crucial factor affecting bioprocess performance and the quality of the final product. Due to their complex composition these media are inherently unstable, and significant compositional variations can occur particularly when in the prepared liquid state. For example photo-degradation of cell culture media can have adverse effects on cell viability and thus process performance. There is therefore, from quality control, quality assurance and process management view points, an urgent demand for the development of rapid and inexpensive tools for the stability monitoring of these complex mixtures. Spectroscopic methods, based on fluorescence or Raman measurements, have now become viable alternatives to more time-consuming and expensive (on a unit analysis cost) chromatographic and/or mass spectrometry based methods for routine analysis of media. Here we demonstrate the application of surface enhanced Raman scattering (SERS) spectroscopy for the simple, fast, analysis of cell culture media degradation. Once stringent reproducibility controls are implemented, chemometric data analysis methods can then be used to rapidly monitor the compositional changes in chemically defined media. SERS shows clearly that even when media are stored at low temperature (2-8°C) and in the dark, significant chemical changes occur, particularly with regard to cysteine/cystine concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

Computer Code for Nanostructure Simulation

NASA Technical Reports Server (NTRS)

Filikhin, Igor; Vlahovic, Branislav

2009-01-01

Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.

New propolis type from north-east Brazil: chemical composition, antioxidant activity and botanical origin.

PubMed

Ferreira, Joselena M; Fernandes-Silva, Caroline C; Salatino, Antonio; Negri, Giuseppina; Message, Dejair

2017-08-01

Propolis is a bee product with wide diversity of biological activity. It has a complex composition, which is dependent on its botanical source. The present study aimed to determine the chemical profile, antioxidant activity and botanical origin of two samples of a propolis type from two locations of the state of Rio Grande do Norte (RN, north-east Brazil). The standard chemical characteristics of the RN propolis are similar or superior to the internationally marketed Brazilian green propolis. RN propolis from two locations have high antioxidant activity, corresponding to 10% (municipality of Afonso Bezerra) and 13% (municipality of Alto do Rodrigues) of quercetin activity by the 2,2-diphenyl-1-picrylhydrazyl method and to 15% (both locations) by the β-carotene discoloration method. High-performance liquid chromatography with diode array detection (HPLC-DAD)-electrospray ionization-tandem mass spectrometry analyses revealed that most constituents of the RN propolis are flavonoids, mainly flavonols and chalcones. HPLC-DAD analysis of ethanol extracts revealed a great similarity between the chemical profile of RN propolis and shoot apices of 'jurema-preta' (Mimosa tenuiflora, Leguminosae, Mimosoideae). 'Jurema-preta' shoot apices are likely resin sources of RN propolis. The chemical characteristics and antioxidant property of RN propolis provide promising prospects for the introduction of this type of propolis into the apicultural market. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Efficiency of Composite Binders with Antifreezing Agents

NASA Astrophysics Data System (ADS)

Ogurtsova, Y. N.; Zhernovsky, I. V.; Botsman, L. N.

2017-11-01

One of the non-heating methods of cold-weather concreting is using concretes hardening at negative temperatures. This method consists in using chemical additives which reduce the freezing temperature of the liquid phase and provide for concrete hardening at negative temperatures. The non-heating cold-weather concreting, due to antifreezing agents, allows saving heat and electric energy at the more flexible work performance technology. At selecting the antifreezing components, the possibility of concreting at temperatures up to minus 20 °C and combination with a plasticizer contained in the composite binder were taken into account. The optimal proportions of antifreezing and complex agents produced by MC-Bauchemie Russia for fine-grained concretes were determined. So, the introduction of antifreezing and complex agents allows obtaining a structure of composite characteristic for cement stone in the conditions of below zero temperatures at using different binders; the hydration of such composite proceeded naturally. Low-water-demand binders (LWDB) based composites are characterized by a higher density and homogeneity due to a high dispersity of a binder and its complicated surface providing for a lot of crystallization centers. LWDB contains small pores keeping water in a liquid form and promoting a more complete hydration process.

The system controlling the composition of clastic sediments

USGS Publications Warehouse

Johnsson, Mark J.

1993-01-01

The composition of clastic sediments and rocks is controlled by a complex suite of parameters operating during pedogenesis, erosion, transport, deposition, and burial. The principal first-order parameters include source rock composition, modification by chemical weathering, mechanical disaggregation and abrasion, authigenic inputs, hydrodynamic sorting, and diagenesis. Each of these first-order parameters is influenced to varying degrees by such factors as the tectonic settings of the source region, transportational system and depositional environment, climate, vegetation, relief, slope, and the nature and energy of transportational and depositional systems. These factors are not independent; rather a complicated web of interrelationships and feedback mechanisms causes many factors to be modulated by others. Accordingly, processes controlling the composition of clastic sediments are best viewed as constituting a system, and in evaluating compositional information the dynamics of the system must be considered as whole.

A novel model for estimating organic chemical bioconcentration in agricultural plants

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

Hung, H.; Mackay, D.; Di Guardo, A.

1995-12-31

There is increasing recognition that much human and wildlife exposure to organic contaminants can be traced through the food chain to bioconcentration in vegetation. For risk assessment, there is a need for an accurate model to predict organic chemical concentrations in plants. Existing models range from relatively simple correlations of concentrations using octanol-water or octanol-air partition coefficients, to complex models involving extensive physiological data. To satisfy the need for a relatively accurate model of intermediate complexity, a novel approach has been devised to predict organic chemical concentrations in agricultural plants as a function of soil and air concentrations, without themore » need for extensive plant physiological data. The plant is treated as three compartments, namely, leaves, roots and stems (including fruit and seeds). Data readily available from the literature, including chemical properties, volume, density and composition of each compartment; metabolic and growth rate of plant; and readily obtainable environmental conditions at the site are required as input. Results calculated from the model are compared with observed and experimentally-determined concentrations. It is suggested that the model, which includes a physiological database for agricultural plants, gives acceptably accurate predictions of chemical partitioning between plants, air and soil.« less

Quantum-chemical insights from deep tensor neural networks

PubMed Central

Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R.; Tkatchenko, Alexandre

2017-01-01

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol−1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems. PMID:28067221

Identifying new persistent and bioaccumulative organics among chemicals in commerce.

PubMed

Howard, Philip H; Muir, Derek C G

2010-04-01

The goal of this study was to identify commercial chemicals that might be persistent and bioaccumulative (P&B) and that were not being considered in current Great Lakes, North American, and Arctic contaminant measurement programs. We combined the Canadian Domestic Substance List (DSL), a list of 3059 substances of "unknown or variable composition complex reaction products and biological materials" (UVCBs), and the U.S. Environmental Protection Agency (U.S. EPA) Toxic Substances Control Act (TSCA) Inventory Update Rule (IUR) database for years 1986, 1990, 1994, 1998, 2002, and 2006 yielding a database of 22263 commercial chemicals. From that list, 610 chemicals were identified by estimates from U.S EPA EPISuite software and using expert judgment. This study has yielded some interesting and probable P&B chemicals that should be considered for further study. Recent studies, following up our initial reports and presentations on this work, have confirmed the presence of many of these chemicals in the environment.

Quantum-chemical insights from deep tensor neural networks.

PubMed

Schütt, Kristof T; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R; Tkatchenko, Alexandre

2017-01-09

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol -1 ) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems.

Quantum-chemical insights from deep tensor neural networks

NASA Astrophysics Data System (ADS)

Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R.; Tkatchenko, Alexandre

2017-01-01

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol-1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems.

Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

DOE PAGES

Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; ...

2016-02-02

Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less

Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

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

Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.

Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less

Application of mass spectrometry in the characterization of chemicals in coal-derived liquids.

PubMed

Liu, Fang-Jing; Fan, Maohong; Wei, Xian-Yong; Zong, Zhi-Min

2017-07-01

Coal-derived liquids (CDLs) are primarily generated from pyrolysis, carbonization, gasification, direct liquefaction, low-temperature extraction, thermal dissolution, and mild oxidation. CDLs are important feedstocks for producing value-added chemicals and clean liquid fuels as well as high performance carbon materials. Accordingly, the compositional characterization of chemicals in CDLs at the molecular level with advanced analytical techniques is significant for the efficient utilization of CDLs. Although reviews on advancements have been rarely reported, great progress has been achieved in this area by using gas chromatography/mass spectrometry (GC/MS), two-dimensional GC-time of flight mass spectrometry (GC × GC-TOFMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This review focuses on characterizing hydrocarbon, oxygen-containing, nitrogen-containing, sulfur-containing, and halogen-containing chemicals in various CDLs with these three mass spectrometry techniques. Small molecular (< 500 u), volatile and semi-volatile, and less polar chemicals in CDLs have been identified with GC/MS and GC × GC-TOFMS. By equipped with two-dimensional GC, GC × GC-TOFMS can achieve a clearly chromatographic separation of complex chemicals in CDLs without prior fractionation, and thus can overcome the disadvantages of co-elution and serious peak overlap in GC/MS analysis, providing much more compositional information. With ultrahigh resolving power and mass accuracy, FT-ICR MS reveals a huge number of compositionally distinct compounds assigned to various chemical classes in CDLs. It shows excellent performance in resolving and characterizing higher-molecular, less volatile, and polar chemicals that cannot be detected by GC/MS and GC × GC-TOFMS. The application of GC × GC-TOFMS and FT-ICR MS to chemical characterization of CDLs is not as prevalent as that of petroleum and largely remains to be developed in many respects. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:543-579, 2017. © 2016 Wiley Periodicals, Inc.

Astrochemical evolution along star formation: overview of the IRAM Large Program ASAI

NASA Astrophysics Data System (ADS)

Lefloch, Bertrand; Bachiller, R.; Ceccarelli, C.; Cernicharo, J.; Codella, C.; Fuente, A.; Kahane, C.; López-Sepulcre, A.; Tafalla, M.; Vastel, C.; Caux, E.; González-García, M.; Bianchi, E.; Gómez-Ruiz, A.; Holdship, J.; Mendoza, E.; Ospina-Zamudio, J.; Podio, L.; Quénard, D.; Roueff, E.; Sakai, N.; Viti, S.; Yamamoto, S.; Yoshida, K.; Favre, C.; Monfredini, T.; Quitián-Lara, H. M.; Marcelino, N.; Boechat-Roberty, H. M.; Cabrit, S.

2018-07-01

Evidence is mounting that the small bodies of our Solar system, such as comets and asteroids, have at least partially inherited their chemical composition from the first phases of the Solar system formation. It then appears that the molecular complexity of these small bodies is most likely related to the earliest stages of star formation. It is therefore important to characterize and to understand how the chemical evolution changes with solar-type protostellar evolution. We present here the Large Program `Astrochemical Surveys At IRAM' (ASAI). Its goal is to carry out unbiased millimetre line surveys between 80 and 272 GHz of a sample of 10 template sources, which fully cover the first stages of the formation process of solar-type stars, from pre-stellar cores to the late protostellar phase. In this paper, we present an overview of the surveys and results obtained from the analysis of the 3 mm band observations. The number of detected main isotopic species barely varies with the evolutionary stage and is found to be very similar to that of massive star-forming regions. The molecular content in O- and C-bearing species allows us to define two chemical classes of envelopes, whose composition is dominated by either (a) a rich content in O-rich complex organic molecules, associated with hot corino sources, or (b) a rich content in hydrocarbons, typical of warm carbon-chain chemistry sources. Overall, a high chemical richness is found to be present already in the initial phases of solar-type star formation.

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

PubMed

Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

PubMed Central

Van Wyngarden, A. L.; Pérez-Montaño, S.; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.

2016-01-01

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface. PMID:27212937

Processing and Structural Advantages of the Sylramic-iBN SiC Fiber for SiC/SiC Components

NASA Technical Reports Server (NTRS)

Yun, H. M.; Dicarlo, J. A.; Bhatt, R. T.; Hurst, J. B.

2008-01-01

The successful high-temperature application of complex-shaped SiC/SiC components will depend on achieving as high a fraction of the as-produced fiber strength as possible during component fabrication and service. Key issues center on a variety of component architecture, processing, and service-related factors that can reduce fiber strength, such as fiber-fiber abrasion during architecture shaping, surface chemical attack during interphase deposition and service, and intrinsic flaw growth during high-temperature matrix formation and composite creep. The objective of this paper is to show that the NASA-developed Sylramic-iBN SiC fiber minimizes many of these issues for state-of-the-art melt-infiltrated (MI) SiC/BN/SiC composites. To accomplish this, data from various mechanical tests are presented that compare how different high performance SiC fiber types retain strength during formation of complex architectures, during processing of BN interphases and MI matrices, and during simulated composite service at high temperatures.

Insect-gene-activity detection system for chemical and biological warfare agents and toxic industrial chemicals

NASA Astrophysics Data System (ADS)

Mackie, Ryan S.; Schilling, Amanda S.; Lopez, Arturo M.; Rayms-Keller, Alfredo

2002-02-01

Detection of multiple chemical and biological weapons (CBW) agents and/or complex mixtures of toxic industrial chemicals (TIC) is imperative for both the commercial and military sectors. In a military scenario, a multi-CBW attack would create confusion, thereby delaying decontamination and therapeutic efforts. In the commercial sector, polluted sites invariably contain a mixture of TIC. Novel detection systems capable of detecting CBW and TIC are sorely needed. While it may be impossible to build a detector capable of discriminating all the possible combinations of CBW, a detection system capable of statistically predicting the most likely composition of a given mixture is within the reach of current emerging technologies. Aquatic insect-gene activity may prove to be a sensitive, discriminating, and elegant paradigm for the detection of CBW and TIC. We propose to systematically establish the expression patterns of selected protein markers in insects exposed to specific mixtures of chemical and biological warfare agents to generate a library of biosignatures of exposure. The predicting capabilities of an operational library of biosignatures of exposures will allow the detection of emerging novel or genetically engineered agents, as well as complex mixtures of chemical and biological weapons agents. CBW and TIC are discussed in the context of war, terrorism, and pollution.

A GHS-consistent approach to health hazard classification of petroleum substances, a class of UVCB substances.

PubMed

Clark, Charles R; McKee, Richard H; Freeman, James J; Swick, Derek; Mahagaokar, Suneeta; Pigram, Glenda; Roberts, Linda G; Smulders, Chantal J; Beatty, Patrick W

2013-12-01

The process streams refined from petroleum crude oil for use in petroleum products are among those designated by USEPA as UVCB substances (unknown or variable composition, complex reaction products and biological materials). They are identified on global chemical inventories with unique Chemical Abstract Services (CAS) numbers and names. The chemical complexity of most petroleum substances presents challenges when evaluating their hazards and can result in differing evaluations due to the varying level of hazardous constituents and differences in national chemical control regulations. Global efforts to harmonize the identification of chemical hazards are aimed at promoting the use of consistent hazard evaluation criteria. This paper discusses a systematic approach for the health hazard evaluation of petroleum substances using chemical categories and the United Nations (UN) Globally Harmonized System (GHS) of classification and labeling. Also described are historical efforts to characterize the hazard of these substances and how they led to the development of categories, the identification of potentially hazardous constituents which should be considered, and a summary of the toxicology of the major petroleum product groups. The use of these categories can increase the utility of existing data, provide better informed hazard evaluations, and reduce the amount of animal testing required. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

NMR Quantification of Carbohydrates in Complex Mixtures. A Challenge on Honey.

PubMed

Schievano, Elisabetta; Tonoli, Marco; Rastrelli, Federico

2017-12-19

The knowledge of carbohydrate composition is greatly important to determine the properties of natural matrices such as foodstuff and food ingredients. However, because of the structural similarity and the multiple isomeric forms of carbohydrates in solution, their analysis is often a complex task. Here we propose an NMR analytical procedure based on highly selective chemical shift filters followed by TOCSY, which allows us to acquire specific background-free signals for each sugar. The method was tested on raw honey samples dissolved in water with no other pretreatment. In total, 22 sugars typically found in honey were quantified: 4 monosaccharides (glucose, fructose, mannose, rhamnose), 11 disaccharides (sucrose, trehalose, turanose, maltose, maltulose, palatinose, melibiose and melezitose, isomaltose, gentiobiose nigerose, and kojibiose), and 7 trisaccharides (raffinose, isomaltotriose, erlose, melezitose, maltotriose, panose, and 1-kestose). Satisfactory results in terms of limit of quantification (0.03-0.4 g/100g honey), precision (% RSD: 0.99-4.03), trueness (bias % 0.4-4.2), and recovery (97-104%) were obtained. An accurate control of the instrumental temperature and of the sample pH endows an optimal chemical shift reproducibility, making the procedure amenable to automation and suitable to routine analysis. While validated on honey, which is one of the most complex natural matrices in terms of saccharides composition, this innovative approach can be easily transferred to other natural matrices.

Search for Chemical Biomarkers on Mars Using the Sample Analysis at Mars Instrument Suite on the Mars Science Laboratory

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Conrad, P.; Dworkin, J. P.; Eigenbrode, J.; Mahaffy, P. R.

2011-01-01

One key goal for the future exploration of Mars is the search for chemical biomarkers including complex organic compounds important in life on Earth. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) will provide the most sensitive measurements of the organic composition of rocks and regolith samples ever carried out in situ on Mars. SAM consists of a gas chromatograph (GC), quadrupole mass spectrometer (QMS), and tunable laser spectrometer to measure volatiles in the atmosphere and released from rock powders heated up to 1000 C. The measurement of organics in solid samples will be accomplished by three experiments: (1) pyrolysis QMS to identify alkane fragments and simple aromatic compounds; pyrolysis GCMS to separate and identify complex mixtures of larger hydrocarbons; and (3) chemical derivatization and GCMS extract less volatile compounds including amino and carboxylic acids that are not detectable by the other two experiments.

Application of surface analytical methods in thin film analysis

NASA Astrophysics Data System (ADS)

Wen, Xingu

Self-assembly and the sol-gel process are two promising methods for the preparation of novel materials and thin films. In this research, these two methods were utilized to prepare two types of thin films: self-assembled monolayers of peptides on gold and SiO2 sol-gel thin films modified with Ru(II) complexes. The properties of the resulting thin films were investigated by several analytical techniques in order to explore their potential applications in biomaterials, chemical sensors, nonlinear optics and catalysis. Among the analytical techniques employed in the study, surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS) and grazing angle reflection absorption Fourier transform infrared spectroscopy (RA-FTIR), are particularly useful in providing information regarding the compositions and structures of the thin films. In the preparation of peptide thin films, monodisperse peptides were self-assembled on gold substrate via the N-terminus-coupled lipoic acid. The film compositions were investigated by XPS and agreed well with the theoretical values. XPS results also revealed that the surface coverage of the self-assembled films was significantly larger than that of the physisorbed films and that the chemisorption between the peptides and gold surface was stable in solvent. Studies by angle dependent XPS (ADXPS) and grazing angle RA-FTIR indicated that the peptides were on average oriented at a small angle from the surface normal. By using a model of orientation distribution function, both the peptide tilt angle and film thickness can be well calculated. Ru(II) complex doped SiO2 sol-gel thin films were prepared by low temperature sol-gel process. The ability of XPS coupled with Ar + ion sputtering to provide both chemical and compositional depth profile information of these sol-gel films was evaluated. This technique, together with UV-VIS and electrochemical measurements, was used to investigate the stability of Ru complexes in the composite films. The stability of Ru complexes with respect to dopant leaching was dependent on the film microstructures. Three methods aiming to improve the dopant stability were also explored. In addition, the ion exchange properties of the composite films, upon exposure to various ions in aqueous solutions, were investigated by XPS, and the ion exchange mechanism was elucidated.

Information-Theoretical Complexity Analysis of Selected Elementary Chemical Reactions

NASA Astrophysics Data System (ADS)

Molina-Espíritu, M.; Esquivel, R. O.; Dehesa, J. S.

We investigate the complexity of selected elementary chemical reactions (namely, the hydrogenic-abstraction reaction and the identity SN2 exchange reaction) by means of the following single and composite information-theoretic measures: disequilibrium (D), exponential entropy(L), Fisher information (I), power entropy (J), I-D, D-L and I-J planes and Fisher-Shannon (FS) and Lopez-Mancini-Calbet (LMC) shape complexities. These quantities, which are functionals of the one-particle density, are computed in both position (r) and momentum (p) spaces. The analysis revealed that the chemically significant regions of these reactions can be identified through most of the single information-theoretic measures and the two-component planes, not only the ones which are commonly revealed by the energy, such as the reactant/product (R/P) and the transition state (TS), but also those that are not present in the energy profile such as the bond cleavage energy region (BCER), the bond breaking/forming regions (B-B/F) and the charge transfer process (CT). The analysis of the complexities shows that the energy profile of the abstraction reaction bears the same information-theoretical features of the LMC and FS measures, however for the identity SN2 exchange reaction does not hold a simple behavior with respect to the LMC and FS measures. Most of the chemical features of interest (BCER, B-B/F and CT) are only revealed when particular information-theoretic aspects of localizability (L or J), uniformity (D) and disorder (I) are considered.

Composition of the lower crust of the Arabian Plate: a xenolith perspective

NASA Astrophysics Data System (ADS)

Al-Mishwat, Ali T.; Nasir, Sobhi J.

2004-01-01

Petrological and geochemical data for a suite of mafic granulite xenoliths in Cenozoic alkali basalts from Saudi Arabia, Jordan and Syria provide a unique opportunity to explore the composition and nature of the lower crust beneath the Arabian Plate. Two mineralogically and chemically distinct groups of xenoliths occur. Group I is composed of two pyroxenes and plagioclase approximately in equal amounts. Group II is plagioclase rich and has variable proportions of orthopyroxene and clinopyroxene. The xenolith mineral assemblages and geothermobarometry of coexisting minerals suggest that these xenoliths represent basaltic cumulates that crystallized under high-pressure conditions in the lower crust. The xenoliths possibly form a part of a lower crustal gabbroic intrusive complex that underlies the Arabian Plate and may represent mafic roots of an arc complex of Pan-African age beneath Arabia. The xenolith data are compatible with available geophysical models on crust thickness and layering. The crust is between 20 and 40 km thick, and its lower part consists of mafic meta-igneous granulites. The chemical averages of xenoliths from different parts of the Arabian Plate are more mafic than the estimated present-day average of model lower crust.

Polyphenols in foods are more complex than often thought.

PubMed

Cheynier, Véronique

2005-01-01

Dietary polyphenols show a great diversity of structures, ranging from rather simple molecules (monomers and oligomers) to polymers. Higher-molecular-weight structures (with molecular weights of > 500) are usually designated as tannins, which refers to their ability to interact with proteins. Among them, condensed tannins (proanthocyanidins) are particularly important because of their wide distribution in plants and their contributions to major food qualities. All phenolic compounds are highly unstable and rapidly transformed into various reaction products when the plant cells are damaged (for instance, during food processing), thus adding to the complexity of dietary polyphenol composition. The polyphenol composition of plant-derived foods and beverages depends on that of the raw material used but also on the extraction process and subsequent biochemical and chemical reactions of plant polyphenols. The occurrence of specific tannin-like compounds (ie, thearubigins and theaflavins) arising from enzymatic oxidation is well documented in black tea. Various chemical reactions involving anthocyanins and/or flavanols have been demonstrated to occur during red wine aging. Current knowledge regarding the reaction mechanisms involved in some of these processes and the structures of the resulting products is reviewed. Their effects on organoleptic and nutritional quality are also discussed.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins.

PubMed

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-03-24

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks ("seeds") for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn's largest moon, Titan.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins

PubMed Central

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-01-01

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks (“seeds”) for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn’s largest moon, Titan. PMID:27023520

A general computation model based on inverse analysis principle used for rheological analysis of W/O rapeseed and soybean oil emulsions

NASA Astrophysics Data System (ADS)

Vintila, Iuliana; Gavrus, Adinel

2017-10-01

The present research paper proposes the validation of a rigorous computation model used as a numerical tool to identify rheological behavior of complex emulsions W/O. Considering a three-dimensional description of a general viscoplastic flow it is detailed the thermo-mechanical equations used to identify fluid or soft material's rheological laws starting from global experimental measurements. Analyses are conducted for complex emulsions W/O having generally a Bingham behavior using the shear stress - strain rate dependency based on a power law and using an improved analytical model. Experimental results are investigated in case of rheological behavior for crude and refined rapeseed/soybean oils and four types of corresponding W/O emulsions using different physical-chemical composition. The rheological behavior model was correlated with the thermo-mechanical analysis of a plane-plane rheometer, oil content, chemical composition, particle size and emulsifier's concentration. The parameters of rheological laws describing the industrial oils and the W/O concentrated emulsions behavior were computed from estimated shear stresses using a non-linear regression technique and from experimental torques using the inverse analysis tool designed by A. Gavrus (1992-2000).

Chemical mixtures and environmental effects: a pilot study to assess ecological exposure and effects in streams

USGS Publications Warehouse

Buxton, Herbert T.; Reilly, Timothy J.; Kuivila, Kathryn; Kolpin, Dana W.; Bradley, Paul M.; Villeneuve, Daniel L.; Mills, Marc A.

2015-01-01

Assessment and management of the risks of exposure to complex chemical mixtures in streams are priorities for human and environmental health organizations around the world. The current lack of information on the composition and variability of environmental mixtures and a limited understanding of their combined effects are fundamental obstacles to timely identification and prevention of adverse human and ecological effects of exposure. This report describes the design of a field-based study of the composition and biological activity of chemical mixtures in U.S. stream waters affected by a wide range of human activities and contaminant sources. The study is a collaborative effort by the U.S. Geological Survey and the U.S. Environmental Protection Agency. Scientists sampled 38 streams spanning 24 States and Puerto Rico. Thirty-four of the sites were located in watersheds impacted by multiple contaminant sources, including industrial and municipal wastewater discharges, crop and animal agricultural runoff, urban runoff, and other point and nonpoint contaminant sources. The remaining four sites were minimally development reference watersheds. All samples underwent comprehensive chemical and biological characterization, including sensitive and specific direct analysis for over 700 dissolved organic and inorganic chemicals and field parameters, identification of unknown contaminants (environmental diagnostics), and a variety of bioassays to evaluate biological activity and toxicity.

A Terrestrial Analogue from Spitsbergen (Svalbard, Norway) for the Comanche Carbonate at Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Blake, D. F.; Bish, D.; Ming, Douglas W.; Agresti, D. G.; Treiman, A. H.; Steele, A.; Amundsen, H. E. F.

2011-01-01

Carbonate occurs at the Comanche outcrops in Gusev Crater on the basis of analyses made by the Mars Exploration Rover Spirit [1]. Taken together, mineralogical data from Spirit's Moessbauer (MB) and Mini-TES spectrometer and chemical data from the APXS spectrometer show that Comanche carbonate has an Mg-Fe-rich bulk chemical composition, is present at high concentrations, and is distributed throughout the outcrop and not just at the MB and APXS analysis location. The granular outcrop texture and the observation that it appears to be resistant to weathering compared with surrounding material [1] imply that the carbonate may be present as a cement. A hydrothermal origin for the Comanche carbonate was inferred by analogy with laboratory experiments and with a carbonate occurrence within the Bockfjord volcanic complex on the island Spitsbergen (Svalbard, Norway) [1]. The laboratory carbonates, synthesized by precipitation from hydrothermal solutions, have (MB) parameters and average bulk chemical compositions that are characteristic of Comanche carbonate. The connection to Comanche carbonate is only through chemical data for certain occurrences of Spitsbergen carbonates. In fact, the common average bulk chemical composition for these Spitsbergen carbonates, the synthetic carbonates, the Comanche carbonate, and also the carbonate globules found in martian meteorite ALH84001 is a chemical constraint consistent with a hydrothermal formation process for all the carbonates [e.g., 1-3]. We develop here a link between MB data for the Comanche carbonate from MER and MB data for certain Spitsbergen carbonate occurrences from laboratory measurements. We also obtained visible and near- IR spectra on Spitsbergen carbonates for comparison with martian carbonate detections made on the basis of CRISM spectral data, e.g., in Nili Fossae [4].

A procedure to estimate proximate analysis of mixed organic wastes.

PubMed

Zaher, U; Buffiere, P; Steyer, J P; Chen, S

2009-04-01

In waste materials, proximate analysis measuring the total concentration of carbohydrate, protein, and lipid contents from solid wastes is challenging, as a result of the heterogeneous and solid nature of wastes. This paper presents a new procedure that was developed to estimate such complex chemical composition of the waste using conventional practical measurements, such as chemical oxygen demand (COD) and total organic carbon. The procedure is based on mass balance of macronutrient elements (carbon, hydrogen, nitrogen, oxygen, and phosphorus [CHNOP]) (i.e., elemental continuity), in addition to the balance of COD and charge intensity that are applied in mathematical modeling of biological processes. Knowing the composition of such a complex substrate is crucial to study solid waste anaerobic degradation. The procedure was formulated to generate the detailed input required for the International Water Association (London, United Kingdom) Anaerobic Digestion Model number 1 (IWA-ADM1). The complex particulate composition estimated by the procedure was validated with several types of food wastes and animal manures. To make proximate analysis feasible for validation, the wastes were classified into 19 types to allow accurate extraction and proximate analysis. The estimated carbohydrates, proteins, lipids, and inerts concentrations were highly correlated to the proximate analysis; correlation coefficients were 0.94, 0.88, 0.99, and 0.96, respectively. For most of the wastes, carbohydrate was the highest fraction and was estimated accurately by the procedure over an extended range with high linearity. For wastes that are rich in protein and fiber, the procedure was even more consistent compared with the proximate analysis. The new procedure can be used for waste characterization in solid waste treatment design and optimization.

Protein Stains to Detect Antigen on Membranes.

PubMed

Dsouza, Anil; Scofield, R Hal

2015-01-01

Western blotting (protein blotting/electroblotting) is the gold standard in the analysis of complex protein mixtures. Electroblotting drives protein molecules from a polyacrylamide (or less commonly, of an agarose) gel to the surface of a binding membrane, thereby facilitating an increased availability of the sites with affinity for both general and specific protein reagents. The analysis of these complex protein mixtures is achieved by the detection of specific protein bands on a membrane, which in turn is made possible by the visualization of protein bands either by chemical staining or by reaction with an antibody of a conjugated ligand. Chemical methods employ staining with organic dyes, metal chelates, autoradiography, fluorescent dyes, complexing with silver, or prelabeling with fluorophores. All of these methods have differing sensitivities and quantitative determinations vary significantly. This review will describe the various protein staining methods applied to membranes after western blotting. "Detection" precedes and is a prerequisite to obtaining qualitative and quantitative data on the proteins in a sample, as much as to comparing the protein composition of different samples. "Detection" is often synonymous to staining, i.e., the reversible or irreversible binding by the proteins of a colored organic or inorganic chemical.

Chemometrics Methods for Specificity, Authenticity and Traceability Analysis of Olive Oils: Principles, Classifications and Applications.

PubMed

Messai, Habib; Farman, Muhammad; Sarraj-Laabidi, Abir; Hammami-Semmar, Asma; Semmar, Nabil

2016-11-17

Olive oils (OOs) show high chemical variability due to several factors of genetic, environmental and anthropic types. Genetic and environmental factors are responsible for natural compositions and polymorphic diversification resulting in different varietal patterns and phenotypes. Anthropic factors, however, are at the origin of different blends' preparation leading to normative, labelled or adulterated commercial products. Control of complex OO samples requires their (i) characterization by specific markers; (ii) authentication by fingerprint patterns; and (iii) monitoring by traceability analysis. These quality control and management aims require the use of several multivariate statistical tools: specificity highlighting requires ordination methods; authentication checking calls for classification and pattern recognition methods; traceability analysis implies the use of network-based approaches able to separate or extract mixed information and memorized signals from complex matrices. This chapter presents a review of different chemometrics methods applied for the control of OO variability from metabolic and physical-chemical measured characteristics. The different chemometrics methods are illustrated by different study cases on monovarietal and blended OO originated from different countries. Chemometrics tools offer multiple ways for quantitative evaluations and qualitative control of complex chemical variability of OO in relation to several intrinsic and extrinsic factors.

Protein stains to detect antigen on membranes.

PubMed

D'souza, Anil; Scofield, R Hal

2009-01-01

Western blotting (protein blotting/electroblotting) is the gold standard in the analysis of complex protein mixtures. Electroblotting drives protein molecules from a polyacrylamide (or less commonly, of an agarose) gel to the surface of a binding membrane, thereby facilitating an increased availability of the sites with affinity for both general and specific protein reagents. The analysis of these complex protein mixtures is achieved by the detection of specific protein bands on a membrane, which in turn is made possible by the visualization of protein bands either by chemical staining or by reaction with an antibody of a conjugated ligand. Chemical methods employ staining with organic dyes, metal chelates, autoradiography, fluorescent dyes, complexing with silver, or prelabeling with fluorophores. All of these methods have differing sensitivities and quantitative determinations vary significantly. This review will describe the various protein staining methods applied to membranes after electrophoresis. "Detection" precedes and is a prerequisite to obtaining qualitative and quantitative data on the proteins in a sample, as much as to comparing the protein composition of different samples. Detection is often synonymous to staining, i.e., the reversible or irreversible binding by the proteins of a colored organic or inorganic chemical.

Chemical and isotopic diversity in basalts dredged from the East Pacific Rise at 10°S, the fossil Galapagos Rise and the Nazca plate

USGS Publications Warehouse

Batiza, Rodey; Oestrike, Richard; Futa, Kiyoto

1982-01-01

The dredges from the East Pacific Rise at about 10°S recovered unusual transitional, light rare-earth element (LREE) enriched basalts which show a range of fractionation. On the basis of their chemical and isotopic abundances, it is unlikely that the lavas are related by a single simple process of magmatic differentiation. We suggest that the mantle source region of these basalts was chemically and isotopically heterogeneous. The chemistry of LREE-depleted tholeiitic basalt dredged from near the axis of the extinct Galapagos Rise indicates complex petrogenesis and differentiation. The presence of tholeiitic basalts here indicates that unlike the Guadalupe and Mathematician fossil ridges, the Galapagos Rise has not been the site of voluminous post-abandonment alkalic volcanism. Alkalic basalts of picritic bulk composition dredged from an elongate seamount near the Galapagos Rise do not represent liquid compositions. Instead, we suggest that these alkalic liquids contain added olivine and plagioclase xenocrysts. Although most of the samples analyzed are very fresh, a few have been altered. The latter exhibit characteristic chemical and isotopic effects of seawater alteration.

Chemical composition of individual aerosol particles in workplace air during production of manganese alloys.

PubMed

Gunst, S; Weinbruch, S; Wentzel, M; Ortner, H M; Skogstad, A; Hetland, S; Thomassen, Y

2000-02-01

Aerosol particle samples were collected at ELKEM ASA ferromanganese (FeMn) and silicomanganese (SiMn) smelters at Porsgrunn, Norway, during different production steps: raw material mixing, welding of protective steel casings, tapping of FeMn and slag, crane operation moving the ladles with molten metal, operation of the Metal Oxygen Refinement (MOR) reactor and casting of SiMn. Aerosol fractions were assessed for the analysis of the bulk elemental composition as well as for individual particle analysis. The bulk elemental composition was determined by inductively coupled plasma atomic emission spectrometry. For individual particle analysis, an electron microprobe was used in combination with wavelength-dispersive techniques. Most particles show a complex composition and cannot be attributed to a single phase. Therefore, the particles were divided into six groups according to their chemical composition: Group I, particles containing mainly metallic Fe and/or Mn; Group II, slag particles containing mainly Fe and/or Mn oxides; Group III, slag particles consisting predominantly of oxidized flux components such as Si, Al, Mg, Ca, Na and K; Group IV, particles consisting mainly of carbon; Group V, mixtures of particles from Groups II, III and IV; Group VI, mixtures of particles from Groups II and III. In raw material mixing, particles originating from the Mn ores were mostly found. In the welding of steel casings, most particles were assigned to Group II, Mn and Fe oxides. During the tapping of slag and metal, mostly slag particles from Group III were found (oxides of the flux components). During movement of the ladles, most particles came from Group II. At the MOR reactor, most of the particles belonged to the slag phase consisting of the flux components (Group III). The particles collected during the casting of SiMn were mainly attributed to the slag phase (Groups III and V). Due to the compositional complexity of the particles, toxicological investigations on the kinetics of pure compounds may not be easily associated with the results of this study.

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.

2011-01-01

Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

NASA Astrophysics Data System (ADS)

Gunasekera, K.; Boolchand, P.; Micoulaut, M.

2014-04-01

Amorphous GexSixTe1-2x glasses are studied as a function of composition by a combination of experimental and theoretical methods, allowing for a full description of the network structure in relationship with physico-chemical properties. Calorimetric and thermal measurements reveal that such glasses display an anomalous behavior across a range of compositions xc1=7.5% and

Nutritional Characteristics of Forage Grown in South of Benin

PubMed Central

Musco, Nadia; Koura, Ivan B.; Tudisco, Raffaella; Awadjihè, Ghislain; Adjolohoun, Sebastien; Cutrignelli, Monica I.; Mollica, Maria Pina; Houinato, Marcel; Infascelli, Federico; Calabrò, Serena

2016-01-01

In order to provide recommendations on the most useful forage species to smallholder farmers, eleven grass and eleven legume forages grown in Abomey-Calavi in Republic of Benin were investigated for nutritive value (i.e. chemical composition and energy content) and fermentation characteristics (i.e. gas and volatile fatty acid production, organic matter degradability). The in vitro gas production technique was used, incubating the forages for 120 h under anaerobic condition with buffalo rumen fluid. Compared to legume, tropical grass forages showed lower energy (8.07 vs 10.57 MJ/kg dry matter [DM]) and crude protein level (16.10% vs 19.91% DM) and higher cell wall content (neutral detergent fiber: 63.8% vs 40.45% DM), respectively. In grass forages, the chemical composition showed a quite high crude protein content; the in vitro degradability was slightly lower than the range of tropical pasture. The woody legumes were richer in protein and energy and lower in structural carbohydrates than herbaceous plants, however, their in vitro results are influenced by the presence of complex compounds (i.e. tannins). Significant correlations were found between chemical composition and in vitro fermentation characteristics. The in vitro gas production method appears to be a suitable technique for the evaluation of the nutritive value of forages in developing countries. PMID:26732328

Chemical differences between voided and bladder urine in the aye-aye (Daubentonia madagascariensis): implications for olfactory communication studies.

PubMed

Delbarco-Trillo, Javier; Harelimana, Innocent H; Goodwin, Thomas E; Drea, Christine M

2013-07-01

Urine serves a communicative function in many mammalian species. In some species, the signaling function of urine can be enhanced by the addition of chemical compounds from glands along the distal portion of the urogenital tract. Although urine marking is the main mode of chemical communication in many primate species, there has been no study of the contribution of urogenital secretions to the chemical complexity of primate urine. Here, we compared the chemical composition of bladder urine versus voided urine in the aye-aye, Daubentonia madagascariensis, a strepsirrhine primate that relies on urine in intraspecific communication. Both types of urine, collected from each of 11 aye-ayes representing both sexes of varying adult ages, underwent headspace analysis via gas chromatography and mass spectrometry. Although the average number of compounds was similar in bladder and voided urine, 17% of the compounds detected occurred exclusively in voided urine (but only in a subset of individuals). An overall measure of chemical complexity (using a nonmetric multidimensional scaling analysis) showed that both types of urine were chemically different at the individual level. There was no apparent sex or age differences in the chemical components found in aye-aye urine. Nonetheless, the individual dissimilarities between bladder urine and voided urine indicate chemical contributions from structures along the urogenital tract and offer further support for the relevance of urinary communication in the aye-aye. © 2012 Wiley Periodicals, Inc.

Chemical profiles of body surfaces and nests from six Bornean stingless bee species.

PubMed

Leonhardt, Sara Diana; Blüthgen, Nico; Schmitt, Thomas

2011-01-01

Stingless bees (Apidae: Meliponini) are the most diverse group of Apid bees and represent common pollinators in tropical ecosystems. Like honeybees they live in large eusocial colonies and rely on complex chemical recognition and communication systems. In contrast to honeybees, their ecology and especially their chemical ecology have received only little attention, particularly in the Old World. We previously have analyzed the chemical profiles of six paleotropical stingless bee species from Borneo and revealed the presence of species-specific cuticular terpenes- an environmentally derived compound class so far unique among social insects. Here, we compared the bees' surface profiles to the chemistry of their nest material. Terpenes, alkanes, and alkenes were the dominant compound groups on both body surfaces and nest material. However, bee profiles and nests strongly differed in their chemical composition. Body surfaces thus did not merely mirror nests, rendering a passive compound transfer from nests to bees unlikely. The difference between nests and bees was particularly pronounced when all resin-derived compounds (terpenes) were excluded and only genetically determined compounds were considered. When terpenes were included, bee profiles and nest material still differed, because whole groups of terpenes (e.g., sesquiterpenes) were found in nest material of some species, but missing in their chemical profile, indicating that bees are able to influence the terpene composition both in their nests and on their surfaces.

Complex rheological properties of a water-soluble extract from the fronds of the black tree fern, Cyathea medullaris.

PubMed

Goh, Kelvin K T; Matia-Merino, Lara; Hall, Christopher E; Moughan, Paul J; Singh, Harjinder

2007-11-01

A water-soluble extract was obtained from the fronds of a New Zealand native black tree fern (Cyathea medullaris or Mamaku in Māori). The extract exhibited complex rheological behavior. Newtonian, shear-thinning, shear-thickening, thixotropic, antithixotropic, and viscoelastic behaviors were observed depending on polymer concentration, shear rate, and shear history. The extract also displayed rod-climbing and self-siphoning properties typical of viscoelastic fluids. Such complex rheological properties have been reported in synthetic or chemically modified polymers but are less frequent in unmodified biopolymers. Although Mamaku extract obtained from the pith of the fern has been traditionally used by the Māori in New Zealand for treating wounds and diarrhea among other ailments, this material has never been characterized before. This study reports on the chemical composition of the extract and on its viscoelastic properties through rotational and oscillatory rheological measurements. Explanations of the mechanism behind the rheological properties were based on transient network models for associating polymers.

Formation of high-temperature superconductor films during the nonstationary laser heating of liquid metal carboxylate solutions

NASA Astrophysics Data System (ADS)

Borman, V. D.; Dudko, S. A.; Sinitsyn, I. V.; Troian, V. I.; Filippov, E. A.

1989-01-01

It has been shown in earlier studies that high-temperature superconductor films can be produced through the decomposition of metal (Y, Ba, Cu) carboxylates in a liquid solution film. In the present study, the effect of nonstationary laser heating on the composition and properties of the complex oxide films formed by this method is examined with reference to experimental results obtained for YBa2Cu3O(x) films. It is shown that the chemical composition and properties of films formed in metal carboxylate solutions can be controlled by varying the time of laser heating.

Studies on a lipopolysaccharide-protein complex from Yersinia pseudotuberculosis. 1 isolation and characterization.

PubMed

Solov'eva, T F; Yermak, I M; Bondarenko, O D; Frolova, G M; Ovodov, Y S

1979-01-01

A comparative study of various procedures of a lipopolysaccharide-protein complex (LPPC) from Yersinia pseudotuberculosis was carried out. The materials obtained were fractionated by molecular-sieve chromatography on Sepharose 2B resulting in highly aggregated complexes with antigen activity. LPPC aggregates dissociated in the presence of sodium dodecylsulphate (SDS) and urea. The chemical composition and serologic properties of fractions obtained are under consideration. The protein component of the complex consists of two major polypeptides (molecular weights--45,000 and 20,000) and some minor ones. The LPS component appeared to give 2--3 narrow bands in gel under conditions of SDS-polyacrylamide gel electrophoresis. It is suggested that such fractionation is caused by LPS association-dissociation in the course of electrophoresis.

Comparison of Metabolomics Approaches for Evaluating the Variability of Complex Botanical Preparations: Green Tea (Camellia sinensis) as a Case Study.

PubMed

Kellogg, Joshua J; Graf, Tyler N; Paine, Mary F; McCune, Jeannine S; Kvalheim, Olav M; Oberlies, Nicholas H; Cech, Nadja B

2017-05-26

A challenge that must be addressed when conducting studies with complex natural products is how to evaluate their complexity and variability. Traditional methods of quantifying a single or a small range of metabolites may not capture the full chemical complexity of multiple samples. Different metabolomics approaches were evaluated to discern how they facilitated comparison of the chemical composition of commercial green tea [Camellia sinensis (L.) Kuntze] products, with the goal of capturing the variability of commercially used products and selecting representative products for in vitro or clinical evaluation. Three metabolomic-related methods-untargeted ultraperformance liquid chromatography-mass spectrometry (UPLC-MS), targeted UPLC-MS, and untargeted, quantitative 1 HNMR-were employed to characterize 34 commercially available green tea samples. Of these methods, untargeted UPLC-MS was most effective at discriminating between green tea, green tea supplement, and non-green-tea products. A method using reproduced correlation coefficients calculated from principal component analysis models was developed to quantitatively compare differences among samples. The obtained results demonstrated the utility of metabolomics employing UPLC-MS data for evaluating similarities and differences between complex botanical products.

Comparison of Metabolomics Approaches for Evaluating the Variability of Complex Botanical Preparations: Green Tea (Camellia sinensis) as a Case Study

PubMed Central

2017-01-01

A challenge that must be addressed when conducting studies with complex natural products is how to evaluate their complexity and variability. Traditional methods of quantifying a single or a small range of metabolites may not capture the full chemical complexity of multiple samples. Different metabolomics approaches were evaluated to discern how they facilitated comparison of the chemical composition of commercial green tea [Camellia sinensis (L.) Kuntze] products, with the goal of capturing the variability of commercially used products and selecting representative products for in vitro or clinical evaluation. Three metabolomic-related methods—untargeted ultraperformance liquid chromatography–mass spectrometry (UPLC-MS), targeted UPLC-MS, and untargeted, quantitative 1HNMR—were employed to characterize 34 commercially available green tea samples. Of these methods, untargeted UPLC-MS was most effective at discriminating between green tea, green tea supplement, and non-green-tea products. A method using reproduced correlation coefficients calculated from principal component analysis models was developed to quantitatively compare differences among samples. The obtained results demonstrated the utility of metabolomics employing UPLC-MS data for evaluating similarities and differences between complex botanical products. PMID:28453261

Covariant C and O Isotope Trends in Arctic Carbonate Crusts and ALH 84001: Potential Biomarker or Indicator of Cryogenic Formation Environment?

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Niles, Paul B.; Blake, Weston; Leveille, Richard

2009-01-01

This work seeks to use the chemical, isotopic, and mineralogical characteristics of secondary carbonate minerals produced during brief aqueous events to identify the conditions of the aqueous environment in which they formed. Liquid water near the surface of Mars is subject to either rapid freezing and/or evaporation. These processes are also active on Earth, and produce secondary minerals that have complex chemical, mineralogical, and isotopic textures and compositions that can include covariant relationships between Delta C-13 (sub VPDB) and delta O-18 (sub VSMOW). The extremely well studied four billion year old carbonates preserved in martian meteorite ALH 84001 also show covariant delta C-13 and delta O-18 compositions, but these variations are manifested on a micro-scale in a single thin section while the variation observed so far in terrestrial carbonates is seen between different hand samples.

Untargeted Identification of Wood Type-Specific Markers in Particulate Matter from Wood Combustion.

PubMed

Weggler, Benedikt A; Ly-Verdu, Saray; Jennerwein, Maximilian; Sippula, Olli; Reda, Ahmed A; Orasche, Jürgen; Gröger, Thomas; Jokiniemi, Jorma; Zimmermann, Ralf

2016-09-20

Residential wood combustion emissions are one of the major global sources of particulate and gaseous organic pollutants. However, the detailed chemical compositions of these emissions are poorly characterized due to their highly complex molecular compositions, nonideal combustion conditions, and sample preparation steps. In this study, the particulate organic emissions from a masonry heater using three types of wood logs, namely, beech, birch, and spruce, were chemically characterized using thermal desorption in situ derivatization coupled to a GCxGC-ToF/MS system. Untargeted data analyses were performed using the comprehensive measurements. Univariate and multivariate chemometric tools, such as analysis of variance (ANOVA), principal component analysis (PCA), and ANOVA simultaneous component analysis (ASCA), were used to reduce the data to highly significant and wood type-specific features. This study reveals substances not previously considered in the literature as meaningful markers for differentiation among wood types.

The composition of heavy molecular ions inside the ionopause of Comet Halley

NASA Technical Reports Server (NTRS)

Mitchell, David L.; Lin, R. P.; Anderson, K. A.; Carlson, C. W.; Curtis, D. W.; Korth, A.; Reme, H.; Sauvaud, J. A.; Duston, C.; Mendis, D. A.

1989-01-01

The RPA2-PICCA instrument aboard the Giotto spacecraft obtained 10-210 amu mass spectral of cold thermal molecular ions in the coma of Comet Halley. The dissociation products of the long chain formaldehyde polymer polyoxymethylene (POM) have recently been proposed as the dominant complex molecules in the coma of Comet Halley; however, POM alone cannot account for all of the features of the high resolution spectrum. An important component of the dust at Comet Halley is particles highly enriched in carbon, hydrogen, oxygen, and nitrogen relative to the composition of carbonaceous chondrites. Since this dust could be a source for the heavy molecules observed by PICCA, a search was conducted for other chemical species by determining all the molecules with mass between 20 and 120 amu which can be made from the relatively abundant C, H, O, and N, without regard to chemical structure.

Satellite Observations of the Effect of Natural and Anthropogenic Aerosols on Clouds

NASA Technical Reports Server (NTRS)

Kaufman, Yoram J.

2006-01-01

Our knowledge of atmospheric aerosols (smoke, pollution, dust or sea salt particles, small enough to be suspended in the air), their evolution, composition, variability in space and time and interaction with clouds and precipitation is still lacking despite decades of research. Understanding the global aerosol system is critical to quantifying anthropogenic climate change, to determine climate sensitivity from observations and to understand the hydrological cycle. While a single instrument was used to demonstrate 50 years ago that the global CO2 levels are rising, posing threat of global warming, we need an array of satellites and field measurements coupled with chemical transport models to understand the global aerosol system. This complexity of the aerosol problem results from their short lifetime (1 week) and variable chemical composition. A new generation of satellites provides exciting opportunities to measure the global distribution of aerosols, distinguishing natural from anthropogenic aerosol and measuring their interaction with clouds and climate.

Secondary mineral growth in fractures in the Miravalles geothermal system, Costa Rica

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

Rochelle, C.A.; Milodowski, A.E.; Savage, D.

1989-01-01

A mineralogical, fluid-chemical, and theoretical study of hydrothermal alteration in veins from drillcore from the Miravalles geothermal field, Costa Rica has revealed a complex history of mineral-fluid reaction which may be used to characterize changes in temperature and fluid composition with time. Mineralogical and mineral-chemical data are consistent with hydrothermal alteration in the temperature range 200{sup 0}-270{sup 0}C, with deeper portions of the system having undergone temperatures in excess of 300{sup 0}C. Thermodynamic calculations suggest that the observed alteration assemblage is not equilibrium with current well fluids, unless estimates of reservoir pH are incorrect. Fe-Al zoning of prehnite and epidotemore » in veins is consistent with rapid, isothermal fluctuations in fluid composition at current reservoir temperatures, and may be due to changes in volatile content of the fluid due to tectonic activity.« less

Overview of Aerosol Distribution

NASA Technical Reports Server (NTRS)

Kaufman, Yoram

2005-01-01

Our knowledge of atmospheric aerosols (smoke, pollution, dust or sea salt particles, small enough to be suspended in the air), their evolution, composition, variability in space and time and interaction with clouds and precipitation is still lacking despite decades of research. Understanding the global aerosol system is fundamental for progress in climate change and hydrological cycle research. While a single instrument was used to demonstrate 50 years ago that the global CO2 levels are rising, posing threat of global warming, we need an array of satellites and field measurements coupled with chemical transport models to understand the global aerosol system. This complexity of the aerosol problem results from their short lifetime (1 week) and variable chemical composition. A new generation of satellites provides exciting opportunities to measure the global distribution of aerosols, distinguishing natural from anthropogenic aerosol and measuring their interaction with clouds and climate. I shall discuss these topics and application of the data to air quality monitoring.

Safety evaluation of food contact paper and board using chemical tests and in vitro bioassays: role of known and unknown substances.

PubMed

Honkalampi-Hämäläinen, U; Bradley, E L; Castle, L; Severin, I; Dahbi, L; Dahlman, O; Lhuguenot, J-C; Andersson, M A; Hakulinen, P; Hoornstra, D; Mäki-Paakkanen, J; Salkinoja-Salonen, M; Turco, L; Stammati, A; Zucco, F; Weber, A; von Wright, A

2010-03-01

In vitro toxicological tests have been proposed as an approach to complement the chemical safety assessment of food contact materials, particularly those with a complex or unknown chemical composition such as paper and board. Among the concerns raised regarding the applicability of in vitro tests are the effects of interference of the extractables on the outcome of the cytotoxicity and genotoxicity tests applied and the role of known compounds present in chemically complex materials, such as paper and board, either as constituents or contaminants. To answer these questions, a series of experiments were performed to assess the role of natural substances (wood extracts, resin acids), some additives (diisopropylnaphthalene, phthalates, acrylamide, fluorescent whitening agents) and contaminants (2,4-diaminotoluene, benzo[a]pyrene) in the toxicological profile of paper and board. These substances were individually tested or used to spike actual paper and board extracts. The toxic concentrations of diisopropylnaphthalenes and phthalates were compared with those actually detected in paper and board extracts showing conspicuous toxicity. According to the results of the spiking experiments, the extracts did not affect the toxicity of tested chemicals nor was there any significant metabolic interference in the cases where two compounds were used in tests involving xenobiotic metabolism by the target cells. While the identified substances apparently have a role in the cytotoxicity of some of the project samples, their presence does not explain the total toxicological profile of the extracts. In conclusion, in vitro toxicological testing can have a role in the safety assessment of chemically complex materials in detecting potentially harmful activities not predictable by chemical analysis alone.

Chemical composition of aerosol measurements in the air pollution plume during KORUS-AQ

NASA Astrophysics Data System (ADS)

Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Park, J. S.; Soo, C. J.; Kim, J.; Park, S.; Lee, Y.; Desyaterik, Y.; Collett, J. L., Jr.; Lee, T.

2017-12-01

The Korean peninsula is a great place to study different sources of the aerosols: urban, rural and marine. In addition, Seoul is one of the large metropolitan areas in the world and has a variety of sources because half of the Korean population lives in Seoul, which comprises only 12% of the country's area. To understand the chemical composition of aerosol form long-range transport and local sources better, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on an airborne platform (NASA DC-8 aircraft). The HR-ToF-AMS is capable of measuring non-refractory size resolved chemical composition of submicron particle(NR-PM1) in the air pollution plume, including mass concentration of organic carbon, nitrate, sulfate, and ammonium with 10 seconds time resolution. The measurements were performed twenty times research flight for understanding characteristic of the air pollution from May to June, 2016 on the South Korean peninsula during KORUS-AQ 2016 campaign. The scientific goal of this study is to characterize aerosol chemical properties and mass concentration in order to understand the role of the long-range transport from northeast Asia to South Korea, and influence of the local sources. To brief, organics dominated during all of flights. Also, organics and nitrate were dominant around energy industrial complex near by Taean, South Korea. The presentation will provide an overview of the composition of NR-PM1 measured in air pollution plumes, and deliver detail information about width, depth and spatial distribution of the pollutant in the air pollution plumes. The results of this study will provide high temporal and spatial resolved details on the air pollution plumes, which are valuable input parameters of aerosol properties for the current air quality models.

Single Particle Analysis by Combined Chemical Imaging to Study Episodic Air Pollution Events in Vienna

NASA Astrophysics Data System (ADS)

Ofner, Johannes; Eitenberger, Elisabeth; Friedbacher, Gernot; Brenner, Florian; Hutter, Herbert; Schauer, Gerhard; Kistler, Magdalena; Greilinger, Marion; Lohninger, Hans; Lendl, Bernhard; Kasper-Giebl, Anne

2017-04-01

The aerosol composition of a city like Vienna is characterized by a complex interaction of local emissions and atmospheric input on a regional and continental scale. The identification of major aerosol constituents for basic source appointment and air quality issues needs a high analytical effort. Exceptional episodic air pollution events strongly change the typical aerosol composition of a city like Vienna on a time-scale of few hours to several days. Analyzing the chemistry of particulate matter from these events is often hampered by the sampling time and related sample amount necessary to apply the full range of bulk analytical methods needed for chemical characterization. Additionally, morphological and single particle features are hardly accessible. Chemical Imaging evolved to a powerful tool for image-based chemical analysis of complex samples. As a complementary technique to bulk analytical methods, chemical imaging can address a new access to study air pollution events by obtaining major aerosol constituents with single particle features at high temporal resolutions and small sample volumes. The analysis of the chemical imaging datasets is assisted by multivariate statistics with the benefit of image-based chemical structure determination for direct aerosol source appointment. A novel approach in chemical imaging is combined chemical imaging or so-called multisensor hyperspectral imaging, involving elemental imaging (electron microscopy-based energy dispersive X-ray imaging), vibrational imaging (Raman micro-spectroscopy) and mass spectrometric imaging (Time-of-Flight Secondary Ion Mass Spectrometry) with subsequent combined multivariate analytics. Combined chemical imaging of precipitated aerosol particles will be demonstrated by the following examples of air pollution events in Vienna: Exceptional episodic events like the transformation of Saharan dust by the impact of the city of Vienna will be discussed and compared to samples obtained at a high alpine background site (Sonnblick Observatory, Saharan Dust Event from April 2016). Further, chemical imaging of biological aerosol constituents of an autumnal pollen breakout in Vienna, with background samples from nearby locations from November 2016 will demonstrate the advantages of the chemical imaging approach. Additionally, the chemical fingerprint of an exceptional air pollution event from a local emission source, caused by the pull down process of a building in Vienna will unravel the needs for multisensor imaging, especially the combinational access. Obtained chemical images will be correlated to bulk analytical results. Benefits of the overall methodical access by combining bulk analytics and combined chemical imaging of exceptional episodic air pollution events will be discussed.

Sedimentary Geochemistry of Martian Samples from the Pathfinder Mission

NASA Technical Reports Server (NTRS)

McLennan, Scott M.

2001-01-01

The purpose of this research project was to evaluate the APXS data collected on soils and rocks at the Pathfinder site in terms of sedimentary geochemistry. Below are described the major findings of this research: (1) An influential model to explain the chemical variation among Pathfinder soils and rocks is a two component mixing model where rocks of fairly uniform composition mix with soil of uniform composition; (2) The very strong positive correlation between MgO and SO, points to a control by a MgSO4 mineral however, spectroscopic data continue to suggest that Fe-sulfates, notably schwertmannite and jarosite, may be important components; (3) In an attempt to better understand the causes of complexities in mixing relationships, the possible influence of sedimentary transport has been evaluated; (4) Another aspect of this research has been to examine the possibility of sedimentary silica being a significant phase on Mars; and (5) On Earth, the geochemistry of sedimentary rocks has been used to constrain the chemical composition of the continental crust and an important part of this research was to evaluate this approach for Mars.

Magnetic field tunable ac electrical transport of LaFeO3-wax nanocomposites

NASA Astrophysics Data System (ADS)

Roy, Supratim; Mandal, S. K.; Debnath, Rajesh; Nath, Debajyoti; Dey, P.

2018-04-01

Single phase perovskite LaFeO3 nanoparticles have been prepared through chemical pyrophoric reaction process. It is further grinded with paraffin wax of quantity 0.5 wt% of total composition to obtain an organic composite 99.5%LaFeO3-0.5%Wax. Studies of ac electrical properties viz. complex impedance, dielectric response, loss coefficient have been done in presence of external dc magnetic field, which reveals a good magnetoimpedance (˜221%) and a negative magnetodielectric (˜ 64%). The value of impedance, its real and imaginary part is observed to increase with dc field. The composite exhibits high dielectric constant (˜4760). The ac conductivity is found to decrease with applied field and increase with ac frequency.

Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

DOEpatents

Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

2015-01-13

Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

Naval Research Reviews, Volume 32, Number 4

DTIC Science & Technology

1980-01-01

iron while (e.g., carbon, chlorine, phosphorous, sulfur, zinc other areas are still covered by an oxide . An XPS and boron). An example of the chemical...picture. Metallic bearing components, for ex- major impact on tribology. The first is the develop- ample, usually have complex oxide films on their...the composition or thickncs. IThe optical image is m,.chanisms responsible for ion beam degradation of rotated slightly withrespecttoelectronimages

REM-containing silicate concentrates

NASA Astrophysics Data System (ADS)

Pavlov, V. F.; Shabanova, O. V.; Pavlov, I. V.; Pavlov, M. V.; Shabanov, A. V.

2016-01-01

A new method of advanced complex processing of ores containing rare-earth elements (REE) is proposed to obtain porous X-ray amorphous aluminosilicate material with a stable chemical composition which concentrates oxides of rare-earth metals (REM). The ferromanganese oxide ores of Chuktukon deposit (Krasnoyarsk Region, RF) were used for the experiment. The obtained aluminosilicate material is appropriate for treatment with 5 - 15% solutions of mineral acids to leach REM.

The Navy Medical Technology Watch: Hemostatic Dressing Products for the Battlefield

DTIC Science & Technology

2006-09-09

composition and ingredients, external bleeding cessation agents all work to help the rapid formation of a thrombus (clot) or other blockage at the...clotting agent Contraindicated for internal bleeding or deep tissue wounds Collagen. Collagen-like natural substances are created from chemically...2003) Experimental (swine) Complex groin injury, arterial, venous QuikClot produced 0% mortality; RDH had a 66% mortality rate. QuikClot

Origin of the Moon: In search of the holy grail. [volcanic glass

NASA Technical Reports Server (NTRS)

Delano, J. W.

1984-01-01

The Moon's origin could be deduced with certainty if its bulk chemistry were known. However, determination of this chemistry is difficult because of the profound and complex redistribution of elements that occurred in the outer portions of the Moon during crystallization of the magma ocean. The compositions of 23 varieties of volcanic glass, erupted from depths approaching 300 miles, were used to predict the chemistry of a special glass (genesis glass) having a direct link to primordial lunar matter. A sample of glass with the predicted composition was discovered. This allows a new estimate to be made of the Moon's bulk composition. The data indicate that the Moon shares some intriquing chemical similarities with the Earth's mantle. Both genesis glass and lunar gas are furnishing definitive data on the Moon's composition and origin.

Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

2017-12-01

Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

Evidences of Multiple Magma Injections in Quaternary Balerang and Rajabasa Volcanoes, Indonesia

NASA Astrophysics Data System (ADS)

Hasibuan, R. F.; Ohba, T.; Abdurrachman, M.

2016-12-01

Quaternary Balerang and Rajabasa volcanoes are situated along the nearly north-south lineament with a most explosive Krakatau volcanic complex in the south and effusive Sukadana basalt plateau in the north. Some studies have elucidated that Krakatau volcano has multiple magma storage regions beneath together with evidences of magma mixing process. By considering these circumstances, it is necessary to know lateral variations of magmas and to characterize volcanic rocks from Rajabasa volcanic complex which is located between these distinct magmatic systems, in terms of magmatic processes and evolution. Methodologies we used are X-ray fluorescence to determine the whole rock chemistry, K-Ar isotope dating to determine the lifespan of the volcano, as well as EPMA analysis to obtain the chemical composition of minerals. The rock chemistry or TAS plot shows a linear trend, ranging from basaltic (51 wt.%) to rhyolitic (75 wt.%), indicating a chemical heterogeneity of magma. When SiO2 contents are correlated with the relative ages, we found a broad tendency that SiO2 contents progressively decrease with age. The Rajabasa volcano lifespan is known formed at 0.31 Ma while one of the youngest lava is identified erupted at 0.12 Ma. Some plagioclase crystals exhibit disequilibrium textures, like highly sieved core and clear rim regions, also overgrowth rim on the plagioclase and pyroxene crystals whose composition more primitive than the core's composition, indicating magmatic recharge events. Reverse zoning and resorption textures associated with compositional step zoning or progressive zoning are quite common as well in clinopyroxene and plagioclase crystals. By considering these evidences, we conclude that injection of a hotter basaltic magma into colder and more felsic magma occurred beneath the volcanoes.

Aerosol chemistry in Titan's ionosphere: simultaneous growth and etching processes

NASA Astrophysics Data System (ADS)

Carrasco, Nathalie; Cernogora, Guy; Jomard, François; Etcheberry, Arnaud; Vigneron, Jackie

2016-10-01

Since the Cassini-CAPS measurements, organic aerosols are known to be present and formed at high altitudes in the diluted and partially ionized medium that is Titan's ionosphere [1]. This unexpected chemistry can be further investigated in the laboratory with plasma experiments simulating the complex ion-neutral chemistry starting from N2-CH4 [2]. Two sorts of solid organic samples can be produced in laboratory experiments simulating Titan's atmospheric reactivity: grains in the volume and thin films on the reactor walls. We expect that grains are more representative of Titan's atmospheric aerosols, but films are used to provide optical indices for radiative models of Titan's atmosphere.The aim of the present study is to address if these two sorts of analogues are chemically equivalent or not, when produced in the same N2-CH4 plasma discharge. The chemical compositions of both these materials are measured by using elemental analysis, XPS analysis and Secondary Ion Mass Spectrometry. We find that films are homogeneous but significantly less rich in nitrogen and hydrogen than grains produced in the same experimental conditions. This surprising difference in their chemical compositions is explained by the efficient etching occurring on the films, which stay in the discharge during the whole plasma duration, whereas the grains are ejected after a few minutes [3]. The impact for our understanding of Titan's aerosols chemical composition is important. Our study shows that chemical growth and etching process are simultaneously at stake in Titan's ionosphere. The more the aerosols stay in the ionosphere, the more graphitized they get through etching process. In order to infer Titan's aerosols composition, our work highlights a need for constraints on the residence time of aerosols in Titan's ionosphere. [1] Waite et al. (2009) Science , 316, p. 870[2] Szopa et al. (2006) PSS, 54, p. 394[3] Carrasco et al. (2016) PSS, 128, p. 52

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.

Rubber-like Quasi-thermosetting Polyetheramine-cured Epoxy Asphalt Composites Capable of Being Opened to Traffic Immediately

NASA Astrophysics Data System (ADS)

Kang, Yang; Wu, Qiang; Jin, Rui; Yu, Pengfei; Cheng, Jixiang

2016-01-01

This paper reports the facile preparation, mechanical performance and linear viscoelasticity of polyetheramine-cured rubber-like epoxy asphalt composites (EACs) with different asphalt contents. Compared with previous EACs prepared via complex chemical reactions and time-consuming high-temperature curing, the EACs reported here were obtained by using a compatible, bi-functional polyetheramine and a simple physical co-blend process, which make the EACs feasibly scalable for production at a lower cost. The EACs were cured for 1 h at 160 °C and 3 d at 60 °C therefore, these composites can be opened to traffic immediately. The EACs have a much greater temperature stability than common thermoplastic polymer-modified asphalt composites from -30 °C to 120 °C, but their complex shear moduli at higher temperatures slightly decrease instead of remaining constant when temperatures are greater than 80 °C, especially for the higher asphalt content composites; that is, these composites are quasi-thermosetting. Wicket plots illustrate that the EACs reported here are thermorheological simple materials, and the master curves are constructed and well-fitted by generalized logistic sigmoidal model functions. This research provides a facile, low-cost method for the preparation of polyetheramine-cured EACs that can be opened to traffic immediately, and the concept of quasi-thermosetting may facilitate the development of cheaper EACs for advanced applications.

Rubber-like Quasi-thermosetting Polyetheramine-cured Epoxy Asphalt Composites Capable of Being Opened to Traffic Immediately.

PubMed

Kang, Yang; Wu, Qiang; Jin, Rui; Yu, Pengfei; Cheng, Jixiang

2016-01-06

This paper reports the facile preparation, mechanical performance and linear viscoelasticity of polyetheramine-cured rubber-like epoxy asphalt composites (EACs) with different asphalt contents. Compared with previous EACs prepared via complex chemical reactions and time-consuming high-temperature curing, the EACs reported here were obtained by using a compatible, bi-functional polyetheramine and a simple physical co-blend process, which make the EACs feasibly scalable for production at a lower cost. The EACs were cured for 1 h at 160 °C and 3 d at 60 °C; therefore, these composites can be opened to traffic immediately. The EACs have a much greater temperature stability than common thermoplastic polymer-modified asphalt composites from -30 °C to 120 °C, but their complex shear moduli at higher temperatures slightly decrease instead of remaining constant when temperatures are greater than 80 °C, especially for the higher asphalt content composites; that is, these composites are quasi-thermosetting. Wicket plots illustrate that the EACs reported here are thermorheological simple materials, and the master curves are constructed and well-fitted by generalized logistic sigmoidal model functions. This research provides a facile, low-cost method for the preparation of polyetheramine-cured EACs that can be opened to traffic immediately, and the concept of quasi-thermosetting may facilitate the development of cheaper EACs for advanced applications.

Rubber-like Quasi-thermosetting Polyetheramine-cured Epoxy Asphalt Composites Capable of Being Opened to Traffic Immediately

PubMed Central

Kang, Yang; Wu, Qiang; Jin, Rui; Yu, Pengfei; Cheng, Jixiang

2016-01-01

This paper reports the facile preparation, mechanical performance and linear viscoelasticity of polyetheramine-cured rubber-like epoxy asphalt composites (EACs) with different asphalt contents. Compared with previous EACs prepared via complex chemical reactions and time-consuming high-temperature curing, the EACs reported here were obtained by using a compatible, bi-functional polyetheramine and a simple physical co-blend process, which make the EACs feasibly scalable for production at a lower cost. The EACs were cured for 1 h at 160 °C and 3 d at 60 °C; therefore, these composites can be opened to traffic immediately. The EACs have a much greater temperature stability than common thermoplastic polymer-modified asphalt composites from −30 °C to 120 °C, but their complex shear moduli at higher temperatures slightly decrease instead of remaining constant when temperatures are greater than 80 °C, especially for the higher asphalt content composites; that is, these composites are quasi-thermosetting. Wicket plots illustrate that the EACs reported here are thermorheological simple materials, and the master curves are constructed and well-fitted by generalized logistic sigmoidal model functions. This research provides a facile, low-cost method for the preparation of polyetheramine-cured EACs that can be opened to traffic immediately, and the concept of quasi-thermosetting may facilitate the development of cheaper EACs for advanced applications. PMID:26733315

Chemical evolution of a pleistocene rhyolitic center: Sierra La Primavera, Jalisco, México

NASA Astrophysics Data System (ADS)

Mahood, Gail A.

1981-06-01

The late Pleistocene caldera complex of the Sierra La Primavera, Jalisco, México, contains well-exposed lava flows and domes, ash-flow tuff, air-fall pumice, and caldera-lake sediments. All eruptive units are high-silica rhyolites, but systematic chemical differences correlate with age and eruptive mode. The caldera-producing unit, the 45-km3 Tala Tuff, is zoned from a mildly peralkaline first-erupted portion enriched in Na, Rb, Cs, Cl, F, Zn, Y, Zr, Hf, Ta, Nb, Sb, HREE, Pb, Th, and U to a metaluminous last-erupted part enriched in K, LREE, Sc, and Ti; Al, Ca, Mg, Mn, Fe, and Eu are constant within analytical errors. The earliest post-caldera lava, the south-central dome, is nearly identical to the last-erupted portion of the Tala Tuff, whereas the slightly younger north-central dome is chemically transitional from the south-central dome to later, moremafic, ring domes. This sequence of ash-flow tuff and domes represents the tapping of progressively deeper levels of a zoned magma chamber 95,000 ± 5,000 years ago. Since that time, the lavas that erupted 75,000, 60,000, and 30,000 years ago have become decreasingly peralkaline and progressively enriched only in Si, Rb, Cs, and possibly U. They represent successive eruption of the uppermost magma in the post-95,000-year magma chamber. Eruptive units of La Primavera are either aphyric or contain up to 15% phenocrysts of sodic sanidine ≧quartz >ferrohedenbergite >fayalite>ilmenite±titanomagnetite. Whereas major-element compositions of sanidine, clinopyroxene, and fayalite phenocrysts changed only slightly between eruptive groups, concentrations of many trace elements changed by factors of 5 to 10, resulting in crystal/glass partition coefficients that differ by factors of up to 20 between successively erupted units. The extreme variations in partitioning behavior are attributed to small changes in bulk composition of the melt because major-element compositions of the phenocrysts and temperature, pressure, and oxygen fugacity of the magma all remained essentially constant. Crystal settling and incremental partial melting by themselves appear incapable of producing either the chemical gradients within the Tala Tuff magma chamber or the trends with time in the post-caldera lavas. Transport of trace metals as volatile complexes within the thermal and gravitational gradient in volatilerich but water-undersaturated magma is considered the dominant process responsible for compositional zonation in the Tala Tuff. The evolution of the post-caldera lavas with time is thought to involve the diffusive emigration of trace elements from a relatively dry magma as a decreasing proportion of network modifiers and/or a decreasing concentration of complexing ligands progressively reduced trace-metal-site availability in the silicate melt.

Garnet: featured mineral group at the 1993 Tucson Show

USGS Publications Warehouse

Modreski, P.J.

1993-01-01

The garnets are a common but complex group of minerals. They are perhaps the mineral kingdom's best example of solid solution: a relationship in which minerals have chemical compositions that are intermediate between two or more ideal end-member species. In garnet, we deal with a complex group of solid-solution series between as many as 14 end-member minerals. The varying intergradations of solid solution between these different end-members help to explain the garnet group's variety of color, environment of occurrence, gem use, and variation in such physical properties as specific gravity, refractive index, and hardness. -from Author

Transformation of juvenile Izu-Bonin-Mariana oceanic arc into mature continental crust: An example from the Neogene Izu collision zone granitoid plutons, Central Japan

NASA Astrophysics Data System (ADS)

Saito, Satoshi; Tani, Kenichiro

2017-04-01

Granitic rocks (sensulato) are major constituents of upper continental crust. Recent reviews reveal that the average composition of Phanerozoic upper continental crust is granodioritic. Although oceanic arcs are regarded as a site producing continental crust material in an oceanic setting, intermediate to felsic igneous rocks occurring in modern oceanic arcs are dominantly tonalitic to trondhjemitic in composition and have lower incompatible element contents than the average upper continental crust. Therefore, juvenile oceanic arcs require additional processes in order to get transformed into mature continental crust enriched in incompatible elements. Neogene granitoid plutons are widely exposed in the Izu Collision Zone in central Japan, where the northern end of the Izu-Bonin-Mariana (IBM) arc (juvenile oceanic arc) has been colliding with the Honshu arc (mature island arc) since Middle Miocene. The plutons in this area are composed of various types of granitoids ranging from tonalite to trondhjemite, granodiorite, monzogranite and granite. Three main granitoid plutons are distributed in this area: Tanzawa plutonic complex, Kofu granitic complex, and Kaikomagatake granitoid pluton. Tanzawa plutonic complex is dominantly composed of tonalite and trondhjemite and characterized by low concentration of incompatible elements and shows geochemical similarity with modern juvenile oceanic arcs. In contrast, Kofu granitic complex and Kaikomagatake granitoid pluton consists mainly of granodiorite, monzogranite and granite and their incompatible element abundances are comparable to the average upper continental crust. Previous petrogenetic studies on these plutons suggested that (1) the Tanzawa plutonic complex formed by lower crustal anatexis of juvenile basaltic rocks occurring in the IBM arc, (2) the Kofu granitic complex formed by anatexis of 'hybrid lower crust' comprising of both basaltic rocks of the IBM arc and metasedimentary rocks of the Honshu arc, and (3) the Kaikomagatake granitoid pluton formed by anatexis of 'hybrid lower crust' consisting of K-rich rear-arc crust of the IBM arc and metasedimentary rocks of the Honshu arc. These studies collectively suggest that the chemical diversity within the Izu Collision Zone granitoid plutons reflects the chemical variation of basaltic sources (i.e., across-arc chemical variation in the IBM arc) as well as variable contribution of the metasedimentary component in the source region. The petrogenetic models of the Izu Collision Zone granitoid plutons suggest that collision with another mature arc/continent, hybrid lower crust formation and subsequent hybrid source anatexis are required for juvenile oceanic arcs to produce granitoid magmas with enriched compositions. The Izu Collision Zone granitoid plutons provide an exceptional example of the collision-induced transformation from a juvenile oceanic arc to the mature continental crust.

Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol

PubMed Central

Prather, Kimberly A.; Bertram, Timothy H.; Grassian, Vicki H.; Deane, Grant B.; Stokes, M. Dale; DeMott, Paul J.; Aluwihare, Lihini I.; Palenik, Brian P.; Azam, Farooq; Seinfeld, John H.; Moffet, Ryan C.; Molina, Mario J.; Cappa, Christopher D.; Geiger, Franz M.; Roberts, Gregory C.; Russell, Lynn M.; Ault, Andrew P.; Baltrusaitis, Jonas; Collins, Douglas B.; Corrigan, Craig E.; Cuadra-Rodriguez, Luis A.; Ebben, Carlena J.; Forestieri, Sara D.; Guasco, Timothy L.; Hersey, Scott P.; Kim, Michelle J.; Lambert, William F.; Modini, Robin L.; Mui, Wilton; Pedler, Byron E.; Ruppel, Matthew J.; Ryder, Olivia S.; Schoepp, Nathan G.; Sullivan, Ryan C.; Zhao, Defeng

2013-01-01

The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60–180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties. PMID:23620519

Paramagnetic Europium Salen Complex and Sickle-Cell Anemia

NASA Astrophysics Data System (ADS)

Wynter, Clive I.; Ryan, D. H.; May, Leopold; Oliver, F. W.; Brown, Eugene; Hoffman, Eugene J.; Bernstein, David

2005-04-01

A new europium salen complex, Eu(salen)2NH4, was synthesized, and its composition was confirmed by chemical analysis and infrared spectroscopy. Further characterization was carried out by 151 Eu Mössbauer spectroscopy and magnetic susceptibility measurements. Mössbauer spectroscopic measurements were made at varying temperatures between 9 K and room temperature and a value of Debye temperature of 133 ±5 K was computed. Both Mössbauer and magnetic susceptibility measurements confirmed the paramagnetic behavior of this complex and the trivalent state of the europium ion. In view of the fact that the "odd" paramagnetic molecule NO has been shown to reverse sickling of red blood cells in sickle cell anemia, the interaction between the paramagnetic europium salen complex and sickle cells was examined after incubation with this europium complex and shown to have similar effects.

Chemical and stable-radiogenic isotope compositions of Polatlı-Haymana thermal waters (Ankara, Turkey)

NASA Astrophysics Data System (ADS)

Akilli, Hafize; Mutlu, Halim

2016-04-01

Complex tectono-magmatic evolution of the Anatolian land resulted in development of numerous geothermal areas through Turkey. The Ankara region in central Anatolia is surrounded by several basins which are filled with upper Cretaceous-Tertiary sediments. Overlying Miocene volcanics and step faulting along the margins of these basins played a significant role in formation of a number of low-enthalpy thermal waters. In this study, chemical and isotopic compositions of Polatlı and Haymana geothermal waters in the Ankara region are investigated. The Polatlı-Haymana waters with a temperature range of 24 to 43 °C are represented by Ca-(Na)-HCO3 composition implying derivation from carbonate type reservoir rocks. Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and point to a meteoric origin. The carbon isotopic composition in dissolved inorganic carbon (DIC) of the studied waters is between -21.8 and -1.34 permil (vs. VPDB). Marine carbonates and organic rocks are the main sources of carbon. There is a high correlation between oxygen (3.7 to 15.0 permil; VSMOW) and sulfur (-9.2 to 19.5 permil; VCDT) isotope compositions of sulfate in waters. The mixing of sulfate from dissolution of marine carbonates and terrestrial evaporite units is the chief process behind the observed sulfate isotope systematics of the samples. 87Sr/86Sr ratios of waters varying from 0.705883 to 0.707827 are consistent with those of reservoir rocks. The temperatures calculated by SO4-H2O isotope geothermometry are between 81 and 138 °C nearly doubling the estimates from chemical geothermometers.

In situ study at high pressure and temperature of the environment of water in hydrous Na and Ca aluminosilicate melts and coexisting aqueous fluids

NASA Astrophysics Data System (ADS)

Le Losq, Charles; Dalou, Célia; Mysen, Bjorn O.

2017-07-01

The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature Tg, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near Tg. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different.

Nonlinear mechanics of hybrid polymer networks that mimic the complex mechanical environment of cells

NASA Astrophysics Data System (ADS)

Jaspers, Maarten; Vaessen, Sarah L.; van Schayik, Pim; Voerman, Dion; Rowan, Alan E.; Kouwer, Paul H. J.

2017-05-01

The mechanical properties of cells and the extracellular environment they reside in are governed by a complex interplay of biopolymers. These biopolymers, which possess a wide range of stiffnesses, self-assemble into fibrous composite networks such as the cytoskeleton and extracellular matrix. They interact with each other both physically and chemically to create a highly responsive and adaptive mechanical environment that stiffens when stressed or strained. Here we show that hybrid networks of a synthetic mimic of biological networks and either stiff, flexible and semi-flexible components, even very low concentrations of these added components, strongly affect the network stiffness and/or its strain-responsive character. The stiffness (persistence length) of the second network, its concentration and the interaction between the components are all parameters that can be used to tune the mechanics of the hybrids. The equivalence of these hybrids with biological composites is striking.

Cambrian nepheline syenite complex at Jabal Sawda, Midyan region, Kingdom of Saudi Arabia

USGS Publications Warehouse

Liddicoat, W.K.; Ramsay, C.R.; Hedge, C.E.

1986-01-01

The only nepheline syenite complex presently known in the Arabian Shield is at Jabal Sawda, about 30 km S of Haql in the extreme NW of Saudi Arabia. It is a post-tectonic, composite intrusion with a crudely concentric structure. A core of leuco-nepheline syenite, a partial ring of mela-nepheline syenite, and an almost complete outer ring of alkali-feldspar syenite are the main rock units. Several mega-inclusions of porphyritic nepheline syenite, nepheline monzosyenite, malignite and ijolite are present in the leuco-nepheline syenite. The chemical composition is notable for very high values of Al2O3, Na2O, Ba, La, Nb, Sr and Zr. U{single bond}Pb isotope dating indicates an emplacement age of 553 ?? 4 Ma, one of an increasing number of reliable Cambrian isotope dates in the northern Red Sea region. ?? 1986.

Cambrian nepheline syenite complex at Jabal Sawda, Midyan region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Liddicoat, W. K.; Ramsay, C. R.; Hedge, C. E.

The only nepheline syenite complex presently known in the Arabian Shield is at Jabal Sawda, about 30 km S of Haql in the extreme NW of Saudi Arabia. It is a post-tectonic, composite intrusion with a crudely concentric structure. A core of leuco-nepheline syenite, a partial ring of mela-nepheline syenite, and an almost complete outer ring of alkali-feldspar syenite are the main rock units. Several mega-inclusions of porphyritic nepheline syenite, nepheline monzosyenite, malignite and ijolite are present in the leuco-nepheline syenite. The chemical composition is notable for very high values of Al 2O 3, Na 2O, Ba, La, Nb, Sr and Zr. U sbnd Pb isotope dating indicates an emplacement age of 553 ± 4 Ma, one of an increasing number of reliable Cambrian isotope dates in the northern Red Sea region.

Confocal raman microscopy as a non-invasive tool to investigate the phase composition of frozen complex cryopreservation media.

PubMed

Kreiner-Møller, A; Stracke, F; Zimmermann, H

2013-01-01

Various cryoprotective agents (CPA) are added to cell media in order to avoid cell injury during cryo preservation. The resulting complex environment of the preserved cell, consisting of crystalline and liquid phases can however not be investigated non-invasively by established methods in cryobiology. This study shows how scanning confocal Raman microscopy can non-invasively extract information on chemical composition, phase domain and distribution at cryogenic temperatures. The formation of the salt hydrate, hydrohalite NaCl∙H2O, in solutions comprised of phosphate buffered saline (PBS) and dimethyl sulphoxide (DMSO) is studied in particular. Scanning confocal Raman microscopy can be used to unambiguously identify hydrohalite in a medium containing DMSO and saline. The confocal Raman microscopy imaging along with differential scanning calorimetric measurements further show that the hydrohalite is formed without eutectic formation. This method also allows for discrimination between closely packed hydrohalite crystals that are oriented differently.

Effect of SnO2/SiO2 nano particle dispersant on the performance characteristic of complex multi-doped composite coating produced through electrodeposition on oil and gas storage tap

NASA Astrophysics Data System (ADS)

Anawe, P. A. L.; Fayomi, O. S. I.; Ayoola, A. A.; Popoola, A. P. I.

2018-06-01

The effect of SnO2/SiO2 nano particle dispersant on the performance characteristic of complex zinc multi-doped composite coating produced through electrodeposition is studied. The degradation behaviour in term of wear and chemical corrosion activities were considered as a major factor in service. The wear mass loss was carried out with the help of reciprocating tester. The electrochemical corrosion characteristics were investigated using linear polarization technique in 3.5% simulated sodium chloride media. The outcome of the analysis shows that the developed coating was seen to provide a sound anti wear characteristics in its multidoped state. The corrosion resistance properties were observed to be massive compared to the binary based sample. It is expected that this characteristic will impact on the performance life span of storage tap in oil and gas.

A new theoretical approach to analyze complex processes in cytoskeleton proteins.

PubMed

Li, Xin; Kolomeisky, Anatoly B

2014-03-20

Cytoskeleton proteins are filament structures that support a large number of important biological processes. These dynamic biopolymers exist in nonequilibrium conditions stimulated by hydrolysis chemical reactions in their monomers. Current theoretical methods provide a comprehensive picture of biochemical and biophysical processes in cytoskeleton proteins. However, the description is only qualitative under biologically relevant conditions because utilized theoretical mean-field models neglect correlations. We develop a new theoretical method to describe dynamic processes in cytoskeleton proteins that takes into account spatial correlations in the chemical composition of these biopolymers. Our approach is based on analysis of probabilities of different clusters of subunits. It allows us to obtain exact analytical expressions for a variety of dynamic properties of cytoskeleton filaments. By comparing theoretical predictions with Monte Carlo computer simulations, it is shown that our method provides a fully quantitative description of complex dynamic phenomena in cytoskeleton proteins under all conditions.

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

Method of producing hydrogen

DOEpatents

Bingham, Dennis N.; Klingler, Kerry M.; Wilding, Bruce M.; Zollinger, William T.

2006-12-26

A method of producing hydrogen is disclosed and which includes providing a first composition; providing a second composition; reacting the first and second compositions together to produce a chemical hydride; providing a liquid and reacting the chemical hydride with the liquid in a manner to produce a high pressure hydrogen gas and a byproduct which includes the first composition; and reusing the first composition formed as a byproduct in a subsequent chemical reaction to form additional chemical hydride.

From Aeolis Palus to the Bagnold Dunes field: Overview of martian soil analyses performed by ChemCam in Gale Crater

NASA Astrophysics Data System (ADS)

Cousin, A.; Meslin, P. Y.; Dehouck, E.; David, G.; Rapin, W.; Schröder, S.; Forni, O.; Gasnault, O.; Williams, A. J.; Lasue, J.; Stein, N.; Ehlmann, B. L.; Payre, V.; Anderson, R. B.; Blaney, D. L.; Bridges, N. T.; Clark, B. C.; Frydenvang, J.; Gasda, P. J.; Johnson, J. R.; Lanza, N.; l'Haridon, J.; Mangold, N.; Maurice, S.; Newsom, H. E.; Ollila, A.; Pinet, P. C.; Sautter, V.; Thomas, N. H.; Wiens, R. C.

2017-12-01

In situ analysis of the chemical and mineralogical composition of the martian soil, and the determination of its volatile inventory, can provide important constraints on the bulk composition of the martian crust, on its igneous diversity, but also on the physical and chemical weathering processes that have altered its primary igneous constituents. Transport processes that have occurred over long geological time scales, however, make this analysis quite complex, as constituents from different unknown sources are mixed together, and may have been sorted according to grain size or density. A meteoritic contribution is also present. Disentangling the influence of each of these processes requires the use of different analytical techniques, at different spatial scales, and at different locations over the planet. We will present an overview of the soil analyses obtained over the past 5 years by the ChemCam instrument on board MSL/Curiosity. Their specificity lies in their small spatial scale ( 300 μm), close to the average grains' size. At this scale, chemical trends are observed, resulting from the mixing of different end-members with different grain sizes: coarse felsic grains of likely local origin, fine grains with a basaltic composition close to soil compositions observed at other landing sites, but distinct from local rocks, and a fine-grained, Si-poor, volatile-rich component probably associated with the XRD-amorphous component detected by the CheMin instrument. The thin ablation depth associated with each laser shot ( 1 μm) enables us to analyse the surface of the grains, which is characterized by a strong, but variable hydrogen signal. These analyses provide constraints on the composition of a possible alteration rind or coating present at their surface. An extensive, multi-instrument investigation of active dunes (barchan and linear dunes) has also been carried out, revealing slight chemical differences with surrounding soils, and a more homogeneous composition, although chemical variations as a function of grain size are observed, with coarser grains enriched in mafic minerals. These results illustrate the still ongoing influence of aeolian transport on the physical sorting of loose, unconsolidated sediments. These results also provide ground truth for orbital IR observations of aeolian bedforms.

Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

NASA Technical Reports Server (NTRS)

Getty, Stephanie A.; Cook, Jamie E.; Balvin, Manuel; Brinckerhoff, William B.; Li, Xiang; Grubisic, Andrej; Cornish, Timothy; Ferrance, Jerome; Southard, Adrian

2017-01-01

The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

Ankaramite: A New Type of High-Magnesium and High-Calcium Primitive Melt in the Magnitogorsk Island-Arc Zone (Southern Urals)

NASA Astrophysics Data System (ADS)

Pushkarev, E. V.; Ryazancev, A. V.; Gottman, I. A.; Degtyarev, K. E.; Kamenetsky, V. S.

2018-04-01

This work describes the geological position, mineral and chemical composition of high-Mg effusive ankaramites occurring as dykes and lava flows. They were found in the mélange zone of the western margin of the Magnitogorsk island arc zone in the Southern Urals. Data on the liquidus association of phenocrysts and on the composition of the matrix of effusives are given. According to the data obtained, the conclusion was drawn that the ankaramites studied can be attributed to the primary island arc melts, which were not subject to essential differentiation. This type of effusives has not been distinguished previously among island arc volcanogenic formations of the Urals. It is shown that ankaramites can be considered to be primary melts parental for dunite-clinopyroxenites-gabbro complexes of Ural-Alaskan type. The occurrence of ankaramites in the Paleozoic island arc formations of the Urals indicates the wehrlite composition of the mantle as the reason for the extremely wide development of wehrlites and clinopyroxenites in different mafic-ultramafic complexes of the Urals.

Preparation, Fabrication, and Evaluation of Advanced Polymeric and Composite Materials

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.

1997-01-01

The thesis titles are given below: physical and mechanical behavior of amorphous poly(arylene ether-co-imidasole)s and poly(arylene ether-co-imidasole) modification epoxies; the requirements of patentability as applied to the chemical arts; fabrication of thermoplastic polymer composite ribbon; blend of reactive diluents with phenylethynyl-terminated arylene ether oligomers; the synthesis, characterization, and application of ether-containing polyimides; the synthesis of reflective and electrically conductive polyimide films via an in-situ self-metalization procedure using silver (I) complexes; the thermal cure of phenylethynyl terminated polyimides and selected model compounds; and the synthesis, characterization, and molecular modeling of cyclic arylene ether oligomers.

Alginate/sodium caseinate aqueous-core capsules: a pH-responsive matrix.

PubMed

Ben Messaoud, Ghazi; Sánchez-González, Laura; Jacquot, Adrien; Probst, Laurent; Desobry, Stéphane

2015-02-15

Alginate capsules have several applications. Their functionality depends considerably on their permeability, chemical and mechanical stability. Consequently, the creation of composite system by addition of further components is expected to control mechanical and release properties of alginate capsules. Alginate and alginate-sodium caseinate composite liquid-core capsules were prepared by a simple extrusion. The influence of the preparation pH and sodium caseinate concentration on capsules physico-chemical properties was investigated. Results showed that sodium caseinate influenced significantly capsules properties. As regards to the membrane mechanical stability, composite capsules prepared at pH below the isoelectric point of sodium caseinate exhibited the highest surface Young's modulus, increasing with protein content, explained by potential electrostatic interactions between sodium caseinate amino-groups and alginate carboxylic group. The kinetic of cochineal red A release changed significantly for composite capsules and showed a pH-responsive release. Sodium caseinate-dye mixture studied by absorbance and fluorescence spectroscopy confirmed complex formation at pH 2 by electrostatic interactions between sodium caseinate tryptophan residues and cochineal red sulfonate-groups. Consequently, the release mechanism was explained by membrane adsorption process. This global approach is useful to control release mechanism from macro and micro-capsules by incorporating guest molecules which can interact with the entrapped molecule under specific conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

Computer program for calculation of complex chemical equilibrium compositions and applications. Supplement 1: Transport properties

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B.; Zeleznik, F. J.

1984-01-01

An addition to the computer program of NASA SP-273 is given that permits transport property calculations for the gaseous phase. Approximate mixture formulas are used to obtain viscosity and frozen thermal conductivity. Reaction thermal conductivity is obtained by the same method as in NASA TN D-7056. Transport properties for 154 gaseous species were selected for use with the program.

A simple chromatographic method for purification of egg lecithin.

PubMed

Nielsen, J R

1980-06-01

Egg lecithin was purified from the CdCl2-lecithin complex by column chromatography on Alumina. The yield from 5 eggs was 2.8 g. The purified lecithin had correct chemical values for pure lecithin and a fatty acid composition similar to lecithin prepared by other methods. The method probably can be adapted for purification of other lipids containing the phosphocholine moiety and for purification of synthetic lecithin.

Silicon Promotes Exodermal Casparian Band Formation in Si-Accumulating and Si-Excluding Species by Forming Phenol Complexes

PubMed Central

Hinrichs, Martin; Specht, André; Waßmann, Friedrich; Schreiber, Lukas; Schenk, Manfred K.

2015-01-01

We studied the effect of Silicon (Si) on Casparian band (CB) development, chemical composition of the exodermal CB and Si deposition across the root in the Si accumulators rice and maize and the Si non-accumulator onion. Plants were cultivated in nutrient solution with and without Si supply. The CB development was determined in stained root cross-sections. The outer part of the roots containing the exodermis was isolated after enzymatic treatment. The exodermal suberin was transesterified with MeOH/BF3 and the chemical composition was measured using gas chromatography-mass spectroscopy (GC-MS) and flame ionization detector (GC-FID). Laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS) was used to determine the Si deposition across root cross sections. Si promoted CB formation in the roots of Si-accumulator and Si non-accumulator species. The exodermal suberin was decreased in rice and maize due to decreased amounts of aromatic suberin fractions. Si did not affect the concentration of lignin and lignin-like polymers in the outer part of rice, maize and onion roots. The highest Si depositions were found in the tissues containing CB. These data along with literature were used to suggest a mechanism how Si promotes the CB development by forming complexes with phenols. PMID:26383862

COBRA: A Computational Brewing Application for Predicting the Molecular Composition of Organic Aerosols

PubMed Central

Fooshee, David R.; Nguyen, Tran B.; Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander; Baldi, Pierre

2012-01-01

Atmospheric organic aerosols (OA) represent a significant fraction of airborne particulate matter and can impact climate, visibility, and human health. These mixtures are difficult to characterize experimentally due to their complex and dynamic chemical composition. We introduce a novel Computational Brewing Application (COBRA) and apply it to modeling oligomerization chemistry stemming from condensation and addition reactions in OA formed by photooxidation of isoprene. COBRA uses two lists as input: a list of chemical structures comprising the molecular starting pool, and a list of rules defining potential reactions between molecules. Reactions are performed iteratively, with products of all previous iterations serving as reactants for the next. The simulation generated thousands of structures in the mass range of 120–500 Da, and correctly predicted ~70% of the individual OA constituents observed by high-resolution mass spectrometry. Select predicted structures were confirmed with tandem mass spectrometry. Esterification was shown to play the most significant role in oligomer formation, with hemiacetal formation less important, and aldol condensation insignificant. COBRA is not limited to atmospheric aerosol chemistry; it should be applicable to the prediction of reaction products in other complex mixtures for which reasonable reaction mechanisms and seed molecules can be supplied by experimental or theoretical methods. PMID:22568707

FTIR Analysis of Functional Groups in Aerosol Particles

NASA Astrophysics Data System (ADS)

Shokri, S. M.; McKenzie, G.; Dransfield, T. J.

2012-12-01

Secondary organic aerosols (SOA) are suspensions of particulate matter composed of compounds formed from chemical reactions of organic species in the atmosphere. Atmospheric particulate matter can have impacts on climate, the environment and human health. Standardized techniques to analyze the characteristics and composition of complex secondary organic aerosols are necessary to further investigate the formation of SOA and provide a better understanding of the reaction pathways of organic species in the atmosphere. While Aerosol Mass Spectrometry (AMS) can provide detailed information about the elemental composition of a sample, it reveals little about the chemical moieties which make up the particles. This work probes aerosol particles deposited on Teflon filters using FTIR, based on the protocols of Russell, et al. (Journal of Geophysical Research - Atmospheres, 114, 2009) and the spectral fitting algorithm of Takahama, et al (submitted, 2012). To validate the necessary calibration curves for the analysis of complex samples, primary aerosols of key compounds (e.g., citric acid, ammonium sulfate, sodium benzoate) were generated, and the accumulated masses of the aerosol samples were related to their IR absorption intensity. These validated calibration curves were then used to classify and quantify functional groups in SOA samples generated in chamber studies by MIT's Kroll group. The fitting algorithm currently quantifies the following functionalities: alcohols, alkanes, alkenes, amines, aromatics, carbonyls and carboxylic acids.

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

Düchs, Dominik; Delaney, Kris T., E-mail: kdelaney@mrl.ucsb.edu; Fredrickson, Glenn H., E-mail: ghf@mrl.ucsb.edu

Field-theoretic models have been used extensively to study the phase behavior of inhomogeneous polymer melts and solutions, both in self-consistent mean-field calculations and in numerical simulations of the full theory capturing composition fluctuations. The models commonly used can be grouped into two categories, namely, species models and exchange models. Species models involve integrations of functionals that explicitly depend on fields originating both from species density operators and their conjugate chemical potential fields. In contrast, exchange models retain only linear combinations of the chemical potential fields. In the two-component case, development of exchange models has been instrumental in enabling stable complexmore » Langevin (CL) simulations of the full complex-valued theory. No comparable stable CL approach has yet been established for field theories of the species type. Here, we introduce an extension of the exchange model to an arbitrary number of components, namely, the multi-species exchange (MSE) model, which greatly expands the classes of soft material systems that can be accessed by the complex Langevin simulation technique. We demonstrate the stability and accuracy of the MSE-CL sampling approach using numerical simulations of triblock and tetrablock terpolymer melts, and tetrablock quaterpolymer melts. This method should enable studies of a wide range of fluctuation phenomena in multiblock/multi-species polymer blends and composites.« less

The Umov effect in application to an optically thin two-component cloud of cosmic dust

NASA Astrophysics Data System (ADS)

Zubko, Evgenij; Videen, Gorden; Zubko, Nataliya; Shkuratov, Yuriy

2018-04-01

The Umov effect is an inverse correlation between linear polarization of the sunlight scattered by an object and its geometric albedo. The Umov effect has been observed in particulate surfaces, such as planetary regoliths, and recently it also was found in single-scattering small dust particles. Using numerical modeling, we study the Umov effect in a two-component mixture of small irregularly shaped particles. Such a complex chemical composition is suggested in cometary comae and other types of optically thin clouds of cosmic dust. We find that the two-component mixtures of small particles also reveal the Umov effect regardless of the chemical composition of their end-member components. The interrelation between log(Pmax) and log(A) in a two-component mixture of small irregularly shaped particles appears either in a straight linear form or in a slightly curved form. This curvature tends to decrease while the index n in a power-law size distribution r-n grows; at n > 2.5, the log(Pmax)-log(A) diagrams are almost straight linear in appearance. The curvature also noticeably decreases with the packing density of constituent material in irregularly shaped particles forming the mixture. That such a relation exists suggest the Umov effect may also be observed in more complex mixtures.

The Umov effect in application to an optically thin two-component cloud of cosmic dust

NASA Astrophysics Data System (ADS)

Zubko, Evgenij; Videen, Gorden; Zubko, Nataliya; Shkuratov, Yuriy

2018-07-01

The Umov effect is an inverse correlation between linear polarization of the sunlight scattered by an object and its geometric albedo. The Umov effect has been observed in particulate surfaces, such as planetary regoliths, and recently it also was found in single-scattering small dust particles. Using numerical modelling, we study the Umov effect in a two-component mixture of small irregularly shaped particles. Such a complex chemical composition is suggested in cometary comae and other types of optically thin clouds of cosmic dust. We find that the two-component mixtures of small particles also reveal the Umov effect regardless of the chemical composition of their end-member components. The interrelation between log(Pmax) and log(A) in a two-component mixture of small irregularly shaped particles appears either in a straight linear form or in a slightly curved form. This curvature tends to decrease while the index n in a power-law size distribution r-n grows; at n > 2.5, the log(Pmax)-log(A) diagrams are almost straight linear in appearance. The curvature also noticeably decreases with the packing density of constituent material in irregularly shaped particles forming the mixture. That such a relation exists suggests the Umov effect may also be observed in more complex mixtures.

A perspective on the complexity of dietary fiber structures and their potential effect on the gut microbiota.

PubMed

Hamaker, Bruce R; Tuncil, Yunus E

2014-11-25

Even though there are many factors that determine the human colon microbiota composition, diet is an important one because most microorganisms in the colon obtain energy for their growth by degrading complex dietary compounds, particularly dietary fibers. While fiber carbohydrates that escape digestion in the upper gastrointestinal tract are recognized to have a range of structures, the vastness in number of chemical structures from the perspective of the bacteria is not well appreciated. In this article, we introduce the concept of "discrete structure" that is defined as a unique chemical structure, often within a fiber molecule, which aligns with encoded gene clusters in bacterial genomes. The multitude of discrete structures originates from the array of different fiber types coupled with structural variations within types due to genotype and growing environment, anatomical parts of the grain or plant, discrete regions within polymers, and size of oligosaccharides and small polysaccharides. These thousands of discrete structures conceivably could be used to favor bacteria in the competitive colon environment. A global framework needs to be developed to better understand how dietary fibers can be used to obtain predicted changes in microbiota composition for improved health. This will require a multi-disciplinary effort that includes biological scientists, clinicians, and carbohydrate specialists. Copyright © 2014 Elsevier Ltd. All rights reserved.

A comparison of chemical compositions of reported altered oceanic crusts and global MORB data set: implication for isotopic heterogeneity of recycled materials

NASA Astrophysics Data System (ADS)

Shimoda, G.; Kogiso, T.

2017-12-01

Chemical composition of altered oceanic crust is one of important constraints to delineate chemical heterogeneity of the mantle. Accordingly, many researchers have been studied to determine bulk chemical composition of altered oceanic crust mainly based on chemical compositions of old oceanic crusts at Site 801 and Site 417/418, and young crust at Site 504 (e.g., Staudigel et al., 1996; Bach et al. 2003; Kuo et al., 2016). Their careful estimation provided reliable bulk chemical compositions of these Sites and revealed common geochemical feature of alteration. To assess effect of recycling of altered oceanic crust on chemical evolution of the mantle, it might be meaningful to discuss whether the reported chemical compositions of altered oceanic crusts can represent chemical composition of globally subducted oceanic crusts. Reported chemical compositions of fresh glass or less altered samples from Site 801, 417/418 and 504 were highly depleted compared to that of global MORB reported by Gale et al. (2013), suggesting that there might be sampling bias. Hence, it could be important to consider chemical difference between oceanic crusts of these three Sites and global MORB to discuss effect of recycling of oceanic crust on isotopic heterogeneity of the mantle. It has been suggested that one of controlling factors of chemical variation of oceanic crust is crustal spreading rate because different degree of partial melting affects chemical composition of magmas produced at a mid-ocean ridge. Crustal spreading rate could also affect intensity of alteration. Namely, oceanic crusts produced at slow-spreading ridges may prone to be altered due to existence of larger displacement faults compared to fast spreading ridges which have relatively smooth topography. Thus, it might be significant to evaluate isotopic evolution of oceanic crusts those were produced at different spreading rates. In this presentation, we will provide a possible chemical variation of altered oceanic crusts based on reported bulk chemical compositions of altered oceanic crusts and global data sets of MORB. On the basis of the chemical variation, we will discuss isotopic evolution of altered oceanic crusts to delineate isotopic variation of recycled oceanic crusts.

Chemometrics Methods for Specificity, Authenticity and Traceability Analysis of Olive Oils: Principles, Classifications and Applications

PubMed Central

Messai, Habib; Farman, Muhammad; Sarraj-Laabidi, Abir; Hammami-Semmar, Asma; Semmar, Nabil

2016-01-01

Background. Olive oils (OOs) show high chemical variability due to several factors of genetic, environmental and anthropic types. Genetic and environmental factors are responsible for natural compositions and polymorphic diversification resulting in different varietal patterns and phenotypes. Anthropic factors, however, are at the origin of different blends’ preparation leading to normative, labelled or adulterated commercial products. Control of complex OO samples requires their (i) characterization by specific markers; (ii) authentication by fingerprint patterns; and (iii) monitoring by traceability analysis. Methods. These quality control and management aims require the use of several multivariate statistical tools: specificity highlighting requires ordination methods; authentication checking calls for classification and pattern recognition methods; traceability analysis implies the use of network-based approaches able to separate or extract mixed information and memorized signals from complex matrices. Results. This chapter presents a review of different chemometrics methods applied for the control of OO variability from metabolic and physical-chemical measured characteristics. The different chemometrics methods are illustrated by different study cases on monovarietal and blended OO originated from different countries. Conclusion. Chemometrics tools offer multiple ways for quantitative evaluations and qualitative control of complex chemical variability of OO in relation to several intrinsic and extrinsic factors. PMID:28231172

Vibrational spectroscopy for imaging single microbial cells in complex biological samples

DOE PAGES

Harrison, Jesse P.; Berry, David

2017-04-13

Here, vibrational spectroscopy is increasingly used for the rapid and non-destructive imaging of environmental and medical samples. Both Raman and Fourier-transform infrared (FT-IR) imaging have been applied to obtain detailed information on the chemical composition of biological materials, ranging from single microbial cells to tissues. Due to its compatibility with methods such as stable isotope labeling for the monitoring of cellular activities, vibrational spectroscopy also holds considerable power as a tool in microbial ecology. Chemical imaging of undisturbed biological systems (such as live cells in their native habitats) presents unique challenges due to the physical and chemical complexity of themore » samples, potential for spectral interference, and frequent need for real-time measurements. This Mini Review provides a critical synthesis of recent applications of Raman and FT-IR spectroscopy for characterizing complex biological samples, with a focus on developments in single-cell imaging. We also discuss how new spectroscopic methods could be used to overcome current limitations of singlecell analyses. Given the inherent complementarity of Raman and FT-IR spectroscopic methods, we discuss how combining these approaches could enable us to obtain new insights into biological activities either in situ or under conditions that simulate selected properties of the natural environment.« less

Vibrational spectroscopy for imaging single microbial cells in complex biological samples

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

Harrison, Jesse P.; Berry, David

Here, vibrational spectroscopy is increasingly used for the rapid and non-destructive imaging of environmental and medical samples. Both Raman and Fourier-transform infrared (FT-IR) imaging have been applied to obtain detailed information on the chemical composition of biological materials, ranging from single microbial cells to tissues. Due to its compatibility with methods such as stable isotope labeling for the monitoring of cellular activities, vibrational spectroscopy also holds considerable power as a tool in microbial ecology. Chemical imaging of undisturbed biological systems (such as live cells in their native habitats) presents unique challenges due to the physical and chemical complexity of themore » samples, potential for spectral interference, and frequent need for real-time measurements. This Mini Review provides a critical synthesis of recent applications of Raman and FT-IR spectroscopy for characterizing complex biological samples, with a focus on developments in single-cell imaging. We also discuss how new spectroscopic methods could be used to overcome current limitations of singlecell analyses. Given the inherent complementarity of Raman and FT-IR spectroscopic methods, we discuss how combining these approaches could enable us to obtain new insights into biological activities either in situ or under conditions that simulate selected properties of the natural environment.« less

Stability Testing of Herbal Drugs: Challenges, Regulatory Compliance and Perspectives.

PubMed

Bansal, Gulshan; Suthar, Nancy; Kaur, Jasmeen; Jain, Astha

2016-07-01

Stability testing is an important component of herbal drugs and products (HDPs) development process. Drugs regulatory agencies across the globe have recommended guidelines for the conduct of stability studies on HDPs, which require that stability data should be included in the product registration dossier. From the scientific viewpoint, numerous chemical constituents in an herbal drug are liable to varied chemical reactions under the influence of different conditions during its shelf life. These reactions can lead to altered chemical composition of HDP and consequently altered therapeutic profile. Many reports on stability testing of HDPs have appeared in literature since the last 10 years. A review of these reports reveals that there is wide variability in temperature (-80 to 100 °C), humidity (0-100%) and duration (a few hours-36 months) for stability assessment of HDPs. Of these, only 1% studies are conducted in compliance with the regulatory guidelines for stability testing. The present review is aimed at compiling all stability testing reports, understanding key challenges in stability testing of HDPs and suggesting possible solutions for these. The key challenges are classified as chemical complexity and biochemical composition variability in raw material, selection of marker(s) and influences of enzymes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

On the traceability of gaseous reference materials

NASA Astrophysics Data System (ADS)

Brown, Richard J. C.; Brewer, Paul J.; Harris, Peter M.; Davidson, Stuart; van der Veen, Adriaan M. H.; Ent, Hugo

2017-06-01

The complex and multi-parameter nature of chemical composition measurement means that establishing traceability is a challenging task. As a result incorrect interpretations about the origin of the metrological traceability of chemical measurement results can occur. This discussion paper examines why this is the case by scrutinising the peculiarities of the gas metrology area. It considers in particular: primary methods, dissemination of metrological traceability and the role of documentary standards and accreditation bodies in promulgating best practice. There is also a discussion of documentary standards relevant to the NMI and reference material producer community which need clarification, and the impact which key stakeholders in the quality infrastructure can bring to these issues.

Comets - Chemistry and chemical evolution

NASA Technical Reports Server (NTRS)

Donn, B.

1982-01-01

Research on the chemical composition and conditions in comets and their possible role in the origin of life on earth is surveyed. The inorganic and organic compounds and ions indicated in the ultraviolet and visible spectra of comets are noted, and evidence for the existence of at least a small proportion of complex organic molecules in comets is presented. It is then pointed out that while cometary material could have reached the earth and provided volatile elements from which biochemical compounds could have formed, it is unlikely that a cometary nucleus could have withstood the temperatures and pressures necessary to sustain an environment in which life could have originated.

Multinuclear metal-binding ability of a carotene

PubMed Central

Horiuchi, Shinnosuke; Tachibana, Yuki; Yamashita, Mitsuki; Yamamoto, Koji; Masai, Kohei; Takase, Kohei; Matsutani, Teruo; Kawamata, Shiori; Kurashige, Yuki; Yanai, Takeshi; Murahashi, Tetsuro

2015-01-01

Carotenes are naturally abundant unsaturated hydrocarbon pigments, and their fascinating physical and chemical properties have been studied intensively not only for better understanding of the roles in biological processes but also for the use in artificial chemical systems. However, their metal-binding ability has been virtually unexplored. Here we report that β-carotene has the ability to assemble and align ten metal atoms to afford decanuclear homo- and heterometal chain complexes. The metallo–carotenoid framework shows reversible metalation–demetalation reactivity with multiple metals, which allows us to control the size of metal chains as well as the heterobimetallic composition and arrangement of the carotene-supported metal chains. PMID:25857402

Effect of chemical composition on the electrical conductivity of gneiss at high temperatures and pressures

NASA Astrophysics Data System (ADS)

Dai, Lidong; Sun, Wenqing; Li, Heping; Hu, Haiying; Wu, Lei; Jiang, Jianjun

2018-03-01

The electrical conductivity of gneiss samples with different chemical compositions (WA = Na2O + K2O + CaO = 7.12, 7.27 and 7.64 % weight percent) was measured using a complex impedance spectroscopic technique at 623-1073 K and 1.5 GPa and a frequency range of 10-1 to 106 Hz. Simultaneously, a pressure effect on the electrical conductivity was also determined for the WA = 7.12 % gneiss. The results indicated that the gneiss conductivities markedly increase with total alkali and calcium ion content. The sample conductivity and temperature conform to an Arrhenius relationship within a certain temperature range. The influence of pressure on gneiss conductivity is weaker than temperature, although conductivity still increases with pressure. According to various ranges of activation enthalpy (0.35-0.52 and 0.76-0.87 eV) at 1.5 GPa, two main conduction mechanisms are suggested that dominate the electrical conductivity of gneiss: impurity conduction in the lower-temperature region and ionic conduction (charge carriers are K+, Na+ and Ca2+) in the higher-temperature region. The electrical conductivity of gneiss with various chemical compositions cannot be used to interpret the high conductivity anomalies in the Dabie-Sulu ultrahigh-pressure metamorphic belt. However, the conductivity-depth profiles for gneiss may provide an important constraint on the interpretation of field magnetotelluric conductivity results in the regional metamorphic belt.

Dissolution of cerium(IV)-lanthanide(III) oxides: Comparative effect of chemical composition, temperature, and acidity

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

Horlait, D.; Clavier, N.; Szenknect, S.

2012-03-15

The dissolution of Ce{sub 1-x}Ln{sub x}O{sub 2-x/2} solid solutions was undertaken in various acid media in order to evaluate the effects of several physicochemical parameters such as chemical composition, temperature, and acidity on the reaction kinetics. The normalized dissolution rates (R{sub L,0}) were found to be strongly modified by the trivalent lanthanide incorporation rate, due to the presence of oxygen vacancies decreasing the samples cohesion. Conversely, the nature of the trivalent cation considered only weakly impacted the R{sub L,0} values. The dependence of the normalized dissolution rates on the temperature then appeared to be of the same order of magnitudemore » than that of chemical composition. Moreover, it allowed determining the corresponding activation energy (E{sub A} ≅ 60-85 kJ.mol{sup -1}) which accounts for a dissolution driven by surface-controlled reactions. A similar conclusion was made regarding the acidity of the solution: the partial order related to (H{sub 3}O{sup +}) reaching about 0.7. Finally, the prevailing effect of the incorporation of aliovalent cations in the fluorite-type CeO{sub 2} matrix on the dissolution kinetics precluded the observation of slight effects such as those linked to the complexing agents or to the crystal structure of the samples. (authors)« less

Modelling chemical degradation of concrete during leaching with rain and soil water types

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

Jacques, D., E-mail: djacques@sckcen.b; Wang, L.; Martens, E.

2010-08-15

Percolation of external water through concrete results in the degradation of cement and changes the concrete pore water and solid phase composition. The assessment of long-term degradation of concrete is possible by means of model simulation. This paper describes simulations of chemical degradation of cement for different types of rain and soil water at an ambient earth surface temperature (10 {sup o}C). Rain and soil water types were derived using generic equations and measurement of atmospheric boundary conditions representative for North-Belgium. An up-to-date and consistent thermodynamic model is used to calculate the geochemical changes during chemical degradation of the concrete.more » A general pattern of four degradation stages was simulated with the third stage being the geochemically most complex stage involving reactions with calcium-silicate hydrates, AFm and AFt phases. Whereas the sequence of the dissolution reactions was relatively insensitive to the composition of the percolating water, the duration of the different reactions depends strongly on the percolating water composition. Major identified factors influencing the velocity of cement degradation are the effect of dry deposition and biological activity increasing the partial pressure of CO{sub 2(g)} in the soil air phase (and thus increasing the inorganic carbon content in the percolating water). Soil weathering processes have only a minor impact, at least for the relatively inert sandy material considered in this study.« less

Antioxidant activity evaluation and HPLC-photodiode array/MS polyphenols analysis of pomegranate juice from selected italian cultivars: A comparative study.

PubMed

Fanali, Chiara; Belluomo, Maria Giovanna; Cirilli, Marco; Cristofori, Valerio; Zecchini, Maurizio; Cacciola, Francesco; Russo, Marina; Muleo, Rosario; Dugo, Laura

2016-07-01

Chemical composition of pomegranate juice can vary due to cultivar, area of cultivation, ripening, climate, and other variables. This study investigates the polyphenolic composition and antioxidant activity of juices obtained from six old Italian pomegranate cultivars. Fruit accessions physicochemical characteristics were determined. Total polyphenols content (TPC), anthocyanin content (TAC) and proanthocyanidin content (TPAC) were measured in the juice samples. Phenolic bioactive molecules were analyzed by HPLC-photodiode array (PDA)/ESI-MS in all the pomegranate juices. In total, seven nonanthocyanidinic and six anthocyanidinic compounds were identified. The six anthocyanins were found in all juices although at different amounts. These results were correlated with antioxidant activity measured by three different chemical assays: 2,2 diphenyl-1-picrylhydrazyl (DPPH(•) ) scavenging activity assay, Trolox equivalent antioxidant capacity (TEAC) method and ferric reducing-antioxidant power (FRAP) assay. Pomegranate juices obtained by six different varieties show variable polyphenolic content and antioxidant activity. The antioxidant capacity methods used have shown variable sensitivity, supporting the hypothesis that different methods for the assessment of antioxidant capacity of food compounds are indeed necessary, due to complexity of sample composition and assay chemical mechanism and sensitivity. Juices from Italian pomegranate show good levels of polyphenols content and antioxidant activity making them potential candidates for employment in the food industry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Variability of chemical analysis of reinforcing bar produced in Saudi Arabia

NASA Astrophysics Data System (ADS)

Salman, A.; Djavanroodi, F.

2018-04-01

In view of the importance and demanding roles of steel rebar’s in the reinforced concrete structures, accurate information on the properties of the steels is important at the design stage. In the steelmaking process, production variations in chemical composition are unavoidable. The aim of this work is to study the variability of the chemical composition of reinforcing steel produced throughout the Saudi Arabia and asses the quality of steel rebar’s acoording to ASTM A615. 68 samples of ASTM A615 Grade 60 from different manufacturers were collected and tested using the Spectrometer test to obtain Chemical Compositions. EasyFit (5.6) software is utilized to conducted statistical analysis. Chemical compositions distributions and, control charts are generated for the compositions. Results showed that some compositions are above the upper line of the control chart. Finally, the analyses show that less than 3% of the steel failed to meet minimum ASTM standards for chemical composition.

Organic molecules, ions, and rare isotopologues in the remnant of the stellar-merger candidate, CK Vulpeculae (Nova 1670)

NASA Astrophysics Data System (ADS)

Kamiński, T.; Menten, K. M.; Tylenda, R.; Karakas, A.; Belloche, A.; Patel, N. A.

2017-11-01

Context. CK Vulpeculae (CK Vul) is an enigmatic star whose outburst was observed in 1670-72. A stellar-merger event was proposed to explain its ancient eruption. Aims: We aim to investigate the composition of the molecular gas recently discovered in the remnant of CK Vul. Deriving the chemical, elemental, and isotopic composition is crucial for identifying the nature of the object and obtaining clues on its progenitor(s). Methods: We observed millimeter and submillimeter-wave spectra of CK Vul using the IRAM 30 m and APEX telescopes. Radiative-transfer modeling of the observed molecular features was performed to yield isotopic ratios for various elements. Results: The spectra of CK Vul reveal a very rich molecular environment of low excitation (Tex ≲ 12 K). Atomic carbon and twenty-seven different molecules, including two ions, were identified. They range from simple diatomic to complex polyatomic species of up to seven atoms large. The chemical composition of the molecular gas is indicative of carbon and nitrogen-driven chemistry but oxides are also present. Additionally, the abundance of fluorine may be enhanced. The spectra are rich in isotopologues that are very rare in most known sources. All stable isotopes of C, N, O, Si, and S are observed and their isotopic ratios are derived. Conclusions: The composition of the remnant's molecular gas is most peculiar and gives rise to a very unique millimeter and submillimeter spectrum. The observation of ions and complex molecules suggests the presence of a photoionizing source but its nature (a central star or shocks) remains unknown. The elemental and isotopic composition of the gas cannot be easily reconciled with standard stellar nucleosynthesis but processing in hot CNO cycles and partial helium burning can explain most of the chemical peculiarities. The isotopic ratios of CK Vul are remarkably close to those of presolar "nova grains" but the link of Nova 1670 to objects responsible for these grains is unclear. The accuracy of isotopic ratios can be improved by future observations at higher angular resolutions and with realistic models of the kinematical structure of the remnant. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/607/A78

The nature of the MDI/wood bond

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

Marcinko, J.J.; Phanopoulos, C.; Newman, W.H.

1995-12-01

Polymeric diphenylmethane diisocyanate (pMDI) binders have been used in the wood composite industry for 20 years. Almost one half of the oriented strand board (OSB) manufactures in North America are taking advantage of its processing speed and superior board performance. MDI`s current use in Strandboard, MDF (medium density fiber board), LVL (laminated veneer lumber), Plywood, and Particleboard is wide spread. A fundamental understanding of the role of MIDI as a binder in these complex composites is essential for further processing optimization. Experimental data is presented which investigates the nature of the chemical bonding in wood composites. Solid state nuclear magneticmore » resonance (NMR) data is combined with data from thermal analysis and fluorescence microscopy to investigate the chemistry, penetration, and morphology of the isocyanate/wood interphase. Structure property relationships are developed and related to composite performance. The study contrasts isocyanate and phenol formaldehyde binder systems.« less

Time variability and heterogeneity in the coma of 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Hässig, M.; Altwegg, K.; Balsiger, H.; Bar-Nun, A.; Berthelier, J. J.; Bieler, A.; Bochsler, P.; Briois, C.; Calmonte, U.; Combi, M.; De Keyser, J.; Eberhardt, P.; Fiethe, B.; Fuselier, S. A.; Galand, M.; Gasc, S.; Gombosi, T. I.; Hansen, K. C.; Jäckel, A.; Keller, H. U.; Kopp, E.; Korth, A.; Kührt, E.; Le Roy, L.; Mall, U.; Marty, B.; Mousis, O.; Neefs, E.; Owen, T.; Rème, H.; Rubin, M.; Sémon, T.; Tornow, C.; Tzou, C.-Y.; Waite, J. H.; Wurz, P.

2015-01-01

Comets contain the best-preserved material from the beginning of our planetary system. Their nuclei and comae composition reveal clues about physical and chemical conditions during the early solar system when comets formed. ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) onboard the Rosetta spacecraft has measured the coma composition of comet 67P/Churyumov-Gerasimenko with well-sampled time resolution per rotation. Measurements were made over many comet rotation periods and a wide range of latitudes. These measurements show large fluctuations in composition in a heterogeneous coma that has diurnal and possibly seasonal variations in the major outgassing species: water, carbon monoxide, and carbon dioxide. These results indicate a complex coma-nucleus relationship where seasonal variations may be driven by temperature differences just below the comet surface.

The Navy/NASA Engine Program (NNEP89): Interfacing the program for the calculation of complex Chemical Equilibrium Compositions (CEC)

NASA Technical Reports Server (NTRS)

Gordon, Sanford

1991-01-01

The NNEP is a general computer program for calculating aircraft engine performance. NNEP has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, however, there has been increased interest in applications for which NNEP is not capable of simulating, such as the use of alternate fuels including cryogenic fuels and the inclusion of chemical dissociation effects at high temperatures. To overcome these limitations, NNEP was extended by including a general chemical equilibrium method. This permits consideration of any propellant system and the calculation of performance with dissociation effects. The new extended program is referred to as NNEP89.

The chemical composition and source identification of soil dissolved organic matter in riparian buffer zones from Chongming Island, China.

PubMed

Wang, Yulai; Yang, Changming; Li, Jianhua; Shen, Shuo

2014-09-01

Dissolved organic matter (DOM) that is derived from the soil of riparian buffer zones has a complex chemical composition, and it plays an important role in the transport and transformation of pollutants. To identify the source of DOM and to better understand its chemical and structural properties, we collected 33 soil samples from zones with fluctuating water levels along the major rivers on Chongming Island, evaluated the DOM contents in riparian soil, analyzed the chemical composition and functional groups and traced DOM origins by using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) combined with clustering analysis. All sampling sites were divided into four groups by principal component analysis (PCA) on the basis of the DOM molecules. The results showed that there was no significant difference in the DOM contents between every two groups; however, the DOM fractions differed significantly among the different site groups in the following order: Σ lipids and Σ proteins>Σ sugars and Σ fatty acids>Σ amino acids, Σ indoles and Σ alkaloids. DOM in the riparian buffer zones originated from riparian plants, domestic sewage and agricultural activities, and the hydrophobic and amphiphilic fractions accounting for over 60% of the identified molecules were the dominant fractions. Our study has confirmed the heterogeneous properties of DOM, and it is of vital importance to isolate and characterize the various DOM fractions at the molecular level for a better understanding of the behavior and roles of DOM in the natural environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Two-dimensional NMR spectroscopy as a tool to link soil organic matter composition to ecosystem processes

NASA Astrophysics Data System (ADS)

Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Schleucher, Jürgen

2014-05-01

Environmental factors (e.g. temperature and moisture) and the size and composition of soil microbial populations are often considered the main drivers of soil organic matter (SOM) mineralization. Less consideration is given to the role of SOM as a substrate for microbial metabolism and the importance of the organo-chemical composition of SOM on decomposition. In addition, a fraction of the SOM is often considered as recalcitrant to mineralization leading to accumulation of SOM. However, recently the concept of intrinsic recalcitrance of SOM to mineralization has been questioned. The challenge in investigating the role of SOM composition on its mineralization to a large extent stems from the difficulties in obtaining high resolution characterization of a very complex matrix. 13C nuclear magnetic resonance (NMR) spectroscopy is a widely used tool to characterize SOM. However, SOM is a very complex mixture and in the resulting 13C NMR spectra, the identified functional groups may represent different molecular fragments that appear in the same spectral region leading to broad peaks. These overlaps defy attempts to identify molecular moieties, and this makes it impossible to derive information at a resolution needed for evaluating e.g. recalcitrance of SOM. Here we applied a method, developed in wood science for the pulp paper industry, to achieve a better characterization of SOM. We directly dissolved finely ground organic layers of boreal forest floors-litters, fibric and humic horizons of both coniferous and broadleaved stands-in dimethyl sulfoxide and analyzed the resulting solution with a two-dimensional (2D) 1H-13C NMR experiment. We will discuss methodological aspects related to the ability to identify and quantify individual molecular moieties in SOM. We will demonstrate how the spectra resolve signals of CH groups in a 2D plane determined by the 13C and 1H chemical shifts, thereby vastly increasing the resolving power and information content of NMR spectra. The obtained 2D spectra resolve overlaps observed in 1D 13C spectra, so that hundreds of distinct CH moieties can be observed and many individual molecular fragments can be identified. For instance, in the aromatic spectral region, signals originating from various lignin monomers and unsaturated compounds can be resolved. This yields a detailed chemical fingerprint of the SOM samples, and valuable insights on molecular structures. We observed differences in the respective aromatic region of the 2D spectra of the litter layers and the fibric and humic horizons, in relation with humification processes. We were also able to relate the cross-peak complexity and abundance patterns of identifiable molecular moieties to variability in the temperature response of organic matter degradation, as assessed by Q10. To conclude, solution-state 2D NMR spectroscopy is a highly promising new tool to characterize SOM composition at the molecular level, which opens completely new possibilities to link SOM molecular composition to ecosystem processes, and their responses to environmental changes.

Large area sub-micron chemical imaging of magnesium in sea urchin teeth.

PubMed

Masic, Admir; Weaver, James C

2015-03-01

The heterogeneous and site-specific incorporation of inorganic ions can profoundly influence the local mechanical properties of damage tolerant biological composites. Using the sea urchin tooth as a research model, we describe a multi-technique approach to spatially map the distribution of magnesium in this complex multiphase system. Through the combined use of 16-bit backscattered scanning electron microscopy, multi-channel energy dispersive spectroscopy elemental mapping, and diffraction-limited confocal Raman spectroscopy, we demonstrate a new set of high throughput, multi-spectral, high resolution methods for the large scale characterization of mineralized biological materials. In addition, instrument hardware and data collection protocols can be modified such that several of these measurements can be performed on irregularly shaped samples with complex surface geometries and without the need for extensive sample preparation. Using these approaches, in conjunction with whole animal micro-computed tomography studies, we have been able to spatially resolve micron and sub-micron structural features across macroscopic length scales on entire urchin tooth cross-sections and correlate these complex morphological features with local variability in elemental composition. Copyright © 2015 Elsevier Inc. All rights reserved.

Dense Nonaqueous Phase Liquids at Former Manufactured Gas Plants: Challenges to Modeling and Remediation

PubMed Central

Birak, P.S.; Miller, C.T.

2008-01-01

The remediation of dense non-aqueous phase liquids (DNAPLs) in porous media continues to be one of the most challenging problems facing environmental scientists and engineers. Of all the environmentally relevant DNAPLs, tars in the subsurface at former manufactured gas plants (FMGP’s) pose one of the biggest challenges due to their complex chemical composition and tendency to alter wettability. To further our understanding of these complex materials, we consulted historic documentation to evaluate the impact of gas manufacturing on the composition and physicochemical nature of the resulting tars. In the recent literature, most work to date has been focused in a relatively narrow portion of the expected range of tar materials, which has yielded a bias toward samples of relatively low viscosity and density. In this work, we consider the dissolution and movement of tars in the subsurface, models used to predict these phenomena, and approaches used for remediation. We also explore the open issues and detail important gaps in our fundamental understanding of these extraordinarily complex systems that must be resolved to reach a mature level of understanding. PMID:19176266

Photoluminescence spectra of thin films of ZnTPP–C{sub 60} and CuTPP–C{sub 60} molecular complexes

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

Elistratova, M. A., E-mail: marina.elistratova@mail.ioffe.ru; Zakharova, I. B.; Romanov, N. M.

2016-09-15

The results of studies of thin composite films of zinc and copper tetraphenylporphyrins with different fractions of fullerene C{sub 60} are reported. The photoluminescence spectra are recorded, and the composition and surface morphology are analyzed by means of scanning electron microscopy. The results show a difference in the structure of films with two types of metals (Zn, Cu) entering into the complex of the porphyrin macrocycle. An additional long-wavelength photoluminescence band at 1.4 eV is detected for the first time, which is evidence of the formation of ZnTPP–C{sub 60} molecular complexes from a gas-dynamic vapor flow upon condensation. In CuTPPmore » thin films, the processes of self-assembly into nanowires 20 nm in diameter and up to 50 µm in length and the formation of nanoheterojunctions upon the addition of fullerene C{sub 60} are observed. Quantum-chemical calculations in the context of density-functional theory are carried out to interpret the experimental data.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

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

Song, Wentao; Leung, Kevin; Shao, Qian

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

DOE PAGES

Song, Wentao; Leung, Kevin; Shao, Qian; ...

2016-09-15

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

A synthetic study and characterization of the Pt(II) complexes with bipyridines back-born system.

PubMed

Jo, Woongkyu; Son, Seokhwan; Jo, Hyeongjun; Kim, Byeongcheol; Kwak, Cheehun; Jung, Sangchul; Lee, Jihoon; Ahn, Hogeun; Chung, Minchul

2014-08-01

The reaction of platinum [Pt(5,5-dmbpy)]Cl2 (5,5-dmbpy = 5,5'-dimethyl-2,2'-bipyridine) with 4,4'-dimethyl-2,2'-bipyridine (4,4-dmbpy), [Pt(dbbpy)]Cl2 (dbbpy = 4,4'-dibutyl-2,2'-bipyridine), [Pt(dpbpy)]Cl2 (dpbpy = 4,4'-dipentyl-2,2'-bipyridine) with 5,5'-dimethyl-2,2'-bipyridine (5,5-dmbpy) affords the following complexes: [(4,4-dmbpy)Pt(5,5-dmbpy)][PF6]2 (1) and [(dbbpy)Pt(5,5-dmbpy)][PF6]2 (2), [(dpbpy)Pt(5,5-dmbpy)][PF6]2 (3), [(5,5-dmbpy)Pt(5,5-dmbpy)][PF6]2 (4). This study was synthesized new platinum complex compounds utilizing ligand of 5,5'-Dimethyl-2,2'-dipyridyl System. To study the chemical composition was used 1H(13C)-NMR, UV-vis, Spectro photometer and Measurements about optical physics and chemical properties were measured to use spectrofluorometer. UV-vis absorption area was measured 310 nm to 383 nm and luminous wavelength was measured 390 nm to 419 nm.

The compositional and evolutionary logic of metabolism

NASA Astrophysics Data System (ADS)

Braakman, Rogier; Smith, Eric

2013-02-01

Metabolism is built on a foundation of organic chemistry, and employs structures and interactions at many scales. Despite these sources of complexity, metabolism also displays striking and robust regularities in the forms of modularity and hierarchy, which may be described compactly in terms of relatively few principles of composition. These regularities render metabolic architecture comprehensible as a system, and also suggests the order in which layers of that system came into existence. In addition metabolism also serves as a foundational layer in other hierarchies, up to at least the levels of cellular integration including bioenergetics and molecular replication, and trophic ecology. The recapitulation of patterns first seen in metabolism, in these higher levels, motivates us to interpret metabolism as a source of causation or constraint on many forms of organization in the biosphere. Many of the forms of modularity and hierarchy exhibited by metabolism are readily interpreted as stages in the emergence of catalytic control by living systems over organic chemistry, sometimes recapitulating or incorporating geochemical mechanisms. We identify as modules, either subsets of chemicals and reactions, or subsets of functions, that are re-used in many contexts with a conserved internal structure. At the small molecule substrate level, module boundaries are often associated with the most complex reaction mechanisms, catalyzed by highly conserved enzymes. Cofactors form a biosynthetically and functionally distinctive control layer over the small-molecule substrate. The most complex members among the cofactors are often associated with the reactions at module boundaries in the substrate networks, while simpler cofactors participate in widely generalized reactions. The highly tuned chemical structures of cofactors (sometimes exploiting distinctive properties of the elements of the periodic table) thereby act as ‘keys’ that incorporate classes of organic reactions within biochemistry. Module boundaries provide the interfaces where change is concentrated, when we catalogue extant diversity of metabolic phenotypes. The same modules that organize the compositional diversity of metabolism are argued, with many explicit examples, to have governed long-term evolution. Early evolution of core metabolism, and especially of carbon-fixation, appears to have required very few innovations, and to have used few rules of composition of conserved modules, to produce adaptations to simple chemical or energetic differences of environment without diverse solutions and without historical contingency. We demonstrate these features of metabolism at each of several levels of hierarchy, beginning with the small-molecule metabolic substrate and network architecture, continuing with cofactors and key conserved reactions, and culminating in the aggregation of multiple diverse physical and biochemical processes in cells.

Quantum chemical calculations and experimental investigations on 2-aminobenzoic acid-cyclodiphosph(V)azane derivative and its homo-binuclear Cu(II) complex

NASA Astrophysics Data System (ADS)

El-Gogary, Tarek M.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A. A.

2012-03-01

A novel 2-aminobenzoic acid-cyclodiphosph(V)azane ligand H4L and its homo-binuclear Cu(II) complex of the type [Cu2L(H2O)2].2.5 H2O in which L is 1,3-di(-o-pyridyl)-2,4-(dioxo)-2',4'-bis-(2-iminobenzoic acid) cyclodiphosph(V)azane, were synthesized and characterized by different physical techniques. Infrared spectra of the complex indicate deprotonation and coordination of the imine NH and carboxyl COOH groups. It also confirms that nitrogen atom of the pyridine ring contribute to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square-planar geometry for the Cu(II) complex. The elemental analyses and thermogravimetric results have justified the [Cu2L(H2O)2]·2.5H2O composition of the complex. Quantum chemical calculations were utilized to explore the electronic structure and stability of the H4L as well as the binuclear Cu(II) complex. Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of H4L and its binuclear Cu(II) complex. Different tautomers and geometrical isomers of the ligand were optimized at the ab initio DFT level. Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which show good agreement with measured electronic spectra.

Investigation of Mechanism of Action of Modifying Admixtures Based on Products of Petrochemical Synthesis on Concrete Structure

NASA Astrophysics Data System (ADS)

Tukhareli, V. D.; Tukhareli, A. V.; Cherednichenko, T. F.

2017-11-01

The creation of composite materials for generating structural elements with the desired properties has always been and still remains relevant. The basis of a modern concrete technology is the creation of a high-quality artificial stone characterized by low defectiveness and structure stability. Improving the quality of concrete compositions can be achieved by using chemical admixtures from local raw materials which is a very promising task of modern materials’ science for creation of a new generation of concretes. The new generation concretes are high-tech, high-quality, multicomponent concrete mixes and compositions with admixtures that preserve the required properties in service under all operating conditions. The growing complexity of concrete caused by systemic effects that allow you to control the structure formation at all stages of the technology ensures the obtaining of composites with "directional" quality, compositions, structure and properties. The possibility to use the organic fraction of oil refining as a multifunctional hydrophobic-plasticizing admixture in the effective cement concrete is examined.

Magnetically encoded luminescent composite nanoparticles through layer-by-layer self-assembly.

PubMed

Song, Erqun; Han, Weiye; Xu, Hongyan; Jiang, Yunfei; Cheng, Dan; Song, Yang; Swihart, Mark T

2014-11-03

Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO2 @n Fe3 O4 composite nanoparticles, by using a layer-by-layer self-assembly approach based on electrostatic interactions, is described. Silica-coated CdTe quantum dots (CdTe@SiO2 ) serve as core templates for the deposition of alternating layers of Fe3 O4 magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO2 @n Fe3 O4 (n=1, 2, 3, …︁) composite nanoparticles with a defined number (n) of Fe3 O4 layers. Composite nanoparticles were characterized by zeta-potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO2 @n Fe3 O4 composite nanoparticles exhibited excellent luminescence properties coupled with well-defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near-simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO2 @n Fe3 O4 nanoparticles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Advances in research of chemical constituents and pharmacological activities of common used spices].

PubMed

Sun, Chao-nan; Zhu, Yuan; Xu, Xi-ming; Yu, Jiang-nan

2014-11-01

Spices have enjoyed a long history and a worldwide application. Of particular interest is the pharmaceutical value of spices in addition to its basic seasoning function in cooking. Concretely, equipped with complex chemical compositions, spices are of significant importance in pharmacologic actions, like antioxidant, antibacterial, antitumor, as well as therapeutical effects in gastrointestinal disorders and cardiovascular disease. Although increasing evidences in support of its distinct role in the medical field has recently reported, little information is available for substantive, thorough and sophisticated researches on its chemical constituents and pharmacological activities, especially mechanism of these actions. Therefore, in popular wave of studies directed at a single spice, this review presents systematic studies on the chemical constituents and pharmacological activities associated with common used spices, together with current typical individual studies on functional mechanism, in order to pave the way for the exploitation and development of new medicines derived from the chemical compounds of spice (such as, piperine, curcumin, geniposide, cinnamaldehyde, cinnamic acid, linalool, estragole, perillaldehyde, syringic acid, crocin).

Quantitative Mineralogical Analysis of Mars Analogues Using CHEMIN Data and Rietveld Refinement

NASA Technical Reports Server (NTRS)

Bish, D. L.; Sarrazin, P.; Chipera, S. J.; Vaniman, D. T.; Blake, D.

2004-01-01

Mineralogical analysis is a critical component of planetary surface exploration. Chemical data alone leave serious gaps in our understanding of the surfaces of planets where complex minerals may form in combination with H, S, and halogens. On such planets (e.g., Mars) a single chemical composition may represent a range of mineral assemblages. For example, Viking chemical analyses of excavated duricrust indicate that Mg and S are correlated and 10% MgSO4 (anhydrous weight) is a likely cementing agent. Pathfinder chemical data support a similar abundance of MgSO4 in the most altered materials. However, there are many possible Mg-sulfates with widely varying hydration states (including dehydrated and 1-, 2-, 3-, 4-, 5-, 6-, and 7-hydrates). In addition, other sulfate minerals such as gypsum (CaSO4 .2H2O) and other salts containing Cl may also exist. X-ray diffraction (XRD) has the ability to decipher mixtures of these phases that would be difficult, if not impossible to unravel using only chemical or spectral data.

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.

Multimodal correlative investigation of the interplaying micro-architecture, chemical composition and mechanical properties of human cortical bone tissue reveals predominant role of fibrillar organization in determining microelastic tissue properties.

PubMed

Schrof, Susanne; Varga, Peter; Hesse, Bernhard; Schöne, Martin; Schütz, Roman; Masic, Admir; Raum, Kay

2016-10-15

The mechanical competence of bone is crucially determined by its material composition and structural design. To investigate the interaction of the complex hierarchical architecture, the chemical composition and the resulting elastic properties of healthy femoral bone at the level of single bone lamellae and entire structural units, we combined polarized Raman spectroscopy (PRS), scanning acoustic microscopy (SAM) and synchrotron X-ray phase contrast nano tomography (SR-nanoCT). In line with earlier studies, mutual correlation analysis strongly suggested that the characteristic elastic modulations of bone lamellae within single units are the result of the twisting fibrillar orientation, rather than compositional variations, modulations of the mineral particle maturity, or mass density deviations. Furthermore, we show that predominant fibril orientations in entire tissue units can be rapidly assessed from Raman parameter maps. Coexisting twisted and oscillating fibril patterns were observed in all investigated tissue domains. Ultimately, our findings demonstrate in particular the potential of combined PRS and SAM measurements in providing multi-scalar analysis of correlated fundamental tissue properties. In future studies, the presented approach can be applied for non-destructive investigation of small pathologic samples from bone biopsies and a broad range of biological materials and tissues. Bone is a complex structured composite material consisting of collagen fibrils and mineral particles. Various studies have shown that not only composition, maturation, and packing of its components, but also their structural arrangement determine the mechanical performance of the tissue. However, prominent methodologies are usually not able to concurrently describe these factors on the micron scale and complementary tissue characterization remains challenging. In this study we combine X-ray nanoCT, polarized Raman imaging and scanning acoustic microscopy and propose a protocol for fast and easy assessment of predominant fibril orientations in bone. Based on our site-matched analysis of cortical bone, we conclude that the elastic modulations of bone lamellae are mainly determined by the fibril arrangement. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Self-Supporting Nanoclay as Internal Scaffold Material for Direct Printing of Soft Hydrogel Composite Structures in Air.

PubMed

Jin, Yifei; Liu, Chengcheng; Chai, Wenxuan; Compaan, Ashley; Huang, Yong

2017-05-24

Three dimensional (3D) bioprinting technology enables the freeform fabrication of complex constructs from various hydrogels and is receiving increasing attention in tissue engineering. The objective of this study is to develop a novel self-supporting direct hydrogel printing approach to extrude complex 3D hydrogel composite structures in air without the help of a support bath. Laponite, a member of the smectite mineral family, is investigated to serve as an internal scaffold material for the direct printing of hydrogel composite structures in air. In the proposed printing approach, due to its yield-stress property, Laponite nanoclay can be easily extruded through a nozzle as a liquid and self-supported after extrusion as a solid. Its unique crystal structure with positive and negative charges enables it to be mixed with many chemically and physically cross-linked hydrogels, which makes it an ideal internal scaffold material for the fabrication of various hydrogel structures. By mixing Laponite nanoclay with various hydrogel precursors, the hydrogel composites retain their self-supporting capacity and can be printed into 3D structures directly in air and retain their shapes before cross-linking. Then, the whole structures are solidified in situ by applying suitable cross-linking stimuli. The addition of Laponite nanoclay can effectively improve the mechanical and biological properties of hydrogel composites. Specifically, the addition of Laponite nanoclay results in a significant increase in the Young's modulus of each hydrogel-Laponite composite: 1.9-fold increase for the poly(ethylene glycol) diacrylate (PEGDA)-Laponite composite, 7.4-fold increase for the alginate-Laponite composite, and 3.3-fold increase for the gelatin-Laponite composite.

PM2.5 Technology Assessment and Characterization Study in New York - PMTACS-NY: The 2001 Summer Field Intensive in Queens, NY

NASA Astrophysics Data System (ADS)

Demerjian, K. L.

2002-12-01

In the summer of 2001, an intensive field measurement campaign was carried out in Queens, NY as part of the PM2.5 Technology Assessment and Characterization Study in New York (PMTACS-NY) to characterize the physical and chemical composition of particulate matter and related precursors utilizing conventional and advanced instrumentation technologies. The measurement program, involving a team of scientists from federal, state, university and private sector organizations, was designed to provide detailed time resolved chemical and physical characterization of the urban PM2.5/co-pollutant complex in relation to the regional environment. A summary of the chemical and meteorological data defining specific events during the field intensive is presented as are results addressing specific hypothesis designed around PMTACS-NY program objectives. These include initial findings and conclusions related to 1) performance testing and evaluation of emerging measurement technologies and comparison with EPA mandated PM federal reference methods currently operational as part of the New York State and national PM2.5 monitoring network; 2) emissions characterization of CNG, standard diesel and CRT (Continuously Regenerating Technology) diesel retrofit powered vehicles; and 3) compositional comparisons of urban and regional PM2.5.

Unraveling the chemical complexity of biomass burning VOC emissions via H3O+ ToF-CIMS (PTR-ToF): emissions characterization

NASA Astrophysics Data System (ADS)

Koss, A.; Sekimoto, K.; Gilman, J.; Selimovic, V.; Coggon, M.; Zarzana, K. J.; Yuan, B.; Lerner, B. M.; Brown, S. S.; Jimenez, J. L.; Krechmer, J. E.; Warneke, C.; Yokelson, R. J.; De Gouw, J. A.

2017-12-01

Gas-phase biomass burning emissions can include hundreds, if not thousands, of unique volatile and intermediate-volatility organic compounds. It is crucial to know the composition of these emissions to understand secondary organic aerosol formation, ozone formation, and human health effects resulting from fires. However, the composition can vary greatly with fuel type and fire combustion process. During the FIREX 2016 laboratory intensive at the US Forest Service Fire Sciences Laboratory in Missoula, Montana, high-resolution H3O+-CIMS (PTR-ToF) was deployed to characterize VOC emissions. More than 500 ion masses were consistently enhanced in each of 58 fires, which included a wide variety of fuel types representative of the western United States. Using a combination of extensive literature review, H3O+ and NO+ CIMS with GC preseparation, comparison to other instruments, and mass spectral context, we were able to identify the VOC contributors to 90% of the instrument signal. This provides unprecedented chemical detail in high time resolution. We present chemical characteristics of emissions, including OH reactivity and volatility, and highlight areas where better identification is needed.

Dentin biomodification potential depends on polyphenol source.

PubMed

Aguiar, T R; Vidal, C M P; Phansalkar, R S; Todorova, I; Napolitano, J G; McAlpine, J B; Chen, S N; Pauli, G F; Bedran-Russo, A K

2014-04-01

Although proanthocyanidins (PACs) modify dentin, the effectiveness of different PAC sources and the correlation with their specific chemical composition are still unknown. This study describes the chemical profiling of natural PAC-rich extracts from 7 plants using ultra high pressure/performance liquid chromatography (UHPLC) to determine the overall composition of these extracts and, in parallel, comprehensively evaluate their effect on dentin properties. The total polyphenol content of the extracts was determined (as gallic acid equivalents) using Folin-Ciocalteau assays. Dentin biomodification was assessed by the modulus of elasticity, mass change, and resistance to enzymatic biodegradation. Extracts with a high polyphenol and PAC content from Vitis vinifera, Theobroma cacao, Camellia sinensis, and Pinus massoniana induced a significant increase in modulus of elasticity and mass. The UHPLC analysis showed the presence of multiple types of polyphenols, ranging from simple phenolic acids to oligomeric PACs and highly condensed tannins. Protective effect against enzymatic degradation was observed for all experimental groups; however, statistically significant differences were observed between plant extracts. The findings provide clear evidence that the dentin bioactivities of PACs are source dependent, resulting from a combination of concentration and specific chemical constitution of the complex PAC mixtures.

[Experience of the implementation of the method of the integral assessment of drinking water on indicators of chemical harmlessness in St. Petersburg].

PubMed

Mel'tser, A V; Erastova, N V; Kiselev, A V

2013-01-01

Providing population with quality drinking water--one of the priority tasks of the state policy aimed at maintaining the health of citizens. Hygienic rating of the drinking water quality envisages requirements to assurance its safety in the epidemiological and radiation relations, harmlessness of chemical composition and good organoleptic properties. There are numerous data proving the relationship between the chemical composition of drinking water and human health, and therefore the issue of taking a hygienically sound measures to improve the efficiency of water treatment has more and more priority. High water quality--the result of complex solution of tasks, including an integral approach to assessment of the quality of drinking water the use of hygienically sound decisions in the modernization of water treatment systems. The results of the integral assessment of drinking water on the properties of harmlessness have shown its actuality in the development and implementation of management decisions. The use of the spatial characteristics of integrated indices permits to visualize changes in the quality of drinking water in all stages of production and transportation from the position of health risks, evaluate the effectiveness of technological solutions and set priorities for investing.

Mixing of magmatic volatiles with groundwater and interaction with basalt on the summit of Kilauea Volcano, Hawaii

NASA Astrophysics Data System (ADS)

Hurwitz, Shaul; Goff, Fraser; Janik, Cathy J.; Evans, William C.; Counce, Dale A.; Sorey, Michael L.; Ingebritsen, Steven E.

2003-01-01

We interpret new chemical and isotopic data from samples collected between October 1998 and March 2002 from the NSF well (also called the Keller well), the only deep well on the summit of Kilauea Volcano, Hawaii. Sample collection followed cleaning of the well, which renewed access to the hydrothermal system very close to the loci of magmatic and fumarolic activity. The chemical and isotopic compositions of the new samples differ remarkably from data published previously. On the basis of the S/Cl ratio and carbon and helium isotopes we conclude that the thermal fluids formed by condensation of magmatic gas into shallow meteoric groundwater. Gas condensation was followed by a complex pattern of basalt dissolution accompanied by an increase of fluid pH and precipitation of secondary minerals. Geochemical modeling and geothermometry imply that the fluids equilibrated with an assemblage of secondary minerals at temperatures between 90 and 140°C. The significantly different chemical composition of the NSF well fluids from that of springs along the southern coast of the island indicates that mass transport from the summit region toward the lower flanks of the volcano is limited.

Integrating Mass Spectrometry of Intact Protein Complexes into Structural Proteomics

PubMed Central

Hyung, Suk-Joon; Ruotolo, Brandon T.

2013-01-01

Summary Mass spectrometry analysis of intact protein complexes has emerged as an established technology for assessing the composition and connectivity within dynamic, heterogeneous multiprotein complexes at low concentrations and in the context of mixtures. As this technology continues to move forward, one of the main challenges is to integrate the information content of such intact protein complex measurements with other mass spectrometry approaches in structural biology. Methods such as H/D exchange, oxidative foot-printing, chemical cross-linking, affinity purification, and ion mobility separation add complementary information that allows access to every level of protein structure and organization. Here, we survey the structural information that can be retrieved by such experiments, demonstrate the applicability of integrative mass spectrometry approaches in structural proteomics, and look to the future to explore upcoming innovations in this rapidly-advancing area. PMID:22611037

Investigation of carbonates in the Sutter's Mill meteorite grains with hyperspectral infrared imaging micro-spectroscopy

NASA Astrophysics Data System (ADS)

Yesiltas, Mehmet

2018-04-01

Synchrotron-based high spatial resolution hyperspectral infrared imaging technique provides thousands of infrared spectra with high resolution, thus allowing us to acquire detailed spatial maps of chemical molecular structures for many grains in short times. Utilizing this technique, thousands of infrared spectra were analyzed at once instead of inspecting each spectrum separately. Sutter's Mill meteorite is a unique carbonaceous type meteorite with highly heterogeneous chemical composition. Multiple grains from the Sutter's Mill meteorite have been studied using this technique and the presence of both hydrous and anhydrous silicate minerals have been observed. It is observed that the carbonate mineralogy varies from simple to more complex carbonates even within a few microns in the meteorite grains. These variations, the type and distribution of calcite-like vs. dolomite-like carbonates are presented by means of hyperspectral FTIR imaging spectroscopy with high resolution. Various scenarios for the formation of different carbonate compositions in the Sutter's Mill parent body are discussed.

Investigation of chemical vapor deposition of garnet films for bubble domain memories

NASA Technical Reports Server (NTRS)

Besser, P. J.; Hamilton, T. N.

1973-01-01

The important process parameters and control required to grow reproducible device quality ferrimagnetic films by chemical vapor deposition (CVD) were studied. The investigation of the critical parameters in the CVD growth process led to the conclusion that the required reproducibility of film properties cannot be achieved with individually controlled separate metal halide sources. Therefore, the CVD growth effort was directed toward replacement of the halide sources with metallic sources with the ultimate goal being the reproducible growth of complex garnet compositions utilizing a single metal alloy source. The characterization of the YGdGaIG films showed that certain characteristics of this material, primarily the low domain wall energy and the large temperature sensitivity, severely limited its potential as a useful material for bubble domain devices. Consequently, at the time of the change from halide to metallic sources, the target film compositions were shifted to more useful materials such as YGdTmGaIG, YEuGaIG and YSmGaIG.

Simultaneous synthesis and self-assembly of inorganic nanomaterials towards active and stable nanocatalysts

NASA Astrophysics Data System (ADS)

Yao, Zhou

The synthetic process in which the formation of nanoparticles and the self-assembly of those nanoparticles as building blocks are coupled together represents an efficient strategy towards stable nanostructures with relatively large geometric dimensions, well-defined shapes, structural hierarchicy and desirable porosities. In this dissertation, through employing appropriate soft/hard templates and controlling the reaction kinetics and thermodynamics, a series of novel physicochemical processes were developed to generate a wide variety of hierarchical 1D, 2D and 3D nanostructures with complex chemical compositions, structural integrities and/or porosities, which were then evaluated as electrocatalysts, heterogeneous catalysts and adsorbents. Based on the properties of their chemical compositions and potential applications, two types of inorganic nanostructures were obtained, including the noble metal-based nanostructures which could be employed as electrocatalysts and the Al-silicate-based hierarchical nanocomposites which could be used for preparation of supported nanocatalysts. The formation mechanisms underlying different processes are also well investigated.

Environmental and Chemical Aging of Fatty-Acid-Based Vinyl Ester Composites

DTIC Science & Technology

2011-04-01

Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites by Steven E. Boyd and John J. La Scala ARL-TR-5523 April...2011 Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites Steven E. Boyd and John J. La Scala Weapons and Materials...COVERED (From - To) October 2009–September 2010 4. TITLE AND SUBTITLE Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites

Multiple plagioclase crystal populations identified by crystal size distribution and in situ chemical data: Implications for timescales of magma chamber processes associated with the 1915 eruption of Lassen Peak, CA

USGS Publications Warehouse

Salisbury, M.J.; Bohrson, W.A.; Clynne, M.A.; Ramos, F.C.; Hoskin, P.

2008-01-01

Products of the 1915 Lassen Peak eruption reveal evidence for a magma recharge-magma mixing event that may have catalyzed the eruption and from which four compositional members were identified: light dacite, black dacite, andesitic inclusion, and dark andesite. Crystal size distribution, textural, and in situ chemical (major and trace element and Sr isotope) data for plagioclase from these compositional products define three crystal populations that have distinct origins: phenocrysts (long axis > 0??5 mm) that typically have core An contents between 34 and 36 mol %, microphenocrysts (long axis between 0??1 and 0??5 mm) that have core An contents of 66-69, and microlites (long axis < 0??1 mm) with variable An core contents from 64 to 52. Phenocrysts are interpreted to form in an isolated dacitic magma chamber that experienced slow cooling. Based on textural, compositional, and isotopic data for the magma represented by the dacitic component, magma recharge was not an important process until just prior to the 1915 eruption. Average residence times for phenocrysts are in the range of centuries to millennia. Microphenocrysts formed in a hybrid layer that resulted from mixing between end-member reservoir dacite and recharge magma of basaltic andesite composition. High thermal contrast between the two end-member magmas led to relatively high degrees of undercooling, which resulted in faster crystal growth rates and acicular and swallowtail crystal habits. Some plagioclase phenocrysts from the dacitic chamber were incorporated into the hybrid layer and underwent dissolution-precipitation, seen in both crystal textures and rim compositions. Average microphenocryst residence times are of the order of months. Microlites may have formed in response to decompression and/ or syn-eruptive degassing as magma ascended from the chamber through the volcanic conduit. Chemical distinctions in plagioclase microlite An contents reveal that melt of the dark andesite was more mafic than the melt of the other three compositions. We suggest that mixing of an intruding basaltic andesite and reservoir dacite before magma began ascending in the conduit allowed formation of a compositionally distinct microlite population. Melt in the other three products was more evolved because it had undergone differentiation during the months following initial mixing; as a consequence, melt and microlites among these three products have similar compositions. The results of this study highlight the integrated use of crystal size distribution, textural, and in situ chemical data in identifying distinct crystal populations and linking these populations to the thermal and chemical characteristics of complex magma bodies. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

1.13 – Emerging contaminants

USGS Publications Warehouse

Barber, Larry B.

2014-01-01

Since the Industrial Revolution, a diversity of large-scale chemical innovations has impacted aquatic systems in urban environments. Beginning in the 1990s, there has been a growing scientific interest and public awareness of the effects of the chemicals used in domestic, commercial, industrial, and agricultural applications, referred to in this article as ‘emerging contaminants’ (ECs), on ecosystem and human health. The growing global population and its increasing demands on water supplies in conjunction with climate-induced changes in hydrologic regimes place stress on freshwater resources, resulting in a greater reliance on reuse of reclaimed municipal wastewater treatment plant (WWTP) effluents to meet human and environmental needs. WWTP effluents are a major source of ECs, and it is important to have an understanding of the chemical composition of the reclaimed water, because many ECs are biologically active and the effects of chronic exposure to low concentration complex mixtures are unknown. Several classes of ECs that have been shown to be widespread in the aquatic environment are discussed in this chapter, including surfactants, complexing agents, fragrances, antimicrobials, industrial chemicals, pharmaceuticals, natural and synthetic estrogens, and disinfection byproducts. All of these compounds are biologically active via a variety of modes of action, and can occur in aquatic systems at concentrations ranging from <0.001 to >100 μg l−1.

WATER QUALITY MONITORING OF PHARMACEUTICALS ...

EPA Pesticide Factsheets

The demand on freshwater to sustain the needs of the growing population is of worldwide concern. Often this water is used, treated, and released for reuse by other communities. The anthropogenic contaminants present in this water may include complex mixtures of pesticides, prescription and nonprescription drugs, personal care and common consumer products, industrial and domestic-use materials and degradation products of these compounds. Although, the fate of these pharmaceuticals and personal care products (PPCPs) in wastewater treatment facilities is largely unknown, the limited data that does exist suggests that many of these chemicals survive treatment and some others are returned to their biologically active form via deconjugation of metabolites.Traditional water sampling methods (i.e., grab or composite samples) often require the concentration of large amounts of water to detect trace levels of PPCPs. A passive sampler, the polar organic chemical integrative sampler (POCIS), has been developed to integratively concentrate the trace levels of these chemicals, determine the time-weighted average water concentrations, and provide a method of estimating the potential exposure of aquatic organisms to these complex mixtures of waterborne contaminants. The POCIS (U.S. Patent number 6,478,961) consists of a hydrophilic microporous membrane, acting as a semipermeable barrier, enveloping various solid-phase sorbents that retain the sampled chemicals. Sampling rates f

Vector diagram of the chemical compositions of tektites and earth lavas

NASA Technical Reports Server (NTRS)

Kvasha, L. G.; Gorshkov, G. S.

1978-01-01

The chemical compositions of tektites and various volcanic glasses, similar in composition to tektites are compared by a petrochemical method. The advantage of the method is that a large number of chemical analyses of igneous rocks can be graphically compared with the help of vectors, plotted in relation to six parameters. These parameters, calculated from ratios of the main oxides given by silicate analysis, reflect the chief characteristics of igneous rock. Material for the study was suppled by data from chemical analysis characterizing tektites of all known locations and data from chemical analyses of obsidians similar in chemical composition to tektites of various petrographical provinces.

Two-dimensional NMR spectroscopy links structural moieties of soil organic matter to the temperature sensitivity of its decomposition

NASA Astrophysics Data System (ADS)

Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Schleucher, Jürgen

2015-04-01

Soil organic matter (SOM) represents a huge carbon pool, specifically in boreal ecosystems. Warming-induced release of large amounts of CO2 from the soil carbon pool might become a significant exacerbating feedback to global warming, if decomposition rates of boreal soils were more sensitive to increased temperatures. Despite a large number of studies dedicated to the topic, it has proven difficult to elucidate how the organo-chemical composition of SOM influences its decomposition, or its quality as a substrate for microbial metabolism. A great part of this challenge results from our inability to achieve a detailed characterization of the complex composition of SOM on the level of molecular structural moieties. 13C nuclear magnetic resonance (NMR) spectroscopy is a common tool to characterize SOM. However, SOM is a very complex mixture and the chemical shift regions distinguished in the 13C NMR spectra often represent many different molecular fragments. For example, in the carbohydrates region, signals of all monosaccharides present in many different polymers overlap. This overlap thwarts attempts to identify molecular moieties, resulting in insufficient information to characterize SOM composition. We applied two-dimensional (2D) NMR to characterize SOM with highly increased resolution. We directly dissolved finely ground litters and forest floors'fibric and humic horizons'of both coniferous and deciduous boreal forests in dimethyl sulfoxide and analyzed the resulting solution with a 2D 1H-13C NMR experiment. In the 2D planes of these spectra, signals of CH groups can be resolved based on their 13C and 1H chemical shifts, hence the resolving power and information content of these NMR spectra is hugely increased. The 2D spectra indeed resolved overlaps observed in 1D 13C spectra, so that hundreds of distinct CH groups could be observed and many molecular fragments could be identified. For instance, in the aromatics region, signals from individual lignin units could be recognized. It was hence possible to follow the fate of specific structural moieties in soils. We observed differences between litter and soil samples, and were able to relate them to the decomposition of identifiable moieties. Using multivariate data analysis, we aimed at linking the detailed chemical fingerprints of SOM to turnover rates in a soil incubation experiment. With the multivariate models, we were able to relate signal patterns in the 2D spectra and intensities of identifiable molecular moieties to variability in the temperature response of organic matter decomposition, as assessed by Q10. In conclusion, the characterization of SOM composition at the molecular level by solution-state 2D NMR spectroscopy is highly promising; it offers unprecedented possibilities to link SOM molecular composition to ecosystem processes, and their responses to environmental changes.

Tilts, dopants, vacancies and non-stoichiometry: Understanding and designing the properties of complex solid oxide perovskites from first principles

NASA Astrophysics Data System (ADS)

Bennett, Joseph W.

Perovskite oxides of formula ABO3 have a wide range of structural, electrical and mechanical properties, making them vital materials for many applications, such as catalysis, ultrasound machines and communication devices. Perovskite solid solutions with high piezoelectric response, such as ferroelectrics, are of particular interest as they can be employed as sensors in SONAR devices. Ferroelectric materials are unique in that their chemical and electrical properties can be non-invasively and reversibly changed, by switching the bulk polarization. This makes ferroelectrics useful for applications in non-volatile random access memory (NVRAM) devices. Perovskite solid solutions with a lower piezoelectric response than ferroelectrics are important for communication technology, as they function well as electroceramic capacitors. Also of interest is how these materials act as a component in a solid oxide fuel cell, as they can function as an efficient source of energy. Altering the chemical composition of these solid oxide materials offers an opportunity to change the desired properties of the final ceramic, adding a degree of flexibility that is advantageous for a variety of applications. These solid oxides are complex, sometimes disordered systems that are a challenge to study experimentally. However, as it is their complexity which produces favorable properties, highly accurate modeling which captures the essential features of the disordered structure is necessary to explain the behavior of current materials and predict favorable compositions for new materials. Methodological improvements and faster computer speeds have made first-principles and atomistic calculations a viable tool for understanding these complex systems. Offering a combination of accuracy and computational speed, the density functional theory (DFT) approach can reveal details about the microscopic structure and interactions of complex systems. Using DFT and a combination of principles from both inorganic chemistry and materials science, I have been able to gain insights into solid oxide perovskite-based systems.

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

PubMed

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

Mass spectrometry–based relative quantification of proteins in precatalytic and catalytically active spliceosomes by metabolic labeling (SILAC), chemical labeling (iTRAQ), and label-free spectral count

PubMed Central

Schmidt, Carla; Grønborg, Mads; Deckert, Jochen; Bessonov, Sergey; Conrad, Thomas; Lührmann, Reinhard; Urlaub, Henning

2014-01-01

The spliceosome undergoes major changes in protein and RNA composition during pre-mRNA splicing. Knowing the proteins—and their respective quantities—at each spliceosomal assembly stage is critical for understanding the molecular mechanisms and regulation of splicing. Here, we applied three independent mass spectrometry (MS)–based approaches for quantification of these proteins: (1) metabolic labeling by SILAC, (2) chemical labeling by iTRAQ, and (3) label-free spectral count for quantification of the protein composition of the human spliceosomal precatalytic B and catalytic C complexes. In total we were able to quantify 157 proteins by at least two of the three approaches. Our quantification shows that only a very small subset of spliceosomal proteins (the U5 and U2 Sm proteins, a subset of U5 snRNP-specific proteins, and the U2 snRNP-specific proteins U2A′ and U2B′′) remains unaltered upon transition from the B to the C complex. The MS-based quantification approaches classify the majority of proteins as dynamically associated specifically with the B or the C complex. In terms of experimental procedure and the methodical aspect of this work, we show that metabolically labeled spliceosomes are functionally active in terms of their assembly and splicing kinetics and can be utilized for quantitative studies. Moreover, we obtain consistent quantification results from all three methods, including the relatively straightforward and inexpensive label-free spectral count technique. PMID:24448447

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

NASA Astrophysics Data System (ADS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Isotope and trace element insights into heterogeneity of subridge mantle

NASA Astrophysics Data System (ADS)

Mallick, Soumen; Dick, Henry J. B.; Sachi-Kocher, Afi; Salters, Vincent J. M.

2014-06-01

Geochemical data for abyssal peridotites are used to determine the relationship to mid-ocean ridge basalts from several locations at ridge segments on the SW Indian Ridge (SWIR), the Mid-Cayman-Rise (MCR), and the Mid-Atlantic Ridge (MAR). Based on chemical and petrological criteria peridotites are categorized as being either dominantly impregnated with melt or being residual after recent melting. Those that are considered impregnated with melt also have isotopic compositions similar to the basalts indicating impregnation by an aggregate MORB melt. A SWIR and MCR residual peridotite Nd-isotopic compositions partly overlap the Nd-isotopic compositions of the basalts but extend to more radiogenic compositions. The differences between peridotite and basalt Nd-isotopic compositions can be explained by incorporating a low-solidus component with enriched isotopic signature in the subridge mantle: a component that is preferentially sampled by the basalts. At the MAR, peridotites and associated basalts have overlapping Nd-isotopic compositions, suggesting a more homogeneous MORB mantle. The combined chemistry and petrography indicates a complex history with several depletion and enrichment events. The MCR data indicate that a low-solidus component can be a ubiquitous component of the asthenosphere. Residual abyssal peridotites from limited geographic areas also show significant chemical variations that could be associated with initial mantle heterogeneities related to events predating the ridge-melting event. Sm-Nd model ages for possible earlier depletion events suggest these could be as old as 2.4 Ga. This article was corrected on 9 JULY 2014. See the end of the full text for details.

Biodegradation of the chitin-protein complex in crustacean cuticle

USGS Publications Warehouse

Artur, Stankiewicz B.; Mastalerz, Maria; Hof, C.H.J.; Bierstedt, A.; Flannery, M.B.; Briggs, D.E.G.; Evershed, R.P.

1998-01-01

Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative analysis of amino acids (by HPLC) and chitin showed that the major loss of proteins and chitin occurred between weeks 1 and 2. After 8 weeks tyrosine, tryptophan and valine are the most prominent amino acid moieties, showing their resistance to degradation. The presence of cyclic ketones in the pyrolysates indicates that mucopolysaccharides or other bound non-chitinous carbohydrates are also resistant to decay. There is no evidence of structural degradation of chitin prior to 8 weeks when FTIR revealed a reduction in chitin-specific bands. The chemical changes are paralleled by structural changes in the cuticle, which becomes an increasingly open structure consisting of loose chitinous fibres. The rapid rate of decay in the experiments suggests that where chitin and protein are preserved in fossil cuticles degradation must have been inhibited.Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative analysis of amino acids (by HPLC) and chitin showed that the major loss of proteins and chitin occurred between weeks 1 and 2. After 8 weeks tyrosine, tryptophan and valine are the most prominent amino acid moieties, showing their resistance to degradation. The presence of cyclic ketones in the pyrolysates indicates that mucopolysaccharides or other bound non-chitinous carbohydrates are also resistant to decay. There is no evidence of structural degradation of chitin prior to 8 weeks when FTIR revealed a reduction in chitin-specific bands. The chemical changes are paralleled by structural changes in the cuticle, which becomes an increasingly open structure consisting of loose chitinous fibres. The rapid rate of decay in the experiments suggests, that where chitin and protein are preserved in fossil cuticles degradation must have been inhibited.

The phenomenon of cathodoluminescence in tooth hard tissues

NASA Astrophysics Data System (ADS)

Bessudnova, Nadezda O.; Matasov, Maxim D.

2012-03-01

The phenomenon of luminescence in tooth hard tissues under the hits of electrons accelerated up to 3keV has been investigated and the nature of luminescence has been described. It has been discovered that the change in luminescence color depends on the place of the impingement of primary electrons. The latter could be explained by different chemical compositions of compounds and complexes where luminescence is observed. Based on the analysis of RGB color bar charts, the correlation between the color of luminescence and calcium-phosphorus ratio in tooth hard tissues has been investigated. Thus, cathodoluminescence can be considered as a tool for in vitro quantitative assessment of tooth hard tissues compositions.

Complexing agents and pH influence on chemical durability of type I moulded glass containers.

PubMed

Biavati, Alberto; Poncini, Michele; Ferrarini, Arianna; Favaro, Nicola; Scarpa, Martina; Vallotto, Marta

2017-06-16

Among the factors that affect the glass surface chemical durability, pH and complexing agents presence in aqueous solution have the main role (1). Glass surface attack can be also related to the delamination issue with glass particles appearance in the pharmaceutical preparation. A few methods to check for glass containers delamination propensity and some control guidelines have been proposed (2,3). The present study emphasizes the possible synergy between a few complexing agents with pH on the borosilicate glass chemical durability. Hydrolytic attack was performed in small volume 23 ml type I glass containers autoclaved according to EP or USP for 1 hour at 121°C, in order to enhance the chemical attack due to time, temperature and the unfavourable surface/volume ratio. 0,048 M or 0.024 M (moles/liter) solutions of the acids citric, glutaric, acetic, EDTA (ethylenediaminetetraacetic acid) and sodium phosphate with water for comparison, were used for the trials. The pH was adjusted ± 0,05 units at fixed values 5,5-6,6-7-7,4-8-9 by LiOH diluted solution. Since silicon is the main glass network former, silicon release into the attack solutions was chosen as the main index of the glass surface attack and analysed by ICPAES. The work was completed by the analysis of the silicon release in the worst attack conditions, of moulded glass, soda lime type II and tubing borosilicate glass vials to compare different glass compositions and forming technologies. Surface analysis by SEM was finally performed to check for the surface status after the worst chemical attack condition by citric acid. Copyright © 2017, Parenteral Drug Association.

Essential Oils’ Chemical Characterization and Investigation of Some Biological Activities: A Critical Review

PubMed Central

Dhifi, Wissal; Bellili, Sana; Jazi, Sabrine; Bahloul, Nada; Mnif, Wissem

2016-01-01

This review covers literature data summarizing, on one hand, the chemistry of essential oils and, on the other hand, their most important activities. Essential oils, which are complex mixtures of volatile compounds particularly abundant in aromatic plants, are mainly composed of terpenes biogenerated by the mevalonate pathway. These volatile molecules include monoterpenes (hydrocarbon and oxygenated monoterpens), and also sesquiterpenes (hydrocarbon and oxygenated sesquiterpens). Furthermore, they contain phenolic compounds, which are derived via the shikimate pathway. Thanks to their chemical composition, essential oils possess numerous biological activities (antioxidant, anti-inflammatory, antimicrobial, etc…) of great interest in food and cosmetic industries, as well as in the human health field. PMID:28930135

Altering wettability to recover more oil from tight formations

DOE PAGES

Brady, Patrick V.; Bryan, Charles R.; Thyne, Geoffrey; ...

2016-06-03

We describe here a method for chemically modifying fracturing fluids and overflushes to chemically increase oil recovery from tight formations. Oil wetting of tight formations is usually controlled by adhesion to illite, kerogen, or both; adhesion to carbonate minerals may also play a role. Oil-illite adhesion is sensitive to salinity, dissolved divalent cation content, and pH. We measure oil-rock adhesion with middle Bakken formation oil and core to verify a surface complexation model of reservoir wettability. The agreement between the model and experiments suggests that wettability trends in tight formations can be quantitatively predicted and that fracturing fluid and overflushmore » compositions can be individually tailored to increase oil recovery.« less

Altering wettability to recover more oil from tight formations

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

Brady, Patrick V.; Bryan, Charles R.; Thyne, Geoffrey

We describe here a method for chemically modifying fracturing fluids and overflushes to chemically increase oil recovery from tight formations. Oil wetting of tight formations is usually controlled by adhesion to illite, kerogen, or both; adhesion to carbonate minerals may also play a role. Oil-illite adhesion is sensitive to salinity, dissolved divalent cation content, and pH. We measure oil-rock adhesion with middle Bakken formation oil and core to verify a surface complexation model of reservoir wettability. The agreement between the model and experiments suggests that wettability trends in tight formations can be quantitatively predicted and that fracturing fluid and overflushmore » compositions can be individually tailored to increase oil recovery.« less

Nature and geodynamic setting of the protoliths of the UHP metamorphic Complex and migmatites in Bixiling area, the Dabie Orogen, China

NASA Astrophysics Data System (ADS)

Li, H.; Jahn, B.; Wang, D.; Yu, H.; Liu, Z.; Hou, G.

2013-12-01

As the largest coesite-bearing mafic-ultramafic body in the Dabie-Sulu orogen, the Bixiling Complex is composed of meta-ultramafic rocks, MgAl-rich eclogites and FeTi-rich eclogites. The FeTi-rich eclogites are further divided into low-Si-high-Fe type (Type I) and high-Si-low-Fe type (Type II) according to their mineral assemblages and bulk chemical composition. Field, petrographic, petrological and geochemical characteristics of these rocks, although suffered an ultra-high pressure metamorphism, still show a magmatic differentiation process among the protoliths of the meta-ultramafic rocks, MgAl-rich eclogites and Type I FeTi-rich eclogites. A small degree of lower crustal contamination occurred during their magma chamber process. Amphibolite is widespread in the periphery of the complex. Non-foliation and fine-grained texture are their obvious characteristics. Geochemical and isotopic affinities suggest that the amphibolites represent a product of complete retrogression from type II FeTi-rich eclogites. The UHP complex is enclosed in granitic gneisses, which variably include two-mica plagioclase gneiss, epidote two-mica plagioclase gneiss, or white-mica plagioclase gneiss. They all show TTG, especially trondjhemitic composition. A migmatite outcrop was found near the northeastern end of the complex. The migmatites consist of dark colored, non-foliated amphibolites and light-colored, fine-grained trondhjemitic gneisses. Field occurrences, microstructures observed under optical microscope and SEM, Sr-Nd isotopic data suggest an origin of partial melting. Chemical composition of two stages of amphiboles occurred in both the amphibolites and the trondhjemitic gneisses also imply a partial melting process occurred. Trace element, Sr-Nd isotope and SHRIMP zircon U-Pb dating of MgAl-rich eclogite, amphibolites and trondhjemite suggest that the migmatites represent a partial melting of crustal materials at about 780Ma, possibly accompanied by the coeval emplacement of a differentiated mafic intrusive body. These rocks were deeply subducted into a mantle depth during the Triassic continental collision between the Yangtze Craton and North China Craton, and thereafter were exhumed to the surface. Their residual geochemical characteristics and spatial / temporal relationship could impose constraints on the tectonic evolution of the Dabieshan UHP terrane.

Surface Traps in Colloidal Quantum Dots: A Combined Experimental and Theoretical Perspective.

PubMed

Giansante, Carlo; Infante, Ivan

2017-10-19

Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their atomistic origin and manipulating them chemically have capital importance to design defect-free colloidal quantum dots and make a leap forward in the development of efficient optoelectronic devices. Recent advances in computing power established computational chemistry as a powerful tool to describe accurately complex chemical species and nowadays it became conceivable to model colloidal quantum dots with realistic sizes and shapes. In this Perspective, we combine the knowledge gathered in recent experimental findings with the computation of quantum dot electronic structures. We analyze three different systems: namely, CdSe, PbS, and CsPbI 3 as benchmark semiconductor nanocrystals showing how different types of trap states can form at their surface. In addition, we suggest experimental healing of such traps according to their chemical origin and nanocrystal composition.

Mineral and chemical variations within an ash-flow sheet from Aso caldera, Southwestern Japan

USGS Publications Warehouse

Lipman, P.W.

1967-01-01

Although products of individual volcanic eruptions, especially voluminous ash-flow eruptions, have been considered among the best available samples of natural magmas, detailed petrographic and chemical study indicates that bulk compositions of unaltered Pleistocene ash-flow tuffs from Aso caldera, Japan, deviate significantly from original magmatic compositions. The last major ash-flow sheet from Aso caldera is as much as 150 meters thick and shows a general vertical compositional change from phenocryst-poor rhyodacite upward into phenocryst-rich trachyandesite; this change apparently reflects in inverse order a compositionally zoned magma chamber in which more silicic magma overlay more mafic magma. Details of these magmatic variations were obscured, however, by: (1) mixing of compositionally distinct batches of magma during upwelling in the vent, as indicated by layering and other heterogeneities within single pumice lumps; (2) mixing of particulate fragments-pumice lumps, ash, and phenocrysts-of varied compositions during emplacement, with the result that separate pumice lenses from a single small outcrop may have a compositional range nearly as great as the bulk-rook variation of the entire sheet; (3) density sorting of phenocrysts and ash during eruption and emplacement, resulting in systematic modal variations with distance from the caldera; (4) addition of xenocrysts, resulting in significant contamination and modification of proportions of crystals in the tuffs; and (5) ground-water leaching of glassy fractions during hydration after cooling. Similar complexities characterize ash-flow tuffs under study in southwestern Nevada and in the San Juan Mountains, Colorado, and probably are widespread in other ash-flow fields as well. Caution and careful planning are required in study of the magmatic chemistry and phenocryst mineralogy of these rocks. ?? 1967 Springer-Verlag.

CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING

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

Fox, K.; Marra, J.

2014-08-14

The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making itmore » difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} concentrations missing their targeted values by a significant amount for several of the study glasses. SHU is reviewing the fabrication of these glasses and the chemicals used in batching them to identify the source of these issues. The measured sulfate concentrations were all below their targeted values. This is expected, as the targeted concentrations likely exceeded the solubility limit for sulfate in these glass compositions. Some volatilization of sulfate may also have occurred during fabrication of the glasses. Measurements of the other oxides in the study glasses were reasonably close to their targeted values« less

Correlation analyses of phytochemical composition, chemical, and cellular measures of antioxidant activity of broccoli (Brassica oleracea L. Var. italica).

PubMed

Eberhardt, Marian V; Kobira, Kanta; Keck, Anna-Sigrid; Juvik, John A; Jeffery, Elizabeth H

2005-09-21

Chemical measures of antioxidant activity within the plant, such as the oxygen radical absorbance capacity (ORAC) assay, have been reported for many plant-based foods. However, the extent to which chemical measures relate to cellular measures of oxidative stress is unclear. The natural variation in the phytochemical content of 22 broccoli genotypes was used to determine correlations among chemical composition (carotenoids, tocopherols and polyphenolics), chemical antioxidant activity (ORAC), and measures of cellular antioxidation [prevention of DNA oxidative damage and of oxidation of the biomarker dichlorofluorescein (DCFH) in HepG2 cells] using hydrophilic and lipophilic extracts of broccoli. For lipophilic extracts, ORAC (ORAC-L) correlated with inhibition of cellular oxidation of DCFH (DCFH-L, r = 0.596, p = 0.006). Also, DNA damage in the presence of the lipophilic extract was negatively correlated with both chemical and cellular measures of antioxidant activity as measured by ORAC-L (r = -0.705, p = 0.015) and DCFH-L (r = -0.671, p = 0.048), respectively. However, no correlations were observed for hydrophilic (-H) extracts, except between polyphenol content and ORAC (ORAC-H; r = 0.778, p < 0.001). Inhibition of cellular oxidation by hydrophilic extracts (DCFH-H) and ORAC-H were approximately 8- and 4-fold greater than DCFH-L and ORAC-L, respectively. Whether ORAC-H has more biological relevance than ORAC-L because of its magnitude or whether ORAC-L bears more biological relevance because it relates to cellular estimates of antioxidant activity remains to be determined. Chemical estimates of antioxidant capacity within the plant may not accurately reflect the complex nature of the full antioxidant activity of broccoli extracts within cells.

The Hemolymph Proteome of Fed and Starved Drosophila Larvae

PubMed Central

Goetze, Sandra; Ahrens, Christian H.; Omasits, Ulrich; Marty, Florian; Simigdala, Nikiana; Meyer, Imke; Wollscheid, Bernd; Brunner, Erich; Hafen, Ernst; Lehner, Christian F.

2013-01-01

The co-operation of specialized organ systems in complex multicellular organisms depends on effective chemical communication. Thus, body fluids (like blood, lymph or intraspinal fluid) contain myriads of signaling mediators apart from metabolites. Moreover, these fluids are also of crucial importance for immune and wound responses. Compositional analyses of human body fluids are therefore of paramount diagnostic importance. Further improving their comprehensiveness should increase our understanding of inter-organ communication. In arthropods, which have trachea for gas exchange and an open circulatory system, the single dominating interstitial fluid is the hemolymph. Accordingly, a detailed analysis of hemolymph composition should provide an especially comprehensive picture of chemical communication and defense in animals. Therefore we used an extensive protein fractionation workflow in combination with a discovery-driven proteomic approach to map out the detectable protein composition of hemolymph isolated from Drosophila larvae. Combined mass spectrometric analysis revealed more than 700 proteins extending far beyond the previously known Drosophila hemolymph proteome. Moreover, by comparing hemolymph isolated from either fed or starved larvae, we provide initial provisional insights concerning compositional changes in response to nutritional state. Storage proteins in particular were observed to be strongly reduced by starvation. Our hemolymph proteome catalog provides a rich basis for data mining, as exemplified by our identification of potential novel cytokines, as well as for future quantitative analyses by targeted proteomics. PMID:23840627

Chemical Composition and Antioxidant Activity of Euterpe oleracea Roots and Leaflets.

PubMed

Brunschwig, Christel; Leba, Louis-Jérôme; Saout, Mona; Martial, Karine; Bereau, Didier; Robinson, Jean-Charles

2016-12-29

Euterpe oleracea (açaí) is a palm tree well known for the high antioxidant activity of its berries used as dietary supplements. Little is known about the biological activity and the composition of its vegetative organs. The objective of this study was to investigate the antioxidant activity of root and leaflet extracts of Euterpe oleracea ( E . oleracea ) and characterize their phytochemicals. E . oleracea roots and leaflets extracts were screened in different chemical antioxidant assays (DPPH-2,2-diphenyl-1-picrylhydrazyl, FRAP-ferric feducing antioxidant power, and ORAC-oxygen radical absorbance capacity), in a DNA nicking assay and in a cellular antioxidant activity assay. Their polyphenolic profiles were determined by UV and LC-MS/MS. E . oleracea leaflets had higher antioxidant activity than E . oleracea berries, and leaflets of Oenocarpus bacaba and Oenocarpus bataua , as well as similar antioxidant activity to green tea. E. oleracea leaflet extracts were more complex than root extracts, with fourteen compounds, including caffeoylquinic acids and C -glycosyl derivatives of apigenin and luteolin. In the roots, six caffeoylquinic and caffeoylshikimic acids were identified. Qualitative compositions of E. oleracea , Oenocarpus bacaba and Oenocarpus bataua leaflets were quite similar, whereas the quantitative compositions were quite different. These results provide new prospects for the valorization of roots and leaflets of E. oleracea in the pharmaceutical, food or cosmetic industry, as they are currently by-products of the açaí industry.

Chemical Composition and Antioxidant Activity of Euterpe oleracea Roots and Leaflets

PubMed Central

Brunschwig, Christel; Leba, Louis-Jérôme; Saout, Mona; Martial, Karine; Bereau, Didier; Robinson, Jean-Charles

2016-01-01

Euterpe oleracea (açaí) is a palm tree well known for the high antioxidant activity of its berries used as dietary supplements. Little is known about the biological activity and the composition of its vegetative organs. The objective of this study was to investigate the antioxidant activity of root and leaflet extracts of Euterpe oleracea (E. oleracea) and characterize their phytochemicals. E. oleracea roots and leaflets extracts were screened in different chemical antioxidant assays (DPPH—2,2-diphenyl-1-picrylhydrazyl, FRAP—ferric feducing antioxidant power, and ORAC—oxygen radical absorbance capacity), in a DNA nicking assay and in a cellular antioxidant activity assay. Their polyphenolic profiles were determined by UV and LC-MS/MS. E. oleracea leaflets had higher antioxidant activity than E. oleracea berries, and leaflets of Oenocarpus bacaba and Oenocarpus bataua, as well as similar antioxidant activity to green tea. E. oleracea leaflet extracts were more complex than root extracts, with fourteen compounds, including caffeoylquinic acids and C-glycosyl derivatives of apigenin and luteolin. In the roots, six caffeoylquinic and caffeoylshikimic acids were identified. Qualitative compositions of E. oleracea, Oenocarpus bacaba and Oenocarpus bataua leaflets were quite similar, whereas the quantitative compositions were quite different. These results provide new prospects for the valorization of roots and leaflets of E. oleracea in the pharmaceutical, food or cosmetic industry, as they are currently by-products of the açaí industry. PMID:28036089

The hemolymph proteome of fed and starved Drosophila larvae.

PubMed

Handke, Björn; Poernbacher, Ingrid; Goetze, Sandra; Ahrens, Christian H; Omasits, Ulrich; Marty, Florian; Simigdala, Nikiana; Meyer, Imke; Wollscheid, Bernd; Brunner, Erich; Hafen, Ernst; Lehner, Christian F

2013-01-01

The co-operation of specialized organ systems in complex multicellular organisms depends on effective chemical communication. Thus, body fluids (like blood, lymph or intraspinal fluid) contain myriads of signaling mediators apart from metabolites. Moreover, these fluids are also of crucial importance for immune and wound responses. Compositional analyses of human body fluids are therefore of paramount diagnostic importance. Further improving their comprehensiveness should increase our understanding of inter-organ communication. In arthropods, which have trachea for gas exchange and an open circulatory system, the single dominating interstitial fluid is the hemolymph. Accordingly, a detailed analysis of hemolymph composition should provide an especially comprehensive picture of chemical communication and defense in animals. Therefore we used an extensive protein fractionation workflow in combination with a discovery-driven proteomic approach to map out the detectable protein composition of hemolymph isolated from Drosophila larvae. Combined mass spectrometric analysis revealed more than 700 proteins extending far beyond the previously known Drosophila hemolymph proteome. Moreover, by comparing hemolymph isolated from either fed or starved larvae, we provide initial provisional insights concerning compositional changes in response to nutritional state. Storage proteins in particular were observed to be strongly reduced by starvation. Our hemolymph proteome catalog provides a rich basis for data mining, as exemplified by our identification of potential novel cytokines, as well as for future quantitative analyses by targeted proteomics.

Composition and Chemical Stability of Motor Fuels,

DTIC Science & Technology

Fuels, *Hydrocarbons, Cycloalkanes, Chemical analysis, Gasoline, Diesel fuels, Fuel additives, Chemical reactions, Stability, Jet engine fuels...Aviation gasoline, Aviation fuels, Chemical composition, Aromatic hydrocarbons, Unsaturated hydrocarbons, Storage, USSR, Translations, Fuel systems, Alkanes

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

NASA Astrophysics Data System (ADS)

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-10-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

PubMed Central

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-01-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species. PMID:26515033

Scaling violation in fragmentation region at energies above 10-15 eV based on the data on cosmic ray hadron component

NASA Technical Reports Server (NTRS)

1985-01-01

The ratio of intensity of energetic hadrons, having no visible accompaniment, to the total flux of hadrons of the same energy at 4380m above sea level is given. The ratio is much more than expected for scaling model with proton primaries. This result could not be explained by complex chemical composition of primary cosmic ray and indicates the scaling violation in fragmentation region.

Magnetic Spin Effects in Photoprocesses inside Polymeric Photoconductors

NASA Astrophysics Data System (ADS)

Rumyantsev, B. M.; Berendyaev, V. I.; Pebalk, A. V.

2018-06-01

Magnetic spin effects are detected and studied in the processes of sensitized current-carrier photogeneration and luminescence inside polymer photoconductor films based on polyimides and composites of polymers with carbazole moieties combined with electron acceptors (chemical sensitization) and dyes (spectral sensitization). The effect an electric field has on the quantum yield of photogeneration and the luminescence of excited charge-transfer complexes (reversible and irreversible effects) at spectral sensitization is studied in the presence of O2.

Preform For Producing An Optical Fiber And Method Therefor

DOEpatents

Kliner, Dahv A. V.; Koplow, Jeffery P.

2004-08-10

The present invention provides a simple method for fabricating fiber-optic glass preforms having complex refractive index configurations and/or dopant distributions in a radial direction with a high degree of accuracy and precision. The method teaches bundling together a plurality of glass rods of specific physical, chemical, or optical properties and wherein the rod bundle is fused in a manner that maintains the cross-sectional composition and refractive-index profiles established by the position of the rods.

Preform For Producing An Optical Fiber And Method Therefor

DOEpatents

Kliner, Dahv A. V.; Koplow, Jeffery P.

2005-04-19

The present invention provides a simple method for fabricating fiber-optic glass preforms having complex refractive index configurations and/or dopant distributions in a radial direction with a high degree of accuracy and precision. The method teaches bundling together a plurality of glass rods of specific physical, chemical, or optical properties and wherein the rod bundle is fused in a manner that maintains the cross-sectional composition and refractive-index profiles established by the position of the rods.

Structure-activity relationship of sulfated hetero/galactofucan polysaccharides on dopaminergic neuron.

PubMed

Wang, Jing; Liu, Huaide; Jin, Weihua; Zhang, Hong; Zhang, Quanbin

2016-01-01

Parkinson's disease (PD) is associated with progressive loss of dopaminergic neurons and more-widespread neuronal changes that cause complex symptoms. The aim of this study was to investigate the structure-activity relationship of sulfated hetero-polysaccharides (DF1) and sulfated galactofucan polysaccharides (DF2) on dopaminergic neuron in vivo and in vitro. Treatment with samples significantly ameliorated the depletion of both DA and TH-, Bcl-2- and Bax-positive neurons in MPTP-induced PD mice, DF1 showed the highest activity. The in vitro results found that DF1 and DF2 could reverse the decreased mitochondrial activity and the increased LDL release induced by MPP(+) (P<0.01 or P<0.001) which provides further evidence that DF1 and DF2 also exerts a direct protection against the neuronal injury caused by MPP(+). Furthermore, the administration of samples effectively decreased lipid peroxidation and increased the level/activities of GSH, GSH-PX, MDA and CAT in MPTP mice. Thus, the neuron protective effect may be mediated, in part, through antioxidant activity and the prevention of cell apoptosis. The chemical composition of DF1, DF2 and DF differed markedly, the DF1 fraction had the most complex chemical composition and showed the highest neuron protective activity. These results suggest that diverse monosaccharides and uronic acid might contribute to neuron protective activity. Copyright © 2015 Elsevier B.V. All rights reserved.

BASTet: Shareable and Reproducible Analysis and Visualization of Mass Spectrometry Imaging Data via OpenMSI.

PubMed

Rubel, Oliver; Bowen, Benjamin P

2018-01-01

Mass spectrometry imaging (MSI) is a transformative imaging method that supports the untargeted, quantitative measurement of the chemical composition and spatial heterogeneity of complex samples with broad applications in life sciences, bioenergy, and health. While MSI data can be routinely collected, its broad application is currently limited by the lack of easily accessible analysis methods that can process data of the size, volume, diversity, and complexity generated by MSI experiments. The development and application of cutting-edge analytical methods is a core driver in MSI research for new scientific discoveries, medical diagnostics, and commercial-innovation. However, the lack of means to share, apply, and reproduce analyses hinders the broad application, validation, and use of novel MSI analysis methods. To address this central challenge, we introduce the Berkeley Analysis and Storage Toolkit (BASTet), a novel framework for shareable and reproducible data analysis that supports standardized data and analysis interfaces, integrated data storage, data provenance, workflow management, and a broad set of integrated tools. Based on BASTet, we describe the extension of the OpenMSI mass spectrometry imaging science gateway to enable web-based sharing, reuse, analysis, and visualization of data analyses and derived data products. We demonstrate the application of BASTet and OpenMSI in practice to identify and compare characteristic substructures in the mouse brain based on their chemical composition measured via MSI.

Elemental ratios for characterization of quantum-dots populations in complex mixtures by asymmetrical flow field-flow fractionation on-line coupled to fluorescence and inductively coupled plasma mass spectrometry.

PubMed

Menendez-Miranda, Mario; Fernandez-Arguelles, Maria T; Costa-Fernandez, Jose M; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo

2014-08-11

Separation and identification of nanoparticles of different composition, with similar particle diameter, coexisting in heterogeneous suspensions of polymer-coated CdSe/ZnS quantum dots (QDs) have been thoroughly assessed by asymmetric flow field-flow fractionation (AF4) coupled on-line to fluorescence and inductively coupled plasma mass spectrometry (ICPMS) detectors. Chemical characterization of any previously on-line separated nanosized species was achieved by the measurement of the elemental molar ratios of every element involved in the synthesis of the QDs, using inorganic standards and external calibration by flow injection analysis (FIA). Such elemental molar ratios, strongly limited so far to pure single nanoparticles suspensions, have been achieved with adequate accuracy by coupling for the first time an ICP-QQQ instrument to an AF4 system. This hyphenation turned out to be instrumental to assess the chemical composition of the different populations of nanoparticles coexisting in the relatively complex mixtures, due to its capabilities to detect the hardly detectable elements involved in the synthesis. Interestingly such information, complementary to that obtained by fluorescence, was very valuable to detect and identify unexpected nanosized species, present at significant level, produced during QDs synthesis and hardly detectable by standard approaches. Copyright © 2014. Published by Elsevier B.V.

The System of Chemical Elements Distribution in the Hydrosphere

NASA Astrophysics Data System (ADS)

Korzh, Vyacheslav D.

2013-04-01

The chemical composition of the hydrosphere is a result of substance migration and transformation on lithosphere-river, river-sea, and ocean-atmosphere boundaries. The chemical elements composition of oceanic water is a fundamental multi-dimensional constant for our planet. Detailed studies revealed three types of chemical element distribution in the ocean: 1) Conservative: concentration normalized to salinity is the constant in space and time; 2) Nutrient-type: element concentration in the surface waters decreases due to the biosphere consumption; and 3) Litho-generative: complex character of distribution of elements, which enter the ocean with the river runoff and interred almost entirely in sediments. The correlation between the chemical elements compositions of the river and oceanic water is high (r = 0.94). We conclude that biogeochemical features of each chemical element are determined by the relationship between its average concentration in the ocean and the intensity of its migration through hydrosphere boundary zones. In our presentation, we shall show intensities of global migration and average concentrations in the ocean in the co ordinates lgC - lg [tau], where C is an average element concentration and [tau] is its residence time in the ocean. We have derived a relationship between three main geochemical parameters of the dissolved forms of chemical elements in the hydrosphere: 1) average concentration in the ocean, 2) average concentration in the river runoff and 3) the type of distribution in oceanic water. Using knowledge of two of these parameters, it allows gaining theoretical knowledge of the third. The System covers all chemical elements for the entire range of observed concentrations. It even allows to predict the values of the annual river transport of dissolved Be, C, N, Ge, Tl, Re, to refine such estimates for P, V, Zn, Br, I, and to determine the character of distribution in the ocean for Au and U. Furthermore, the System allowed estimating natural (unaffected by anthropogenic influence) mean concentrations of elements in the river runoff and using them as ecological reference data. Finally, due to the long response time of the ocean, the mean concentrations of elements and patterns of their distribution in the ocean can be used to determine pre-techno-generative concentrations of elements in the river runoff. In our presentation, we shall show several examples of implementation of the System for studying the sediments' transport by the rivers of the Arctic slope of Northern Eurasia. References 1. Korzh V.D. 1974: Some general laws governing the turnover of substance within the ocean-atmosphere-continent-ocean cycle. Journal de Recherches Atmospheriques, 8, 653-660. 2. Korzh V.D. 2008: The general laws in the formation of the element composition of the Hydrosphere and Biosphere. J. Ecologica, 15, 13-21. 3. Korzh V.D. 2012: Determination of general laws of the chemical element composition in Hydrosphere. Water: Chemistry & Ecology, Journal of Water Science and its Practical Application. No. 1, 56-62.

Cooling of a magmatic system under thermal chaotic mixing

NASA Astrophysics Data System (ADS)

Petrelli, Maurizio; El Omari, Kamal; Le Guer, Yves; Perugini, Diego

2015-04-01

The cooling of a melt undergoing chaotic advection is studied numerically for a magma with a temperature-dependent viscosity in a 2D cavity with moving boundary. Different statistical mixing and energy indicators are used to characterize the efficiency of cooling by thermal chaotic mixing. We show that different cooling rates can be obtained during the thermal mixing even of a single basaltic magmatic batch undergoing chaotic advection. This process can induce complex temperature patterns inside the magma chamber. The emergence of chaotic dynamics strongly affects the temperature field during time and greatly increases the cooling rates. This mechanism has implications for the lifetime of a magmatic body and may favor the appearance of chemical heterogeneities in igneous systems as a result of different crystallization rates. Results from this study also highlight that even a single magma batch can develop, under chaotic thermal advection, complex thermal and therefore compositional patterns resulting from different cooling rates, which can account for some natural features that, to date, have received unsatisfactory explanations. Among them, the production of magmatic enclaves showing completely different cooling histories compared with the host magma, compositional zoning in mineral phases, and the generation of large-scale compositionally zoning observed in many plutons worldwide.

A chemical model for lunar non-mare rocks

NASA Technical Reports Server (NTRS)

Hubbard, N. J.; Rhodes, J. M.

1974-01-01

Nearly all rocks returned from the moon are readily divided into three broad categories on the basis of their chemical compositions: (1) mare basalts, (2) non-mare rocks of basaltic composition (KREEP, VHA), and (3) anorthositic rocks. Only mare basalts may unambiguously be considered to have original igneous textures and are widely understood to have an igneous origin. Nearly all other lunar rocks have lost their original textures during metamorphic and impact processes. It is shown that for these rocks one must work primarily with chemical data in order to recognize and define rock groups and their possible modes of origin. Non-mare rocks of basaltic composition have chemical compositions consistent with an origin by partial melting of the lunar interior. The simplest origin for rocks of anorthositic chemical composition is the crystallization and removal of ferromagnesian minerals. It is proposed that the rock groups of anorthositic and non-mare basaltic chemical composition could have been generated from a single series of original but not necessarily primitive lunar materials.

Polypyrrole-MWCNT-Ag composites for electromagnetic shielding: Comparison between chemical deposition and UV-reduction approaches

NASA Astrophysics Data System (ADS)

Ebrahimi, Izadyar; Gashti, Mazeyar Parvinzadeh

2018-07-01

In this study, we focused on the synthesis of polypyrrole-MWCNT-Ag composites and we evaluated their electrical properties to determine the electromagnetic interference shielding performance. We reduced silver nanoparticles in composites using two different in situ methods: UV-reduction and chemical deposition. Composites were characterized using spectroscopic and microscopic tools for evaluation of the chemical, morphological, electrical conductivity and electromagnetic shielding effectiveness. Results from Fourier transform infrared spectroscopy and dispersive Raman microscope showed chemical interactions between silver and the polypyrrole-MWCNT composite due to the charge-transfer within the structure. X-ray diffraction confirmed appearance of two new peaks for silver nanoparticles embedded in polypyrrole-MWCNT independent to reduction method. According to microscopy images, silver nanoparticles were homogenously distributed at the PPy-MWCNTs interfaces by UV reduction, while, chemical reduction resulted to deposition of silver within the PPy matrix. Finally, our results revealed that the polypyrrole-MWCNT-Ag composite produced via UV-reduction has higher electrical conductivity and shielding effectiveness in comparison to chemically reduced one.

A chemical model for lunar non-mare rocks

NASA Technical Reports Server (NTRS)

Hubbard, N. J.; Rhodes, J. M.

1977-01-01

Nearly all rocks returned from the moon are readily divided into three broad categories on the basis of their chemical compositions: (1) mare basalts, (2) non-mare rocks of basaltic composition (KREEP, VHA), and (3) anorthositic rocks. Only mare basalts may unambiguously be considered to have original igneous textures and are widely understood to have an igneous origin. Nearly all other lunar rocks have lost their original textures during metamorphic and impact processes. For these rocks one must work primarily with chemical data in order to recognize and define rock groups and their possible modes of origin. Non-mare rocks of basaltic composition have chemical compositions consistent with an origin by partial melting of the lunar interior. The simplest origin for rocks of anorthositic chemical composition is the crystallization and removal of ferromagnesian minerals. It is proposed that the rock groups of anorthositic and non-mare basaltic chemical composition could have been generated from a single series of original, but not necessarily primitive, lunar materials.

Frequency analysis of stress relaxation dynamics in model asphalts

NASA Astrophysics Data System (ADS)

Masoori, Mohammad; Greenfield, Michael L.

2014-09-01

Asphalt is an amorphous or semi-crystalline material whose mechanical performance relies on viscoelastic responses to applied strain or stress. Chemical composition and its effect on the viscoelastic properties of model asphalts have been investigated here by computing complex modulus from molecular dynamics simulation results for two different model asphalts whose compositions each resemble the Strategic Highway Research Program AAA-1 asphalt in different ways. For a model system that contains smaller molecules, simulation results for storage and loss modulus at 443 K reach both the low and high frequency scaling limits of the Maxwell model. Results for a model system composed of larger molecules (molecular weights 300-900 g/mol) with longer branches show a quantitatively higher complex modulus that decreases significantly as temperature increases over 400-533 K. Simulation results for its loss modulus approach the low frequency scaling limit of the Maxwell model at only the highest temperature simulated. A Black plot or van Gurp-Palman plot of complex modulus vs. phase angle for the system of larger molecules suggests some overlap among results at different temperatures for less high frequencies, with an interdependence consistent with the empirical Christensen-Anderson-Marasteanu model. Both model asphalts are thermorheologically complex at very high frequencies, where they show a loss peak that appears to be independent of temperature and density.

Volatile compounds in cryptic species of the Aneura pinguis complex and Aneura maxima (Marchantiophyta, Metzgeriidae).

PubMed

Wawrzyniak, Rafał; Wasiak, Wiesław; Bączkiewicz, Alina; Buczkowska, Katarzyna

2014-09-01

Aneura pinguis is one of the liverwort species complexes that consist of several cryptic species. Ten samples collected from different regions in Poland are in the focus of our research. Eight of the A. pinguis complex belonging to four cryptic species (A, B, C, E) and two samples of closely related species Aneura maxima were tested for the composition of volatile compounds. The HS-SPME technique coupled to GC/FID and GC/MS analysis has been applied. The fiber coated with DVB/CAR/PDMS has been used. The results of the present study, revealed the qualitative and quantitative differences in the composition of the volatile compounds between the studied species. Mainly they are from the group of sesquiterpenoids, oxygenated sesquiterpenoids and aliphatic hydrocarbons. The statistical methods (CA and PCA) showed that detected volatile compounds allow to distinguish cryptic species of A. pinguis. All examined cryptic species of the A. pinguis complex differ from A. maxima. Species A and E of A. pinguis, in CA and PCA, form separate clusters remote from two remaining cryptic species of A. pinguis (B and C) and A. maxima. Relationship between the cryptic species appeared from the chemical studies are in accordance with that revealed on the basis of DNA sequences. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantum mechanical studies of complex ferroelectric perovskites

NASA Astrophysics Data System (ADS)

Ramer, Nicholas John

In many electronic device applications, there is a need to interconvert electrical energy and other types of energy. Ferroelectric materials, which possess a voltage-dependent polarization, can enable this energy conversion process. Because of the broad interest in ferroelectric materials for these devices, there is a critical research effort, both experimental and theoretical, to understand these materials and aid in the development of materials with improved properties. This thesis presents detailed quantum mechanical investigations of the behavior of a complex ferroelectric perovskite under applied stress. In particular, we have chosen to study the solid solution PbZr1-xTix O3 (PZT). Since the study of ferroelectricity involves understanding both its structural and electronic signatures in materials, it has necessitated the development of a novel theoretical technique which improves the accuracy of the pseudopotentials used in our density functional theory calculations as well as a new method for constructing three-dimensional atomistic responses to small amounts of external stress. To examine the material's behavior under larger amounts of stress, we have studied the behavior of a composition of PZT lying near a structural phase boundary. On either side of the phase boundary, the material is characterized by a different polarization direction and may easily be switched between phases by applying external stress. In addition to stress-induced phase transitions, most ferroelectric materials also have composition dependent phase boundaries. Since different compositions of PZT would require increased computational effort, we have formulated an improved virtual crystal approach that makes tractable the study of the entire composition range. Using this method, we have been able to show for the first time via first-principles calculations, a composition dependent phase transition in a ferroelectric material. This thesis has accomplished three important goals: new theoretical methodology has been developed to enable accurate modeling of complex materials; application of these methods has been demonstrated for the study of ferroelectric oxides; and these investigations have revealed new insights into the relationships between stress, chemical composition, and ferroelectricity in oxides. This set of accomplishments enables the future study of even more complex perovskites and other multi-component systems.

Accelerated search for materials with targeted properties by adaptive design

PubMed Central

Xue, Dezhen; Balachandran, Prasanna V.; Hogden, John; Theiler, James; Xue, Deqing; Lookman, Turab

2016-01-01

Finding new materials with targeted properties has traditionally been guided by intuition, and trial and error. With increasing chemical complexity, the combinatorial possibilities are too large for an Edisonian approach to be practical. Here we show how an adaptive design strategy, tightly coupled with experiments, can accelerate the discovery process by sequentially identifying the next experiments or calculations, to effectively navigate the complex search space. Our strategy uses inference and global optimization to balance the trade-off between exploitation and exploration of the search space. We demonstrate this by finding very low thermal hysteresis (ΔT) NiTi-based shape memory alloys, with Ti50.0Ni46.7Cu0.8Fe2.3Pd0.2 possessing the smallest ΔT (1.84 K). We synthesize and characterize 36 predicted compositions (9 feedback loops) from a potential space of ∼800,000 compositions. Of these, 14 had smaller ΔT than any of the 22 in the original data set. PMID:27079901

Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide

PubMed Central

2013-01-01

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation. PMID:23750709

Use Zircon-Ilmenite Concentrate in Steelmaking

NASA Astrophysics Data System (ADS)

Fedoseev, S. N.; Volkova, T. N.

2016-08-01

Market requirements cause a constant search for new materials and technologies, for their immediate use in increasing requirements for material and energy efficiency, as well as to the quality of steel. In practice, steel production in the tended recently of more stringent requirements for the chemical composition of the steel and its contamination by nonmetallic inclusions, gas and non-ferrous metals. The main ways of increasing of strength and performance characteristics fabricated metal products related to the profound and effective influence on the crystallizing metal structure by furnace processing of the melt with refining and modifying additives. It can be argued that the furnace processing of steel and iron chemically active metals (alkali-earth metals, rare-earth metals, and others.) is an integral part of modern production of high quality products and competitive technologies. Important condition for development of methods secondary metallurgy of steel is the use of relatively inexpensive materials in a variety of complex alloys and blends, allowing targeted control of physical and chemical state of the molten metal and, therefore, receive steel with improved performance. In this connection the development of modifying natural materials metallurgy technologies presented complex ores containing titanium and zirconium, is a very urgent task.

Social context influences chemical communication in D. melanogaster males.

PubMed

Kent, Clement; Azanchi, Reza; Smith, Ben; Formosa, Amanda; Levine, Joel D

2008-09-23

Chemical communication mediates social interactions in insects. For the fruit fly, D. melanogaster, the chemical display is a key fitness trait because it leads to mating. An exchange of cues that resembles a dialogue between males and females is enacted by pheromones, chemical signals that pass between individual flies to alter physiology and behavior. Chemical signals also affect the timing of locomotor activity and sleep. We investigated genetic and environmental determinants of chemical communication. To evaluate the role of the social environment, we extracted a chemical blend from individual males selected from groups composed of one genotype and compared these extracts to those from groups of mixed genotypes. To evaluate the role of the physical environment, these comparisons were performed under a light-dark cycle or in constant darkness. Here, we show that chemical signaling is affected by the social environment, light-dark cycle, and genotype as well as the complex interplay of these variables. Gene-by-environment interactions produce highly significant effects on chemical signaling. We also examined individual responses within the groups. Strikingly, the response of one wild-type fly to another is modulated by the genotypic composition of his neighbors. Chemical signaling in D. melanogaster may be a "fickle" trait that depends on the individual's social background.

Enzyme Biosensors for Biomedical Applications: Strategies for Safeguarding Analytical Performances in Biological Fluids

PubMed Central

Rocchitta, Gaia; Spanu, Angela; Babudieri, Sergio; Latte, Gavinella; Madeddu, Giordano; Galleri, Grazia; Nuvoli, Susanna; Bagella, Paola; Demartis, Maria Ilaria; Fiore, Vito; Manetti, Roberto; Serra, Pier Andrea

2016-01-01

Enzyme-based chemical biosensors are based on biological recognition. In order to operate, the enzymes must be available to catalyze a specific biochemical reaction and be stable under the normal operating conditions of the biosensor. Design of biosensors is based on knowledge about the target analyte, as well as the complexity of the matrix in which the analyte has to be quantified. This article reviews the problems resulting from the interaction of enzyme-based amperometric biosensors with complex biological matrices containing the target analyte(s). One of the most challenging disadvantages of amperometric enzyme-based biosensor detection is signal reduction from fouling agents and interference from chemicals present in the sample matrix. This article, therefore, investigates the principles of functioning of enzymatic biosensors, their analytical performance over time and the strategies used to optimize their performance. Moreover, the composition of biological fluids as a function of their interaction with biosensing will be presented. PMID:27249001

Structure and Composition of the Bacillus anthracis Capsule

PubMed Central

Avakyan, A. A.; Katz, L. N.; Levina, K. N.; Pavlova, I. B.

1965-01-01

Avakyan, A. A. (Academy of Medical Sciences, Moscow, USSR), L. N. Katz, K. N. Levina, and I. B. Pavlova. Structure and composition of the Bacillus anthracis capsule. J. Bacteriol. 90:1082–1095. 1965.—Observations by various methods of light microscopy (phase contrast, dark-field, and fluorescence) revealed the complex structure of the Bacillus anthracis capsule, which changes regularly during the growth cycle of the culture. Special cytological methods of staining the capsule made it possible to study its fine structure, which is not revealed by negative staining with India ink. For example, the capsule shows a membranelike outline, fine transverse lines, and interruptions and transverse septa traversing the entire capsule. By using cytochemical methods, it was found that the capsule has a stratified structure and that the various layers of the capsule differ as to the value of the isoelectric point, metachromatic ability, sensitivity to various enzymes, and, consequently, chemical composition. It was thus shown that the membranelike outline of the capsule consists of peptides and neutral mucopolysaccharides. The middle part of the capsule consists of a complex of substances of both polysaccharide and protein nature, and the inner part consists of acid mucopolysaccharides. Observation of the capsular forms of B. anthracis by means of an electron microscope revealed differences in the osmiophilia and submicroscopic structure of the membranelike outline and the middle and inner parts of the capsule. Immunochemical studies conducted by the fluorescent-antibody method revealed localization of antigens in different parts of the capsule, and made it possible to differentiate the capsular antigens according to their serum-staining ability and according of their relations to enzymes, i.e., their chemical composition. This paper concerns the possibility of studying the fine structure of bacterial capsules in fixed preparations, and the differences and similarities of the antigens of the capsule and cell wall of B. anthracis and of the related species, B. megaterium. Images PMID:4954516

Growth of multi-component alloy films with controlled graded chemical composition on sub-nanometer scale

DOEpatents

Bajt, Sasa; Vernon, Stephen P.

2005-03-15

The chemical composition of thin films is modulated during their growth. A computer code has been developed to design specific processes for producing a desired chemical composition for various deposition geometries. Good agreement between theoretical and experimental results was achieved.

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Magma volumes and storage in the middle crust

NASA Astrophysics Data System (ADS)

Memeti, V.; Barnes, C. G.; Paterson, S. R.

2015-12-01

Quantifying magma volumes in magma plumbing systems is mostly done through geophysical means or based on volcanic eruptions. Detailed studies of plutons, however, are useful in revealing depths and evolving volumes of stored magmas over variable lifetimes of magma systems. Knowledge of the location, volume, and longevity of stored magma is critical for understanding where in the crust magmas attain their chemical signature, how these systems physically behave and how source, storage levels, and volcanoes are connected. Detailed field mapping, combined with single mineral geochemistry and geochronology of plutons, allow estimates of size and longevity of melt-interconnected magma batches that existed during the construction of magma storage sites. The Tuolumne intrusive complex (TIC) recorded a 10 myr magmatic history. Detailed maps of the major units in different parts of the TIC indicate overall smaller scale (cm- to <1 km) compositional variation in the oldest, outer Kuna Crest unit and mainly larger scale (>10 km) changes in the younger Half Dome and Cathedral Peak units. Mineral-scale trace element data from hornblende of granodiorites to gabbros from the Kuna Crest lobe show distinct hornblende compositions and zoning patterns. Mixed hornblende populations occur only at the transition to the main TIC. This compositional heterogeneity in the first 1-2 myr points to low volume magmatism resulting in smaller, discrete and not chemically interacting magma bodies. Trace element and Sr- and Pb-isotope data from growth zones of K-feldspar phenocrysts from the two younger granodiorites indicate complex mineral zoning, but general isotopic overlap, suggesting in-situ, inter-unit mixing and fractionation. This is supported by hybrid zones between units, mixing of zircon, hornblende, and K-feldspar populations and late leucogranites. Thus, magma body sizes increased later resulting in overall more homogeneous, but complexly mixing magma mushes that fractionated locally.

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments

NASA Astrophysics Data System (ADS)

Gautier, Thomas; Schmitz-Afonso, Isabelle; Touboul, David; Szopa, Cyril; Buch, Arnaud; Carrasco, Nathalie

2016-09-01

Although the Cassini Spacecraft and the Huygens lander provided vast information about Titan atmospheric chemistry and the formation of its aerosols, the exact composition of these aerosols still remains unknown. A fruitful proxy to investigate these aerosols is the use of laboratory experiments that allow producing and studying analogs of Titan aerosol, the so-called tholins. Even when produced in the laboratory, unveiling the exact composition of the aerosol remains problematic due to the high complexity of the material. Numerous advances have been recently made using high-resolution mass spectrometry (HRMS) (Pernot et al. [2010] Anal. Chem. 82, 1371; Somogyi et al. [2012] Int. J. Mass Spectrom. 316-318, 157-163; Gautier et al. [2014] Earth Planet. Sci. Lett. 404, 33-42) that allowed the separation of isobaric compounds and a robust identification of chemical species composing tholins regarding their molecular formulae. Nevertheless isomeric species cannot be resolved by a simple mass measurement. We propose here an analysis of tholins by high performance liquid chromatography (HPLC) coupled to HRMS to unveil this isomeric ambiguity for some of the major tholins compounds. By comparing chromatograms obtained when analyzing tholins and chemical standards, we strictly identified seven molecules in our tholins samples: melamine, cyanoguanidine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-triaminopyrimidine, 3-amino-1,2,4-triazole, 3,5-Dimethyl-1,2,4-triazole and 2,4-diamino-1,3,5-triazine. Several molecules, including hexamethylenetriamine (HMT) were not present at detectable levels in our sample. The use for the first time of a coupled HPLC-HRMS technique applied to tholins study demonstrated the interest of such a technique compared to single high-resolution mass spectrometry for the study of tholins composition.

Thermodynamic and Kinetic Aspects Involved in the Development of Nanocarriers and Drug Delivery Systems Based on Cationic Biopolymers.

PubMed

Bianco, Ismael D; Alasino, Roxana V; Leonhard, Victoria; Beltramo, Dante M

2016-01-01

During the last years we have seen an increasing number of reports describing new properties and potential applications of cationic polymers and derived nanostructures. This review gives a summary of their applications in drug delivery, the preparation methods for nano and microstructures and will attempt to give a glimpse on how their structure, chemical composition and properties may be affected or modulated as to make them suitable for an intended application as drug delivery nanocarriers. The compositional complexity with the existence of several reacting groups makes cationic nanostructures critically sensitive to the contribution of thermodynamic and kinetic parameters in the determination of the type and stability of a particular structure and its ability to respond to changes in environmental conditions in the right time frame. Curiously, and contrarily to what could be expected, despite the fact that cationic polymers can form strong electrostatic interactions the contribution of the entropic component has been often found to be very important for their association with negatively charged supramolecular structures. Some general considerations indicate that when considering a complex multimolecular system like a nanocarrier containing an active ingredient it is frequently possible to find conditions under which enthalpic and entropic contributions are compensated leading to stable structures with a marginal thermodynamic stability (free energy change close to zero) which make them able to respond relatively fast to changes in the environmental conditions and therefore suitable for the design of smart drug delivery systems. Like with other nanocarriers, it should always be kept in mind that the properties of cationic nanocarriers will depend not only on their chemical composition but also on the properties of the structures formed by them.

Efficacy of Meglumine Antimoniate under Low Polymerization State Orally Administrated in Murine Model of Visceral Leishmaniasis.

PubMed

Kato, Kelly C; de Morais-Teixeira, Eliane; Islam, Arshad; Leite, M Fatima; Demicheli, Cynthia; de Castro, Whocely V; Corrêa-Junior, José D; Rabello, Ana; Frézard, Frédéric

2018-06-04

Progress towards the improvement of meglumine antimoniate (MA) commercially known as Glucantime®, a highly effective but also toxic antileishmanial drug, has been hindered by the lack of knowledge and control on its chemical composition. Here, MA was manipulated chemically with the aim of achieving an orally effective drug. MA compounds were synthesized from either antimony pentachloride (MA-SbCl 5 ) or potassium hexahydroxyantimonate (MA-KSb(OH) 6 ) and prepared under low polymerization state. Those were compared to Glucantime® regarding chemical composition, permeation properties across cellulose membrane and Caco-2 cell monolayer and uptake by peritoneal macrophages. MA-SbCl 5 and MA-KSb(OH) 6 were characterized as less polymerized and more permeable 2:2 Sb-meglumine complexes, when compared to Glucantime® that consisted in a mixture of 2:3 and 3:3 Sb-meglumine complexes. The antileishmanial activity and hepatic uptake of all compounds were evaluated after oral administration in BALB/c mice infected with Leishmania infantum chagasi , as model of visceral leishmaniasis (VL). The synthetic MA compounds given at 300 mg Sb/kg/12h for 30 days reduced significantly spleen and liver parasite burdens, in contrast to Glucantime® at the same dose. The greater activity of synthetic compounds could be attributed to their higher intestinal absorption and accumulation efficiency in the liver. MA-SbCl 5 given orally was as efficacious as Glucantime® by parenteral route (80 mg Sb/kg/24h IP). This data taken altogether suggests that treatment with less polymerized form of MA by oral route may be effective for the treatment of VL. Copyright © 2018 American Society for Microbiology.

Chemical composition of felt-tip pen inks.

PubMed

Germinario, Giulia; Garrappa, Silvia; D'Ambrosio, Valeria; van der Werf, Inez Dorothé; Sabbatini, Luigia

2018-01-01

Felt-tip pens are frequently used for the realization of sketches, drawings, architectural projects, and other technical designs. The formulations of these inks are usually rather complex and may be associated to those of modern paint materials where, next to the binding medium and pigments/dyes, solvents, fillers, emulsifiers, antioxidants, plasticizers, light stabilizers, biocides, and so on are commonly added. Felt-tip pen inks are extremely sensitive to degradation and especially exposure to light may cause chromatic changes and fading. In this study, we report on the complete chemical characterization of modern felt-tip pen inks that are commercially available and commonly used for the realization of artworks. Three brands of felt-tip pens (Faber-Castell, Edding, and Stabilo) were investigated with complementary analytical techniques such as thin-layer chromatography (TLC), VIS-reflectance spectroscopy, μ-Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS), pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), GC-MS, and Fourier transform infrared (FTIR) spectroscopy. The use of TLC proved to be very powerful in the study of complex mixtures of synthetic dyes. First derivatives of the reflectance spectra acquired on the TLC spots were useful in the preliminary identification of the dye, followed by Raman spectroscopy and SERS, which allowed for the unambiguous determination of the chemical composition of the pigments (phthalocyanines, dioxazines, and azo pigments) and dyes (azo dyes, triarylmethanes, xanthenes). FTIR spectroscopy was used especially for the detection of additives, as well as for confirming the nature of solvents and dyes/pigments. Finally, (Py-)GC-MS data provided information on the binders (styrene-acrylic resins, plant gums), solvents, and additives, as well as on pigments and dyes.

Atmo-metabolomics: a new measurement approach for investigating aerosol composition and ecosystem functioning.

NASA Astrophysics Data System (ADS)

Rivas-Ubach, A.; Liu, Y.; Sardans, J.; Tfaily, M. M.; Kim, Y. M.; Bourrianne, E.; Paša-Tolić, L.; Penuelas, J.; Guenther, A. B.

2016-12-01

Aerosols play crucial roles in the processes controlling the composition of the atmosphere and the functioning of ecosystems. Gaining a deeper understanding of the chemical composition of aerosols is one of the major challenges for atmospheric and climate scientists and is beginning to be recognized as important for ecological research. Better comprehension of aerosol chemistry can potentially provide valuable information on atmospheric processes such as oxidation of organics and the production of cloud condensation nuclei as well as provide an approximation of the general status of an ecosystem through the measurement of certain stress biomarkers. In this study, we describe an efficient aerosol sampling method, the metabolite extraction and the analytical procedures for the chemical characterization of aerosols, namely, the atmo-metabolome. We used mass spectrometry (MS) coupled to liquid chromatography (LC-MS), gas chromatography (GC-MS) and Fourier transform ion cyclotron resonance (FT-ICR-MS) to characterize the atmo-metabolome of two marked seasons; spring and summer. Our sampling and extraction methods demonstrated to be suitable for aerosol chemical characterization with any of the analytical platforms used in this study. The atmo-metabolome between spring and summer showed overall statistically differences. We identified several metabolites that can be attributed to pollen and other plant-related aerosols. Spring aerosols exhibit higher concentrations of metabolites linked to higher plant activity while summer samples had higher concentrations of metabolites that may reflect certain oxidative stresses in primary producers. Moreover, the elemental composition of aerosols showed clear different between seasons. Summer aerosols were generally higher in molecular weight and with higher O/C ratios, indicating higher oxidation levels and condensation of compounds relative to spring. Our method represents an advanced approach for characterizing the composition of aerosols that will benefit scientists attempting to understand complex atmospheric processes and the ecosystem status across a whole ecoregion.

Changes in properties of polyacid-modified composite resins (compomers) following storage in acidic solutions.

PubMed

Nicholson, J W; Gjorgievska, E; Bajraktarova, B; McKenzie, M A

2003-06-01

The interaction of three polyacid-modified composite resins (compomers) with various acidic storage solutions, and also water, over periods of time up to 6 months has been studied and compared with those of a glass-ionomer and a composite resin. This interaction has been shown to vary in a complex way with length of storage and nature of the acid, and citric acid was found to be the most aggressive storage medium for glass-ionomer cement, and also for the compomers. The pure composite resin, by contrast, was relatively unaffected by all of the acid solutions examined. In all acids, the compomers showed a distinct buffering effect, i.e. they increased the pH towards neutral, as did the glass-ionomer. The extent of this also varied with duration of storage and nature of the acid. The biaxial flexure strength was determined and found to be essentially unaffected by the complex chemical interactions with acidic storage solutions. Values obtained for the compomers were lower than those of the composite resin, but above those of the glass-ionomer. Fourier-transform infrared (FT-IR) spectroscopy was employed to study the changes in the compomers following storage in the aqueous media, but bands were broad and no detailed assignments could be made. There were changes in the region of the spectra associated with metal carboxylates however, and this indicates that the secondary acid-base reaction had occurred following water uptake.

Improvement of the Correlative AFM and ToF-SIMS Approach Using an Empirical Sputter Model for 3D Chemical Characterization.

PubMed

Terlier, T; Lee, J; Lee, K; Lee, Y

2018-02-06

Technological progress has spurred the development of increasingly sophisticated analytical devices. The full characterization of structures in terms of sample volume and composition is now highly complex. Here, a highly improved solution for 3D characterization of samples, based on an advanced method for 3D data correction, is proposed. Traditionally, secondary ion mass spectrometry (SIMS) provides the chemical distribution of sample surfaces. Combining successive sputtering with 2D surface projections enables a 3D volume rendering to be generated. However, surface topography can distort the volume rendering by necessitating the projection of a nonflat surface onto a planar image. Moreover, the sputtering is highly dependent on the probed material. Local variation of composition affects the sputter yield and the beam-induced roughness, which in turn alters the 3D render. To circumvent these drawbacks, the correlation of atomic force microscopy (AFM) with SIMS has been proposed in previous studies as a solution for the 3D chemical characterization. To extend the applicability of this approach, we have developed a methodology using AFM-time-of-flight (ToF)-SIMS combined with an empirical sputter model, "dynamic-model-based volume correction", to universally correct 3D structures. First, the simulation of 3D structures highlighted the great advantages of this new approach compared with classical methods. Then, we explored the applicability of this new correction to two types of samples, a patterned metallic multilayer and a diblock copolymer film presenting surface asperities. In both cases, the dynamic-model-based volume correction produced an accurate 3D reconstruction of the sample volume and composition. The combination of AFM-SIMS with the dynamic-model-based volume correction improves the understanding of the surface characteristics. Beyond the useful 3D chemical information provided by dynamic-model-based volume correction, the approach permits us to enhance the correlation of chemical information from spectroscopic techniques with the physical properties obtained by AFM.

Graphene Oxide-A Tool for the Preparation of Chemically Crosslinking Free Alginate-Chitosan-Collagen Scaffolds for Bone Tissue Engineering.

PubMed

Kolanthai, Elayaraja; Sindu, Pugazhendhi Abinaya; Khajuria, Deepak Kumar; Veerla, Sarath Chandra; Kuppuswamy, Dhandapani; Catalani, Luiz Henrique; Mahapatra, D Roy

2018-04-18

Developing a biodegradable scaffold remains a major challenge in bone tissue engineering. This study was aimed at developing novel alginate-chitosan-collagen (SA-CS-Col)-based composite scaffolds consisting of graphene oxide (GO) to enrich porous structures, elicited by the freeze-drying technique. To characterize porosity, water absorption, and compressive modulus, GO scaffolds (SA-CS-Col-GO) were prepared with and without Ca 2+ -mediated crosslinking (chemical crosslinking) and analyzed using Raman, Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscopy techniques. The incorporation of GO into the SA-CS-Col matrix increased both crosslinking density as indicated by the reduction of crystalline peaks in the XRD patterns and polyelectrolyte ion complex as confirmed by FTIR. GO scaffolds showed increased mechanical properties which were further increased for chemically crosslinked scaffolds. All scaffolds exhibited interconnected pores of 10-250 μm range. By increasing the crosslinking density with Ca 2+ , a decrease in the porosity/swelling ratio was observed. Moreover, the SA-CS-Col-GO scaffold with or without chemical crosslinking was more stable as compared to SA-CS or SA-CS-Col scaffolds when placed in aqueous solution. To perform in vitro biochemical studies, mouse osteoblast cells were grown on various scaffolds and evaluated for cell proliferation by using MTT assay and mineralization and differentiation by alizarin red S staining. These measurements showed a significant increase for cells attached to the SA-CS-Col-GO scaffold compared to SA-CS or SA-CS-Col composites. However, chemical crosslinking of SA-CS-Col-GO showed no effect on the osteogenic ability of osteoblasts. These studies indicate the potential use of GO to prepare free SA-CS-Col scaffolds with preserved porous structure with elongated Col fibrils and that these composites, which are biocompatible and stable in a biological medium, could be used for application in engineering bone tissues.

X-ray photoelectron spectroscopic analysis of rice kernels and flours: Measurement of surface chemical composition.

PubMed

Nawaz, Malik A; Gaiani, Claire; Fukai, Shu; Bhandari, Bhesh

2016-12-01

The objectives of this study were to evaluate the ability of X-ray photoelectron spectroscopy (XPS) to differentiate rice macromolecules and to calculate the surface composition of rice kernels and flours. The uncooked kernels and flours surface composition of the two selected rice varieties, Thadokkham-11 (TDK11) and Doongara (DG) demonstrated an over-expression of lipids and proteins and an under-expression of starch compared to the bulk composition. The results of the study showed that XPS was able to differentiate rice polysaccharides (mainly starch), proteins and lipids in uncooked rice kernels and flours. Nevertheless, it was unable to distinguish components in cooked rice samples possibly due to complex interactions between gelatinized starch, denatured proteins and lipids. High resolution imaging methods (Scanning Electron Microscopy and Confocal Laser Scanning Microscopy) were employed to obtain complementary information about the properties and location of starch, proteins and lipids in rice kernels and flours. Copyright © 2016. Published by Elsevier Ltd.

Identifying Nanoscale Structure-Function Relationships Using Multimodal Atomic Force Microscopy, Dimensionality Reduction, and Regression Techniques.

PubMed

Kong, Jessica; Giridharagopal, Rajiv; Harrison, Jeffrey S; Ginger, David S

2018-05-31

Correlating nanoscale chemical specificity with operational physics is a long-standing goal of functional scanning probe microscopy (SPM). We employ a data analytic approach combining multiple microscopy modes, using compositional information in infrared vibrational excitation maps acquired via photoinduced force microscopy (PiFM) with electrical information from conductive atomic force microscopy. We study a model polymer blend comprising insulating poly(methyl methacrylate) (PMMA) and semiconducting poly(3-hexylthiophene) (P3HT). We show that PiFM spectra are different from FTIR spectra, but can still be used to identify local composition. We use principal component analysis to extract statistically significant principal components and principal component regression to predict local current and identify local polymer composition. In doing so, we observe evidence of semiconducting P3HT within PMMA aggregates. These methods are generalizable to correlated SPM data and provide a meaningful technique for extracting complex compositional information that are impossible to measure from any one technique.

Method of producing a chemical hydride

DOEpatents

Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

2007-11-13

A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

Simulating the Composite Propellant Manufacturing Process

NASA Technical Reports Server (NTRS)

Williamson, Suzanne; Love, Gregory

2000-01-01

There is a strategic interest in understanding how the propellant manufacturing process contributes to military capabilities outside the United States. The paper will discuss how system dynamics (SD) has been applied to rapidly assess the capabilities and vulnerabilities of a specific composite propellant production complex. These facilities produce a commonly used solid propellant with military applications. The authors will explain how an SD model can be configured to match a specific production facility followed by a series of scenarios designed to analyze operational vulnerabilities. By using the simulation model to rapidly analyze operational risks, the analyst gains a better understanding of production complexities. There are several benefits of developing SD models to simulate chemical production. SD is an effective tool for characterizing complex problems, especially the production process where the cascading effect of outages quickly taxes common understanding. By programming expert knowledge into an SD application, these tools are transformed into a knowledge management resource that facilitates rapid learning without requiring years of experience in production operations. It also permits the analyst to rapidly respond to crisis situations and other time-sensitive missions. Most importantly, the quantitative understanding gained from applying the SD model lends itself to strategic analysis and planning.

Environmental mineralogy - Understanding element behavior in ecosystems

NASA Astrophysics Data System (ADS)

Brown, Gordon E., Jr.; Calas, Georges

2011-02-01

Environmental Mineralogy has developed over the past decade in response to the recognition that minerals are linked in many important ways with the global ecosystem. Minerals are the main repositories of the chemical elements in Earth's crust and thus are the main sources of elements needed for the development of civilization, contaminant and pollutant elements that impact global and local ecosystems, and elements that are essential plant nutrients. These elements are released from minerals through natural processes, such as chemical weathering, and anthropogenic activities, such as mining and energy production, agriculture and industrial activities, and careless waste disposal. Minerals also play key roles in the biogeochemical cycling of the elements, sequestering elements and releasing them as the primary minerals in crustal rocks undergo various structural and compositional transformations in response to physical, chemical, and biological processes that produce secondary minerals and soils. These processes have resulted in the release of toxic elements such as arsenic in groundwater aquifers, which is having a major impact on the health of millions of people in South and Southeast Asia. The interfaces between mineral surfaces and aqueous solutions are the locations of most chemical reactions that control the composition of the natural environment, including the composition of natural waters. The nuclear fuel cycle, from uranium mining to the disposition of high-level nuclear waste, is also intimately related to minerals. A fundamental understanding of these processes requires molecular-scale information about minerals, their bulk structures and properties such as solubility, their surfaces, and their interactions with aqueous solutions, atmospheric and soil gases, natural organic matter, and biological organisms. Gaining this understanding is further complicated by the presence of natural, incidental, and manufactured nanoparticles in the environment, which are becoming increasingly important due to the rapidly developing field of nanotechnology. As a result of this complexity, Environmental Mineralogy requires the use of the most modern molecular-scale analytical and theoretical methods and overlaps substantially with closely related fields such as Environmental Sciences, low-temperature Geochemistry, and Geomicrobiology. This paper provides brief overviews of the above topics and discusses the complexity of minerals, natural vs. anthropogenic inputs of elements and pollutants into the biosphere, the role of minerals in the biogeochemical cycling of elements, natural nanoparticles, and the Environmental Mineralogy of three major potential pollutant elements (Hg, As and U).

A composite of complex and chemical hydrides yields the first Al-based amidoborane with improved hydrogen storage properties.

PubMed

Dovgaliuk, Iurii; Jepsen, Lars H; Safin, Damir A; Łodziana, Zbigniew; Dyadkin, Vadim; Jensen, Torben R; Devillers, Michel; Filinchuk, Yaroslav

2015-10-05

The first Al-based amidoborane Na[Al(NH2 BH3 )4 ] was obtained through a mechanochemical treatment of the NaAlH4 -4 AB (AB=NH3 BH3 ) composite releasing 4.5 wt % of pure hydrogen. The same amidoborane was also produced upon heating the composite at 70 °C. The crystal structure of Na[Al(NH2 BH3 )4 ], elucidated from synchrotron X-ray powder diffraction and confirmed by DFT calculations, contains the previously unknown tetrahedral ion [Al(NH2 BH3 )4 ](-) , with every NH2 BH3 (-) ligand coordinated to aluminum through nitrogen atoms. Combination of complex and chemical hydrides in the same compound was possible due to both the lower stability of the AlH bonds compared to the BH ones in borohydride, and due to the strong Lewis acidity of Al(3+) . According to the thermogravimetric analysis-differential scanning calorimetry-mass spectrometry (TGA-DSC-MS) studies, Na[Al(NH2 BH3 )4 ] releases in two steps 9 wt % of pure hydrogen. As a result of this decomposition, which was also supported by volumetric studies, the formation of NaBH4 and amorphous product(s) of the surmised composition AlN4 B3 H(0-3.6) were observed. Furthermore, volumetric experiments have also shown that the final residue can reversibly absorb about 27 % of the released hydrogen at 250 °C and p(H2 )=150 bar. Hydrogen re-absorption does not regenerate neither Na[Al(NH2 BH3 )4 ] nor starting materials, NaAlH4 and AB, but rather occurs within amorphous product(s). Detailed studies of the latter one(s) can open an avenue for a new family of reversible hydrogen storage materials. Finally, the NaAlH4 -4 AB composite might become a starting point towards a new series of aluminum-based tetraamidoboranes with improved hydrogen storage properties such as hydrogen storage density, hydrogen purity, and reversibility. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Deep Crust Magmatic Refinery, Part 2 : The Magmatic Output of Numerical Models.

NASA Astrophysics Data System (ADS)

Bouilhol, P.; Riel, N., Jr.; Van Hunen, J.

2016-12-01

Metamorphic and magmatic processes occurring in the deep crust ultimately control the chemical and physical characteristic of the continental crust. A complex interplay between magma intrusion, crystallization, and reaction with the pre-existing crust provide a wide range of differentiated magma and cumulates (and / or restites) that will feed the upper crustal levels with evolved melt while constructing the lower crust. With growing evidence from field and experimental studies, it becomes clearer that crystallization and melting processes are non-exclusive but should be considered together. Incoming H2O bearing mantle melts will start to fractionate to a certain extent, forming cumulates but also releasing heat and H2O to the intruded host-rock allowing it to melt in saturated conditions. The end-result of such dynamic system is a function of the amount and composition of melt input, and extent of reaction with the host which is itself dependent on the migration mode of the melts. To better constrain lower crust processes, we have built up a numerical model [see Riel et al. associated abstract for methods] to explore different parameters, unravelling the complex interplay between melt percolation / crystallization and degassing / re-melting in a so called "hot zone" model. We simulated the intrusion of water bearing mantle melts at the base of an amphibolitized lower crust during a magmatic event that lasts 5 Ma. We varied several parameters such as Moho depth and melt rock ratio to better constrain what controls the final melt / lower crust composition.. We show the evolution of the chemical characteristics of the melt that escape the system during this magmatic event, as well as the resulting lower crust characteristics. We illustrate how the evolution of melt major elements composition reflects the progressive replacement of the crust towards compositions that are dominated by the mantle melt input. The resulting magmas cover a wide range of composition from tonalite to granite, and the modelled lower crust shows all the petrological characteristic of observed lower arc-crust.

Uranium adsorption on weathered schist - Intercomparison of modeling approaches

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Ochs, M.; Olin, M.; Tweed, C.J.

2004-01-01

Experimental data for uranium adsorption on a complex weathered rock were simulated by twelve modelling teams from eight countries using surface complexation (SC) models. This intercomparison was part of an international project to evaluate the present capabilities and limitations of SC models in representing sorption by geologic materials. The models were assessed in terms of their predictive ability, data requirements, number of optimised parameters, ability to simulate diverse chemical conditions and transferability to other substrates. A particular aim was to compare the generalised composite (GC) and component additivity (CA) approaches for modelling sorption by complex substrates. Both types of SC models showed a promising capability to simulate sorption data obtained across a range of chemical conditions. However, the models incorporated a wide variety of assumptions, particularly in terms of input parameters such as site densities and surface site types. Furthermore, the methods used to extrapolate the model simulations to different weathered rock samples collected at the same field site tended to be unsatisfactory. The outcome of this modelling exercise provides an overview of the present status of adsorption modelling in the context of radionuclide migration as practised in a number of countries worldwide.

Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

NASA Astrophysics Data System (ADS)

Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

2015-07-01

Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

Review on effect of chemical, thermal, additive treatment on mechanical properties of basalt fiber and their composites

NASA Astrophysics Data System (ADS)

Jain, Naman; Singh, Vinay Kumar; Chauhan, Sakshi

2017-12-01

Basalt fiber is emerging out the new reinforcing material for composites. To overcome some of the disadvantages of fibers such as poor bonding to polymers, low thermal stability and high moisture absorption fiber characteristics are modified with chemical, thermal and additive treatments. Chemical treatment corrosive resistance to alkali and acid were investigated which were used to clean and modify the surface of fiber for higher bonding with resins. To improve the thermal stability and reduce moisture uptake thermal treatment such as plasma and non thermal plasma were used which increased the surface roughness and change the chemical composition of surface of basalt fiber. Additive treatment is used to improve the mechanical properties of fibers, in basalt fiber additive treatment was done with SiO2 additive because of its chemical composition which contains major content of SiO2. In present investigation review on the effect of different treatment such as chemical, thermal and additive were studied. Effect of these treatment on chemical composition of the surface of basalt fiber and corrosion to acidic and alkali solution were studied with their effect on mechanical properties of basalt fiber and their composite.

Cometary science. Time variability and heterogeneity in the coma of 67P/Churyumov-Gerasimenko.

PubMed

Hässig, M; Altwegg, K; Balsiger, H; Bar-Nun, A; Berthelier, J J; Bieler, A; Bochsler, P; Briois, C; Calmonte, U; Combi, M; De Keyser, J; Eberhardt, P; Fiethe, B; Fuselier, S A; Galand, M; Gasc, S; Gombosi, T I; Hansen, K C; Jäckel, A; Keller, H U; Kopp, E; Korth, A; Kührt, E; Le Roy, L; Mall, U; Marty, B; Mousis, O; Neefs, E; Owen, T; Rème, H; Rubin, M; Sémon, T; Tornow, C; Tzou, C-Y; Waite, J H; Wurz, P

2015-01-23

Comets contain the best-preserved material from the beginning of our planetary system. Their nuclei and comae composition reveal clues about physical and chemical conditions during the early solar system when comets formed. ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) onboard the Rosetta spacecraft has measured the coma composition of comet 67P/Churyumov-Gerasimenko with well-sampled time resolution per rotation. Measurements were made over many comet rotation periods and a wide range of latitudes. These measurements show large fluctuations in composition in a heterogeneous coma that has diurnal and possibly seasonal variations in the major outgassing species: water, carbon monoxide, and carbon dioxide. These results indicate a complex coma-nucleus relationship where seasonal variations may be driven by temperature differences just below the comet surface. Copyright © 2015, American Association for the Advancement of Science.

Additive manufacturing of biologically-inspired materials.

PubMed

Studart, André R

2016-01-21

Additive manufacturing (AM) technologies offer an attractive pathway towards the fabrication of functional materials featuring complex heterogeneous architectures inspired by biological systems. In this paper, recent research on the use of AM approaches to program the local chemical composition, structure and properties of biologically-inspired materials is reviewed. A variety of structural motifs found in biological composites have been successfully emulated in synthetic systems using inkjet-based, direct-writing, stereolithography and slip casting technologies. The replication in synthetic systems of design principles underlying such structural motifs has enabled the fabrication of lightweight cellular materials, strong and tough composites, soft robots and autonomously shaping structures with unprecedented properties and functionalities. Pushing the current limits of AM technologies in future research should bring us closer to the manufacturing capabilities of living organisms, opening the way for the digital fabrication of advanced materials with superior performance, lower environmental impact and new functionalities.

Prediction of a New Phase of Cu x S near Stoichiometric Composition

DOE PAGES

Khatri, Prashant; Huda, Muhammad N.

2015-01-01

Cumore » 2 S is known to be a promising solar absorber material due to its suitable band gap and the abundance of its constituent elements. 2 S is known to have complex phase structures depending on the concentration of vacancies. Its instability of phases is due to favorable formation of vacancies and the mobility of atoms within the crystal. Understanding its phase structures is of crucial important for its application as solar absorber material. In this paper, we have predicted a new crystal phase of copper sulfide ( x S) around chemical composition of x = 1.98 by utilizing crystal database search and density functional theory. We have shown that this new crystal phase of x S is more favorable than low chalcocite structure even at stoichiometric composition of x = 2 . However, vacancy formation probability was found to be higher in this new phase than the low chalcocite structure.« less

Profile of Polyphenolic and Essential Oil Composition of Polish Propolis, Black Poplar and Aspens Buds.

PubMed

Okińczyc, Piotr; Szumny, Antoni; Szperlik, Jakub; Kulma, Anna; Franiczek, Roman; Żbikowska, Beata; Krzyżanowska, Barbara; Sroka, Zbigniew

2018-05-25

In this work, we studied similarities and differences between 70% ethanol in water extract (70EE) and essential oils (EOs) obtained from propolis, black poplars ( Populus nigra L.) and aspens ( P. tremula L.) to ascertain which of these is a better indicator of the plant species used by bees to collect propolis precursors. Composition of 70EE was analyzed by UPLC-PDA-MS, while GC-MS was used to research the EOs. Principal component analyses (PCA) and calculations of Spearman's coefficient rank were used for statistical analysis. Statistical analysis exhibited correlation between chemical compositions of propolis and Populus buds' 70EE. In the case of EOs, results were less clear. Compositions of black poplars, aspens EOs and propolises have shown more variability than 70EE. Different factors such as higher instability of EOs compared to 70EE, different degradation pattern of benzyl esters to benzoic acid, differences in plant metabolism and bees' preferences may be responsible for these phenomena. Our research has therefore shown that 70EE of propolis reflected the composition of P. nigra or complex aspen⁻black poplar origin.

Fast classification and compositional analysis of cornstover fractions using Fourier transform near-infrared techniques.

PubMed

Philip Ye, X; Liu, Lu; Hayes, Douglas; Womac, Alvin; Hong, Kunlun; Sokhansanj, Shahab

2008-10-01

The objectives of this research were to determine the variation of chemical composition across botanical fractions of cornstover, and to probe the potential of Fourier transform near-infrared (FT-NIR) techniques in qualitatively classifying separated cornstover fractions and in quantitatively analyzing chemical compositions of cornstover by developing calibration models to predict chemical compositions of cornstover based on FT-NIR spectra. Large variations of cornstover chemical composition for wide calibration ranges, which is required by a reliable calibration model, were achieved by manually separating the cornstover samples into six botanical fractions, and their chemical compositions were determined by conventional wet chemical analyses, which proved that chemical composition varies significantly among different botanical fractions of cornstover. Different botanic fractions, having total saccharide content in descending order, are husk, sheath, pith, rind, leaf, and node. Based on FT-NIR spectra acquired on the biomass, classification by Soft Independent Modeling of Class Analogy (SIMCA) was employed to conduct qualitative classification of cornstover fractions, and partial least square (PLS) regression was used for quantitative chemical composition analysis. SIMCA was successfully demonstrated in classifying botanical fractions of cornstover. The developed PLS model yielded root mean square error of prediction (RMSEP %w/w) of 0.92, 1.03, 0.17, 0.27, 0.21, 1.12, and 0.57 for glucan, xylan, galactan, arabinan, mannan, lignin, and ash, respectively. The results showed the potential of FT-NIR techniques in combination with multivariate analysis to be utilized by biomass feedstock suppliers, bioethanol manufacturers, and bio-power producers in order to better manage bioenergy feedstocks and enhance bioconversion.

Geochemical and physical drivers of microbial community structure in hot spring ecosystems

NASA Astrophysics Data System (ADS)

Havig, J. R.; Hamilton, T. L.; Boyd, E. S.; Meyer-Dombard, D. R.; Shock, E.

2012-12-01

Microbial communities in natural systems are typically characterized using samples collected from a single time point, thereby neglecting the temporal dynamics that characterize natural systems. The composition of these communities obtained from single point samples is then related to the geochemistry and physical parameters of the environment. Since most microbial life is adapted to a relatively narrow ecological niche (multiplicity of physical and chemical parameters that characterize a local habitat), these assessments provide only modest insight into the controls on community composition. Temporal variation in temperature or geochemical composition would be expected to add another dimension to the complexity of niche space available to support microbial diversity, with systems that experience greater variation supporting a greater biodiversity until a point where the variability is too extreme. . Hot springs often exhibit significant temporal variation, both in physical as well as chemical characteristics. This is a result of subsurface processes including boiling, phase separation, and differential mixing of liquid and vapor phase constituents. These characteristics of geothermal systems, which vary significantly over short periods of time, provide ideal natural laboratories for investigating how i) the extent of microbial community biodiversity and ii) the composition of those communities are shaped by temporal fluctuations in geochemistry. Geochemical and molecular samples were collected from 17 temporally variable hot springs across Yellowstone National Park, Wyoming. Temperature measurements using data-logging thermocouples, allowing accurate determination of temperature maximums, minimums, and ranges for each collection site, were collected in parallel, along with multiple geochemical characterizations as conditions varied. There were significant variations in temperature maxima (54.5 to 90.5°C), minima (12.5 to 82.5°C), and range (3.5 to 77.5°C) for the hot spring environments that spanned ranges of pH values (2.2 to 9.0) and geochemical compositions. We characterized the abundance, composition, and phylogenetic diversity of bacterial and archaeal 16S rRNA gene assemblages in sediment/biofilm samples collected from each site. 16S data can be used as proxy for metabolic dissimilarity. We predict that temporally fluctuating environments should provide additional complexity to the system (additional niche space) capable of supporting additional taxa, which should lead to greater 16S rRNA gene diversity. However, systems with too much variability should collapse the diversity. Thus, one would expect an optimal system for variability, with respect to 16S phylogenetic diversity. Community ecology tools were then applied to model the relative influence of physical and chemical characteristics (including temperature dynamics) on the local biodiversity. The results reveal unique insight into the role of temporal environmental variation in the development of biodiverse communities and provide a platform for predicting the response of an ecosystem to temperature perturbation.

Cygnus Orbital ATK OA-6 Liftoff

NASA Image and Video Library

2016-03-22

At Cape Canaveral Air Force Station's Space Launch Complex 41, a United Launch Alliance Atlas V rocket with a single-engine Centaur upper stage stands ready to boost an Orbital ATK Cygnus spacecraft on a resupply mission to the International Space Station. Science payloads include the second generation of a portable onboard printer to demonstrate three-dimensional printing, an instrument for first space-based observations of the chemical composition of meteors entering Earth’s atmosphere and an experiment to study how fires burn in microgravity.

Cygnus Orbital ATK OA-6 Rollout

NASA Image and Video Library

2016-03-21

At Cape Canaveral Air Force Station's Space Launch Complex 41, a United Launch Alliance Atlas V rocket with a single-engine Centaur upper stage stands ready to boost an Orbital ATK Cygnus spacecraft on a resupply mission to the International Space Station. Science payloads include the second generation of a portable onboard printer to demonstrate three-dimensional printing, an instrument for first space-based observations of the chemical composition of meteors entering Earth’s atmosphere and an experiment to study how fires burn in microgravity.

Method of bundling rods so as to form an optical fiber preform

DOEpatents

Kliner, Dahv A. V. [San Ramon, CA; Koplow, Jeffery P [Washington, DC

2004-03-30

The present invention provides a simple method for fabricating fiber-optic glass preforms having complex refractive index configurations and/or dopant distributions in a radial direction with a high degree of accuracy and precision. The method teaches bundling together a plurality of glass rods of specific physical, chemical, or optical properties and wherein the rod bundle is fused in a manner that maintains the cross-sectional composition and refractive-index profiles established by the position of the rods.

Autonomous cycling between excitatory and inhibitory coupling in photosensitive chemical oscillators

NASA Astrophysics Data System (ADS)

Yengi, Desmond; Tinsley, Mark R.; Showalter, Kenneth

2018-04-01

Photochemically coupled Belousov-Zhabotinsky micro-oscillators are studied in experiments and simulations. The photosensitive oscillators exhibit excitatory or inhibitory coupling depending on the surrounding reaction mixture composition, which can be systematically varied. In-phase or out-of-phase synchronization is observed with predominantly excitatory or inhibitory coupling, respectively, and complex frequency cycling between excitatory and inhibitory coupling is found between these extremes. The dynamical behavior is characterized in terms of the corresponding phase response curves, and a map representation of the dynamics is presented.

A composite CdS thin film/TiO2 nanotube structure by ultrafast successive electrochemical deposition toward photovoltaic application

NASA Astrophysics Data System (ADS)

Fu, Han; Liu, Hong; Shen, Wenzhong

2014-11-01

Fabricating functional compounds on substrates with complicated morphology has been an important topic in material science and technology, which remains a challenging issue to simultaneously achieve a high growth rate for a complex nanostructure with simple controlling factors. Here, we present a novel simple and successive method based on chemical reactions in an open reaction system manipulated by an electric field. A uniform CdS/TiO2 composite tubular structure has been fabricated in highly ordered TiO2 nanotube arrays in a very short time period (~90 s) under room temperature (RT). The content of CdS in the resultant and its crystalline structure was tuned by the form and magnitude of external voltage. The as-formed structure has shown a quite broad and bulk-like light absorption spectrum with the absorption of photon energy even below that of the bulk CdS. The as-fabricated-sensitized solar cell based on this composite structure has achieved an efficiency of 1.43% without any chemical doping or co-sensitizing, 210% higher than quantum dot-sensitized solar cell (QDSSC) under a similar condition. Hopefully, this method can also easily grow nanostructures based on a wide range of compound materials for energy science and electronic technologies, especially for fast-deploying devices.

Evaluating Changes in the Molecular Composition and Optical Properties of Pacific Ocean Dissolved Organic Matter (DOM) caused by Borodeuteride Reduction

NASA Astrophysics Data System (ADS)

Bianca, M.; Blough, N. V.; Del Vecchio, R.; Cartisano, C. M.; Schmitt-Kopplin, P.; Gonsior, M.

2016-02-01

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) is a powerful tool to obtain detailed molecular information for complex DOM and was combined in this study with optical measurements to determine the molecular fingerprint of Pacific Ocean DOM before and after borodeuteride reduction. Selective chemical reductions, using sodium borodeuteride, has been previously demonstrated to produce unique mass markers of ketone and aldehyde-containing species in ultrahigh resolution mass spectrometry. These functional groups have also been proposed to be responsible for chromophoric dissolved organic matter (CDOM) long wavelength optical properties through charge transfer interactions and their chemical reduction has shown to irreversibly alter the CDOM optical properties. ESI-FT-ICR MS coupled with borodeuteride reduction was thus applied to reference material, Suwannee River Fulvic Acid (SRFA), and CDOM extracts collected from Station ALOHA, in the North Pacific Ocean during December 2014. Results showed distinct differences between samples collected at different depths, indicating that the combination of FT-ICR-MS with borodeuteride reduction is a useful analytical tool to further understand marine DOM molecular composition. When this method is combined with optical measurements, specific insights into the CDOM composition can also be obtained.

The GSTome Reflects the Chemical Environment of White-Rot Fungi

PubMed Central

Deroy, Aurélie; Saiag, Fanny; Kebbi-Benkeder, Zineb; Touahri, Nassim; Hecker, Arnaud; Morel-Rouhier, Mélanie; Colin, Francis; Dumarcay, Stephane; Gérardin, Philippe; Gelhaye, Eric

2015-01-01

White-rot fungi possess the unique ability to degrade and mineralize all the different components of wood. In other respects, wood durability, among other factors, is due to the presence of extractives that are potential antimicrobial molecules. To cope with these molecules, wood decay fungi have developed a complex detoxification network including glutathione transferases (GST). The interactions between GSTs from two white-rot fungi, Trametes versicolor and Phanerochaete chrysosporium, and an environmental library of wood extracts have been studied. The results demonstrate that the specificity of these interactions is closely related to the chemical composition of the extracts in accordance with the tree species and their localization inside the wood (sapwood vs heartwood vs knotwood). These data suggest that the fungal GSTome could reflect the chemical environment encountered by these fungi during wood degradation and could be a way to study their adaptation to their way of life. PMID:26426695

Cuticular Lipids as a Cross-Talk among Ants, Plants and Butterflies

PubMed Central

Barbero, Francesca

2016-01-01

Even though insects and plants are distantly related organisms, they developed an integument which is functionally and structurally similar. Besides functioning as a physical barrier to cope with abiotic and biotic stress, this interface, called cuticle, is also a source of chemical signaling. Crucial compounds with this respect are surface lipids and especially cuticular hydrocarbons (CHCs). This review is focused on the role of CHCs in fostering multilevel relationships among ants, plants and Lepidoptera (primarily butterflies). Indeed, particular traits of ants as eusocial organisms allowed the evolution and the maintenance of a variety of associations with both plants and animals. Basic concepts of myrmecophilous interactions and chemical deception strategies together with chemical composition, biosynthetic pathways and functions of CHCs as molecular cues of multitrophic systems are provided. Finally, the need to adopt a multidisciplinary and comprehensive approach in the survey of complex models is discussed. PMID:27886144

Surface Traps in Colloidal Quantum Dots: A Combined Experimental and Theoretical Perspective

PubMed Central

2017-01-01

Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their atomistic origin and manipulating them chemically have capital importance to design defect-free colloidal quantum dots and make a leap forward in the development of efficient optoelectronic devices. Recent advances in computing power established computational chemistry as a powerful tool to describe accurately complex chemical species and nowadays it became conceivable to model colloidal quantum dots with realistic sizes and shapes. In this Perspective, we combine the knowledge gathered in recent experimental findings with the computation of quantum dot electronic structures. We analyze three different systems: namely, CdSe, PbS, and CsPbI3 as benchmark semiconductor nanocrystals showing how different types of trap states can form at their surface. In addition, we suggest experimental healing of such traps according to their chemical origin and nanocrystal composition. PMID:28972763

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

Not Available

This purpose of this report is to summarize the activities of the Analytical Chemistry Laboratory (ACL) at Argonne National Laboratory (ANL) for Fiscal Year 1990. The ACL has four technical groups -- Chemical Analysis, Instrumental Analysis, Organic Analysis, and Environmental Analysis. The Chemical Analysis Group uses wet-chemical and instrumental methods for elemental, compositional, and isotopic analyses of solid, liquid, and gaseous samples and provides specialized analytical services. The Instrumental Analysis Group uses nuclear counting techniques in radiochemical analyses over a wide range of sample types from low-level environmental samples to samples of high radioactivity. The Organic Analysis Group uses amore » number of complementary techniques to separate and to quantitatively and qualitatively analyze complex organic mixtures and compounds at the trace level, including synthetic fuels, toxic substances, fossil-fuel residues and emissions, pollutants, biologically active compounds, pesticides, and drugs. The Environmental Analysis Group performs analyses of inorganic environmental and hazardous waste and coal samples.« less

High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

PubMed Central

Rivas-Murias, Beatriz; Manuel Vila-Fungueiriño, José; Rivadulla, Francisco

2015-01-01

Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures. PMID:26153533

Cuticular Lipids as a Cross-Talk among Ants, Plants and Butterflies.

PubMed

Barbero, Francesca

2016-11-24

Even though insects and plants are distantly related organisms, they developed an integument which is functionally and structurally similar. Besides functioning as a physical barrier to cope with abiotic and biotic stress, this interface, called cuticle, is also a source of chemical signaling. Crucial compounds with this respect are surface lipids and especially cuticular hydrocarbons (CHCs). This review is focused on the role of CHCs in fostering multilevel relationships among ants, plants and Lepidoptera (primarily butterflies). Indeed, particular traits of ants as eusocial organisms allowed the evolution and the maintenance of a variety of associations with both plants and animals. Basic concepts of myrmecophilous interactions and chemical deception strategies together with chemical composition, biosynthetic pathways and functions of CHCs as molecular cues of multitrophic systems are provided. Finally, the need to adopt a multidisciplinary and comprehensive approach in the survey of complex models is discussed.

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones.

PubMed

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-12-16

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ 66 Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ 66 Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO 4 2- complexes preferentially incorporate heavy δ 66 Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge.

Chemical composition of distillers grains, a review.

PubMed

Liu, KeShun

2011-03-09

In recent years, increasing demand for ethanol as a fuel additive and decreasing dependency on fossil fuels have resulted in a dramatic increase in the amount of grains used for ethanol production. Dry-grind is the major process, resulting in distillers dried grains with solubles (DDGS) as a major coproduct. Like fuel ethanol, DDGS has quickly become a global commodity. However, high compositional variation has been the main problem hindering its use as a feed ingredient. This review provides updated information on the chemical composition of distillers grains in terms of nutrient levels, changes during dry-grind processing, and causes for large variation. The occurrence in grain feedstock and the fate of mycotoxins during processing are also covered. During processing, starch is converted to glucose and then to ethanol and carbon dioxide. Most other components are relatively unchanged but concentrated in DDGS about 3-fold over the original feedstock. Mycotoxins, if present in the original feedstock, are also concentrated. Higher fold of increases in S, Na, and Ca are mostly due to exogenous addition during processing, whereas unusual changes in inorganic phosphorus (P) and phytate P indicate phytate hydrolysis by yeast phytase. Fermentation causes major changes, but other processing steps are also responsible. The causes for varying DDGS composition are multiple, including differences in feedstock species and composition, process methods and parameters, the amount of condensed solubles added to distiller wet grains, the effect of fermentation yeast, and analytical methodology. Most of them can be attributed to the complexity of the dry-grind process itself. It is hoped that information provided in this review will improve the understanding of the dry-grind process and aid in the development of strategies to control the compositional variation in DDGS.

Chemical composition and digestibility of Trifolium exposed to elevated ozone and carbon dioxide in a free-air (FACE) fumigation system

Treesearch

R.B. Muntifering; A.H. Chappelka; J.C. Lin; D.F. Karnosky; G.L. Somers

2006-01-01

Tropospheric ozone (O3) and carbon dioxide (CO2) are significant drivers of plant growth and chemical composition. We hypothesized that exposure to elevated concentrations of O3 and CO2, singly and in combination, would modify the chemical composition of Trifolium...

Synthesis, structural, photophysical and thermal studies of benzoate bridged Sm(III) complexes

NASA Astrophysics Data System (ADS)

Singh, Udai P.; Kumar, Rajeev; Upreti, Shailesh

2007-04-01

One samarium coordination polymer (chain like) 1 with composition [{Sm(OBz) 3(MeO) 2} 2] n has been prepared from the reaction of SmCl 3 and sodium benzoate in 1:3 ratio whereas four binuclear samarium complexes with chemical composition [{(tp)Sm(μ- p-X-OBz) 2} 2] have been prepared by the reaction of SmCl 3, potassium hydrotris(pyrazol-1-yl)borate [K(tp)] and sodium p-X-benzoate (where X = H, Cl, F, NO 2) in 1:1:2 ratio. These complexes have been characterized by elemental analysis, IR spectroscopy, thermogravimetry, optical properties, X-ray and magnetic measurement studies. The X-ray structure shows that the complexes 2- 5 are isostructural whereas the structure of 1 is different. The coordination number around metal center in 1 is eight whereas in complexes 2- 5, each samarium is seven coordinate. The X-ray studies indicate that the complex 1 crystallizes in monoclinic space group P2(1)/ c with the cell dimensions a = 9.75(7), b = 21.83(15), c = 22.28(15) Å, whereas the complexes 2 and 3 crystallizes isostructurally in the triclinic space group P1¯ with the cell dimension a = 11.77(10), b = 12.60(10), c = 17.57(13) Å and a = 9.55(3), b = 12.80(4), c = 14.47(5) Å, respectively. The samarium ions in 2 and 3 are coordinated by three N atoms of pyrazolylborate ligand and four O atoms from benzoate groups. The photophysical properties of above complexes have been studied with ultraviolet absorption, excitation and emission spectral studies. The complexes 1- 5 excited at 240 nm wavelength produced characteristic luminescence features, arising mostly due to the f-f transitions.

Ion Formation Resulting from Freezing, Thawing, and Collisional Processes in Plumes Emitted from Planetary Bodies: Implications for Plume Chemistry and the Detection of Trace Organics Present in Enceladus Geysers

NASA Astrophysics Data System (ADS)

Beauchamp, J. L.; Wiley, J. S.; Thomas, D. A.

2014-12-01

Icy plumes emitted into space from Enceladus and other planetary bodies offer the intriguing possibility of sampling the composition of subsurface liquid reservoirs that may comprise habitable zones of particular astrobiological significance in our solar system. Mass spectrometric sampling of plume materials enables the detection of molecules that facilitate an assessment of the extent of chemical and biological evolution that may have occurred in a subsurface sea. In laboratory experiments we have investigated the physical and chemical processes that occur in the complex plume environment that lead to ionization of trace organic constituents, both as a result of the freezing of liquid droplets and the thawing of icy particles. We also demonstrate that collisions between icy particles lead to triboelectric charging. Subsequent discharges between oppositely charged particles result not only in the ionization of trace organics but to chemical reactions between molecular components present in the particles. For example, nitriles react with water to form amides and acids. In particular, icy particles doped with small amounts of aminoacetonitrile and water lead to the formation of the simplest amino acid glycine. The implications which these observations may have for sampling plume composition from orbit in a future mission to Enceladus will be discussed.

Elemental analysis of scorpion venoms.

PubMed

Al-Asmari, AbdulRahman K; Kunnathodi, Faisal; Al Saadon, Khalid; Idris, Mohammed M

2016-01-01

Scorpion venom is a rich source of biomolecules, which can perturb physiological activity of the host on envenomation and may also have a therapeutic potential. Scorpion venoms produced by the columnar cells of venom gland are complex mixture of mucopolysaccharides, neurotoxic peptides and other components. This study was aimed at cataloguing the elemental composition of venoms obtained from medically important scorpions found in the Arabian peninsula. The global elemental composition of the crude venom obtained from Androctonus bicolor, Androctonus crassicauda and Leiurus quinquestriatus scorpions were estimated using ICP-MS analyzer. The study catalogued several chemical elements present in the scorpion venom using ICP-MS total quant analysis and quantitation of nine elements exclusively using appropriate standards. Fifteen chemical elements including sodium, potassium and calcium were found abundantly in the scorpion venom at PPM concentrations. Thirty six chemical elements of different mass ranges were detected in the venom at PPB level. Quantitative analysis of the venoms revealed copper to be the most abundant element in Androctonus sp. venom but at lower level in Leiurus quinquestriatus venom; whereas zinc and manganese was found at higher levels in Leiurus sp. venom but at lower level in Androctonus sp. venom. These data and the concentrations of other different elements present in the various venoms are likely to increase our understanding of the mechanisms of venom activity and their pharmacological potentials.

Comparison of the structure, crystallography and composition of eggshells of the guinea fowl and graylag goose.

PubMed

Pérez-Huerta, Alberto; Dauphin, Yannicke

2016-02-01

The structure and composition of the eggshells of two commercial species (guinea fowl and greylag goose) have been studied. Thin sections and scanning electron microcopy show the similarity of the overall structure, but the relative thickness of the layers differs in these two taxa. Atomic force microscopy shows that the different layers are composed of rounded, heterogeneous granules, the diameter of which is between 50 and 100 nm, with a thin cortex. Infrared data and thermogravimetric analyses show that both eggshells are made of calcite, but differing on the quality and quantity when the organic component is considered. Chemical maps show that chemical element distribution is not uniform within a sample, and differs between the species, but with low magnesium content. Electron back scattered diffraction confirms the eggshells are calcite, but the microtexture strongly differs between the two species. Based on the chemical-structural differences, a species-specific biological control on the biomineralization is found, despite the rapid formation of an eggshell. Overall results indicate that to estimate the quality of eggshells, such as resistance to breakage, is not a straightforward process because of the high complexity of avian eggshell biomineralization. Copyright © 2015 Elsevier GmbH. All rights reserved.

Hydrogeology of northern Sierra de Chiapas, Mexico: a conceptual model based on a geochemical characterization of sulfide-rich karst brackish springs

NASA Astrophysics Data System (ADS)

Rosales Lagarde, Laura; Boston, Penelope J.; Campbell, Andrew R.; Hose, Louise D.; Axen, Gary; Stafford, Kevin W.

2014-09-01

Conspicuous sulfide-rich karst springs flow from Cretaceous carbonates in northern Sierra de Chiapas, Mexico. This is a geologically complex, tropical karst area. The physical, geologic, hydrologic and chemical attributes of these springs were determined and integrated into a conceptual hydrogeologic model. A meteoric source and a recharge elevation below 1,500 m are estimated from the spring-water isotopic signature regardless of their chemical composition. Brackish spring water flows at a maximum depth of 2,000 m, as inferred from similar chemical attributes to the produced water from a nearby oil well. Oil reservoirs may be found at depths below 2,000 m. Three subsurface environments or aquifers are identified based on the B, Li+, K+ and SiO2 concentrations, spring water temperatures, and CO2 pressures. There is mixing between these aquifers. The aquifer designated Local is shallow and contains potable water vulnerable to pollution. The aquifer named Northern receives some brackish produced water. The composition of the Southern aquifer is influenced by halite dissolution enhanced at fault detachment surfaces. Epigenic speleogenesis is associated with the Local springs. In contrast, hypogenic speleogenesis is associated with the brackish sulfidic springs from the Northern and the Southern environments.

Characterization of soil and postlaunch pad debris from Cape Canaveral launch complex and analysis of soil interaction with aqueous HCl

NASA Technical Reports Server (NTRS)

Pellett, G. L.; Spangler, L. W.; Storey, R. W.; Bendura, R. J.

1982-01-01

Soil samples were fractionated and analyzed in order to assess the physical and chemical interactions of entrained soil with solid-rocket exhaust clouds. The sandy soil consisted primarily of quartz (silica) particles, 30 to 500 microns in diameter, and also contained seashell fragments. Differential and cumulative soil-mass size distributions are presented along with mineralogy, elemental compositions, and solution pH histories. About 90 percent of the soil mass consisted of particles 165 microns in diameter. Characteristic reaction times in aqueous HC1 slurries varied from a few minutes to several days, and capacities for reaction under acidic conditions varied from 10 to 40 g HCl/kg soil, depending on particle size. Airborne lifetimes of particles 165 microns are conservatively 30 min, and this major grouping is predicted to represent a small short-term chemical sink for up to 5% of the total HC1. The smaller and more minor fractions, below a 165 micron diameter, may act as giant cloud condensation nuclei over much longer airborne lifetimes. Finally, the demonstrated time dependency of neutralization is a complicating factor; it can influence the ability to deduce in-cloud HCl scavenging with reaction and can affect the accuracy of measured chemical compositions of near-field wet deposition.

Analysis of the relation between the cellulose, hemicellulose and lignin content and the thermal behavior of residual biomass from olive trees.

PubMed

Garcia-Maraver, A; Salvachúa, D; Martínez, M J; Diaz, L F; Zamorano, M

2013-11-01

The heterogeneity of biomass makes it difficult if not impossible to make sweeping generalizations concerning thermochemical treatment systems and the optimal equipment to be used in them. Chemical differences in the structural components of the biomass (cellulose, hemicellulose, and lignin) have a direct impact on its chemical reactivity. The aim of this research was to study the influence of the organic components of the raw material from olive trees (leaves, pruning residues, and wood) in the combustion behavior of this biomass, as well as to find the component responsible for the higher ash content of olive leaves. Accordingly, the study used a thermogravimetric analyzer to monitor the different states and complex transitions that occurred in the biomass as the temperature varied. The decomposition rates of the different samples were analyzed in order to establish a link between each combustion phase and the composition of the raw materials. Two methods were used to determine the hemicellulose and cellulose contents of biomass from olive trees. Significant differences among the results obtained by the different methods were observed, as well as important variations regarding the chemical composition and consequently the thermal behavior of the raw materials tested. Copyright © 2013 Elsevier Ltd. All rights reserved.

An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

Airborne single particle mass spectrometers (SPLAT II & miniSPLAT) and new software for data visualization and analysis in a geo-spatial context.

PubMed

Zelenyuk, Alla; Imre, Dan; Wilson, Jacqueline; Zhang, Zhiyuan; Wang, Jun; Mueller, Klaus

2015-02-01

Understanding the effect of aerosols on climate requires knowledge of the size and chemical composition of individual aerosol particles-two fundamental properties that determine an aerosol's optical properties and ability to serve as cloud condensation or ice nuclei. Here we present our aircraft-compatible single particle mass spectrometers, SPLAT II and its new, miniaturized version, miniSPLAT that measure in-situ and in real-time the size and chemical composition of individual aerosol particles with extremely high sensitivity, temporal resolution, and sizing precision on the order of a monolayer. Although miniSPLAT's size, weight, and power consumption are significantly smaller, its performance is on par with SPLAT II. Both instruments operate in dual data acquisition mode to measure, in addition to single particle size and composition, particle number concentrations, size distributions, density, and asphericity with high temporal resolution. We also present ND-Scope, our newly developed interactive visual analytics software package. ND-Scope is designed to explore and visualize the vast amount of complex, multidimensional data acquired by our single particle mass spectrometers, along with other aerosol and cloud characterization instruments on-board aircraft. We demonstrate that ND-Scope makes it possible to visualize the relationships between different observables and to view the data in a geo-spatial context, using the interactive and fully coupled Google Earth and Parallel Coordinates displays. Here we illustrate the utility of ND-Scope to visualize the spatial distribution of atmospheric particles of different compositions, and explore the relationship between individual particle compositions and their activity as cloud condensation nuclei.

Some General Laws of Chemical Elements Composition Dynamics in the Hydrosphere

NASA Astrophysics Data System (ADS)

Korzh, V.

2012-12-01

The biophysical oceanic composition is a result of substance migration and transformation on river-sea and ocean- atmosphere boundaries. Chemical composition of oceanic water is a fundamental multi-dimensional constant for our planet. Detailed studies revealed three types of chemical element distribution in the ocean: 1) Conservative: concentration normalized to salinity is constant in space and time; 2) Nutrient-type: element concentration in the surface waters decreases due to the biosphere consumption; and 3) Litho-generative: complex character of distribution of elements, which enter the ocean with the river runoff and interred almost entirely in sediments (Fig. 1). The correlation between the chemical compositions of the river and oceanic water is high (r = 0.94). We conclude that biogeochemical features of each element are determined by the relationship between its average concentration in the ocean and the intensity of its migration through hydrosphere boundary zones. In Fig.1 we show intensities of global migration and average concentrations in the ocean in the coordinates lgC - lg τ, where C is an average element concentration and τ is its residual time in the ocean. Fig. 1 shows a relationship between three main geochemical parameters of the dissolved forms of chemical elements in the hydrosphere: 1) average concentration in the ocean, 2) average concentration in the river runoff and 3) the type of distribution in oceanic water. Using knowledge of two of these parameters, it allows gaining theoretical knowledge of the third. The System covers all chemical elements for the entire range of observed concentrations. It even allows to predict the values of the annual river transport of dissolved Be, C, N, Ge, Tl, Re, to refine such estimates for P, V, Zn, Br, I, and to determine the character of distribution in the ocean for Au and U. Furthermore, the System allowed to estimate natural (unaffected by anthropogenic influence) mean concentrations of elements in the river runoff and use them as ecological reference data. Finally, due to the long response time of the ocean, the mean concentrations of elements and patterns of their distribution in the ocean can be used to determine pre-technogenic concentrations of elements in the river runoff. An example of such studies for the Northern Eurasia Arctic Rivers will be presented at the conference. References Korzh 1974: J. de Recher. Atmos, 8, 653-660. Korzh 2008: J. Ecol., 15, 13-21. Korzh 2012: Water: Chem. & Ecol., No. 1, 56-62; Fig.1. The System of chemical elements distribution in the hydrosphere. Types of distribution in the ocean: 1) conservative; 2) nutrient-type; 3) litho-generative.

Unravelling the chemical characteristics of YSOs

NASA Astrophysics Data System (ADS)

van Dishoeck, Ewine F.

1999-10-01

The formation of stars is accompanied by orders of magnitude changes in the physical conditions, with densities in the envelopes and disks increasing from 104 cm-3 to > 1013 cm-3 and temperatures from ~ 10 K in the cold quiescent gas to 10,000 K in shocked regions. The abundances and excitation of the various molecules respond to these changes, and are therefore excellent probes of the physical evolution of YSOs. Moreover, a comprehensive inventory of the chemical composition of envelopes and disks at different evolutionary stages is essential to study the chemistry of matter as it is incorporated into new solar systems. Recent observations of the envelopes of YSOs using single-dish telescopes and millimeter interferometers clearly reveal the potential of submillimeter lines to probe these physical and chemical changes. However, the existing data generally lack the spatial resolution to separate the different physical components, such as the warm inner envelope or `hot core', the region of interaction of the outflow with the envelope and any possible circumstellar disk. ALMA will be essential to provide an `unblurred' view of the YSO environment and unravel the chemical evolution during star formation. In this talk, an overview will be given of recent single-dish and interferometer results of the chemistry in the envelopes and disks around low- and high-mass young stellar objects. Together with ISO data on solid-state material, these observations lead to a chemical scenario in which both gas-phase and gas-grain chemistry (in particular freeze-out and evaporation) play an important role. The evaporated molecules drive a rich chemistry in the warm gas, which can result in complex organic molecules. The potential of ALMA to test chemical theories and determine the composition of gas and dust as it enters forming planetary systems will be illustrated.

Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Mcbride, Bonnie J.

1994-01-01

This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

Synthesis and characterization of a novel tube-in-tube nanostructured PPy/MnO{sub 2}/CNTs composite for supercapacitor

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

Li, Juan, E-mail: lj-panpan@163.com; Beijing National Laboratory for Molecular Sciences; Que, Tingli

2013-02-15

Graphical abstract: A novel tube-in-tube nanostructured PPy/MnO{sub 2}/CNTs composite have been successfully fabricated. Its inner tubules are CNTs and the outer tubules are template-synthesized PPy. Most MnO{sub 2} nanoparticles are sandwiched between the inner and outer wall, some relatively large particles are also latched onto the outside wall of the PPy tube. The composite yields a good electrochemical reversibility through 1000 cycles’ cyclic voltammogram (CV) test and galvanostatic charge–discharge experiments at different current densities. Display Omitted Highlights: ► We fabricate a ternary organic–inorganic complex of PPy/MnO{sub 2}/CNTs composite. ► We characterize its morphological structures and properties by several techniques. ►more » The composite possesses the typical tube-in-tube nanostructures. ► Most MnO{sub 2} nanoparticles are sandwiched between the inner CNTs and outer PPy wall. ► The composite has good electrochemical reversibility for supercapacitor. -- Abstract: Ternary organic–inorganic complex of polypyrrole/manganese dioxide/carbon nanotubes (PPy/MnO{sub 2}/CNTs) composite was prepared by in situ chemical oxidation polymerization of pyrrole in the host of inorganic matrix of MnO{sub 2} and CNTs, using complex of methyl orange (MO)/FeCl{sub 3} was used as a reactive self-degraded soft-template. The morphological structures of the composite were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopic (HRTEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD), respectively. All the results indicate that the PPy/MnO{sub 2}/CNTs composite possesses the typical tube-in-tube nanostructures: the inner tubules are CNTs and the outer tubules are template-synthesized PPy. MnO{sub 2} nanoparticles may either sandwich the space between the inner and outer tubules or directly latch onto the wall of the PPy tubes. The composite yields a good electrochemical reversibility through 1000 cycles’ cyclic voltammogram (CV) test in the potential range of −0.6 to 0.4 V and its specific capacitance was up to 402.7 F g{sup −1} at a current density of 1 A g{sup −1} in galvanostatic charge–discharge experiment.« less

The interdependence between screening methods and screening libraries.

PubMed

Shelat, Anang A; Guy, R Kiplin

2007-06-01

The most common methods for discovery of chemical compounds capable of manipulating biological function involves some form of screening. The success of such screens is highly dependent on the chemical materials - commonly referred to as libraries - that are assayed. Classic methods for the design of screening libraries have depended on knowledge of target structure and relevant pharmacophores for target focus, and on simple count-based measures to assess other properties. The recent proliferation of two novel screening paradigms, structure-based screening and high-content screening, prompts a profound rethink about the ideal composition of small-molecule screening libraries. We suggest that currently utilized libraries are not optimal for addressing new targets by high-throughput screening, or complex phenotypes by high-content screening.

Structural and morphological study of chemically synthesized CdSe thin films

NASA Astrophysics Data System (ADS)

Agrawal, P.; Singh, Randhir; Sharma, Jeewan; Sachdeva, M.; Singh, Anupinder; Bhargava, A.

2018-05-01

Nanocrystalline CdSe thin films were prepared by Chemical Bath Deposition (CBD) method using potassium nitrilo-triacetic acid cadmium complex and sodium selenosulphite. The as deposited films were red in color, uniform and well adherent to the glass substrate. These films were strongly dependent on the deposition parameters such as bath composition, deposition temperature and time. Films were annealed at 350 °C for four hours. The morphological, structural and optical properties were studied using X-ray diffraction (XRD), UV-VIS spectrophotometer measurements, scanning electron microscopy and atomic force microscopy. The XRD analysis confirmed that films are predominantly in hexagonal phase. Scanning electron micrograph shows that the grains are uniformly spread all over the film and each grain contains many nanocrystals with spherical shapes.

The Allende multicompound chondrule (ACC)—Chondrule formation in a local super-dense region of the early solar system

NASA Astrophysics Data System (ADS)

Bischoff, Addi; Wurm, Gerhard; Chaussidon, Marc; Horstmann, Marian; Metzler, Knut; Weyrauch, Mona; Weinauer, Julia

2017-05-01

In Allende, a very complex compound chondrule (Allende compound chondrule; ACC) was found consisting of at least 16 subchondrules (14 siblings and 2 independents). Its overall texture can roughly be described as a barred olivine object (BO). The BO texture is similar in all siblings, but does not exist in the two independents, which appear as relatively compact olivine-rich units. Because of secondary alteration of pristine Allende components and the ACC in particular, only limited predictions can be made concerning the original compositions of the colliding melt droplets. Based on textural and mineralogical characteristics, the siblings must have been formed on a very short time scale in a dense, local environment. This is also supported by oxygen isotope systematics showing similar compositions for all 16 subchondrules. Furthermore, the ACC subchondrules are isotopically distinct from typical Allende chondrules, indicating formation in or reaction with a more 16O-poor reservoir. We modeled constraints on the particle density required at the ACC formation location, using textural, mineral-chemical, and isotopic observations on this multicompound chondrule to define melt droplet collision conditions. In this context, we discuss the possible relationship between the formation of complex chondrules and the formation of macrochondrules and cluster chondrites. While macrochondrules may have formed under similar or related conditions as complex chondrules, cluster chondrites certainly require different formation conditions. Cluster chondrites represent a mixture of viscously deformed, seemingly young chondrules of different chemical and textural types and a population of older chondrules. Concerning the formation of ACC calculations suggest the existence of very local, kilometer-sized, and super-dense chondrule-forming regions with extremely high solid-to-gas mass ratios of 1000 or more.

Geology is the Key to Explain Igneous Activity in the Mediterranean Area

NASA Astrophysics Data System (ADS)

Lustrino, M.

2014-12-01

Igneous activity in tectonically complex areas can be interpreted in many different ways, producing completely different petrogenetic models. Processes such as oceanic and continental subduction, lithospheric delamination, changes in subduction polarity, slab break-off and mantle plumes have all been advocated as causes for changes in plate boundaries and magma production, including rate and temporal distribution, in the circum-Mediterranean area. This region thus provides a natural laboratory to investigate a range of geodynamic and magmatic processes. Although many petrologic and tectonic models have been proposed, a number of highly controversial questions still remain. No consensus has yet been reached about the capacity of plate-tectonic processes to explain the origin and style of the magmatism. Similarly, there is still not consensus on the ability of geochemical and petrological arguments to reveal the geodynamic evolution of the area. The wide range of chemical and mineralogical magma compositions produced within and around the Mediterranean, from carbonatites to strongly silica-undersaturated silico-carbonatites and melilitites to strongly silica-oversaturated rhyolites, complicate models and usually require a large number of unconstrained assumptions. Can the calcalkaline-sodic alkaline transition be related to any common petrogenetic point? Is igneous activity plate-tectonic- (top-down) or deep-mantle-controlled (bottom-up)? Do the rare carbonatites and carbonate-rich igneous rocks derive from the deep mantle or a normal, CO2-bearing upper mantle? Do ultrapotassic compositions require continental subduction? Understanding chemically complex magmas emplaced in tectonically complex areas require open minds, and avoiding dogma and assumptions. Studying the geology and shallow dynamics, not speculating about the deep lower mantle, is the key to understanding the igneous activity.

Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts.

PubMed

Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

2013-01-15

New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts

NASA Astrophysics Data System (ADS)

Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

2013-01-01

New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals.

Estimation of chemical carcass composition from 8th rib characteristics with Belgian blue double-muscled bulls.

PubMed

De Campeneere, S; Fiems, L O; Van de Voorde, G; Vanacker, J M; Boucque, C V; Demeyer, D I

1999-01-01

Characteristics from the 8th rib cut: chemical composition, tissue composition after dissection, specific gravity (SG) and m. longissimus thoracis (LT) composition, collected on 17 Belgian Blue double-muscled fattening bulls were used to generate equations for predicting chemical carcass composition. Carcass composition was best predicted from chemical analysis of the 8th rib cut and the empty body weight (EBW) of the bull. Carcass chemical fat content (CCF, kg) was predicted from the 8th rib cut fat content (ether extract, 8RF, kg) by the following regression: CCF=1.94+27.37 8RF (R(2)=0.957, RSD =9.89%). A higher coefficient was found for carcass water (CCW, kg) predicted from 8RF and EBW: CCW=-2.26+0.28 EBW-34.28 8RF (R(2)=0.997, RSD=1.48%). No parameter was found to improve the prediction of CCP from EBW solely: CCP=-0.86+0.08 EBW (R(2) =0.992, RSD=2.61%). Prediction equations based solely on LT composition had low R(2) values of between 0.38 and 0.67, whereas no significant equations were found using SG. However, equations based on EBW had R(2) values between 0.78 and 0.99. Chemical components of the 8th rib cut in combination with EBW are most useful in predicting the chemical composition of the carcass of Belgian-Blue double-muscled bulls.

Study of chloride ion transport of composite by using cement and starch as a binder

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

Armynah, Bidayatul; Halide, Halmar; Zahrawani,

This study presents the chemical bonding and the structural properties of composites from accelerator chloride test migration (ACTM). The volume fractions between binder (cement and starch) and charcoal in composites are 20:80 and 60:40. The effect of the binder to the chemical composition, chemical bonding, and structural properties before and after chloride ion passing through the composites was determined by X-ray fluorescence (XRF), by Fourier transform infra-red (FTIR), and x-ray diffraction (XRD), respectively. From the XRD data, XRF data, and the FTIR data shows the amount of chemical composition, the type of binding, and the structure of composites are dependingmore » on the type of binder. The amount of chloride migration using starch as binder is higher than that of cement as a binder due to the density effects.« less

Pulsed plasma chemical synthesis of SixCyOz composite nanopowder

NASA Astrophysics Data System (ADS)

Kholodnaya, G.; Sazonov, R.; Ponomarev, D.; Remnev, G.

2017-05-01

SixCyOz composite nanopowder with an average size of particles about 10-50 nm was produced using the pulsed plasma chemical method. The experiments on the synthesis of nanosized composite were carried out using a TEA-500 pulsed electron accelerator. To produce a composite, SiCl4, O2, and CH4 were used. The major part of experiments was conducted using a plasma chemical reactor (quartz, 140 mm diameter, 6 l volume). The initial reagents were injected into the reactor, then a pulsed electron beam was injected which initiated the chemical reactions whose products were the SixCyOz composite nanopowder. To define the morphology of the particles, the JEOL-II-100 transmission electron microscope (TEM) with an accelerating voltage of 100 kV was used. The substances in the composition of the composite nanopowder were identified using the infrared absorption optical spectrum. To conduct this analysis, the Nicolet 5700 FT-IR spectrometer was used.

Method for Forming Fiber Reinforced Composite Bodies with Graded Composition and Stress Zones

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay (Inventor); Levine, Stanley R. (Inventor); Smialek, James A. (Inventor)

1999-01-01

A near-net, complex shaped ceramic fiber reinforced silicon carbide based composite bodies with graded compositions and stress zones is disclosed. To provide the composite a fiber preform is first fabricated and an interphase is applied by chemical vapor infiltration, sol-gel or polymer processes. This first body is further infiltrated with a polymer mixture containing carbon, and/or silicon carbide, and additional oxide, carbide, or nitride phases forming a second body. One side of the second body is spray coated or infiltrated with slurries containing high thermal expansion and oxidation resistant. crack sealant phases and the other side of this second body is coated with low expansion phase materials to form a third body. This third body consisting of porous carbonaceous matrix surrounding the previously applied interphase materials, is then infiltrated with molten silicon or molten silicon-refractory metal alloys to form a fourth body. The resulting fourth body comprises dense composites consisting of fibers with the desired interphase which are surrounded by silicon carbide and other second phases materials at the outer and inner surfaces comprising material of silicon, germanium, refractory metal suicides, borides, carbides, oxides, and combinations thereof The resulting composite fourth body has different compositional patterns from one side to the other.

Supramolecular Interactions in Secondary Plant Cell Walls: Effect of Lignin Chemical Composition Revealed with the Molecular Theory of Solvation.

PubMed

Silveira, Rodrigo L; Stoyanov, Stanislav R; Gusarov, Sergey; Skaf, Munir S; Kovalenko, Andriy

2015-01-02

Plant biomass recalcitrance, a major obstacle to achieving sustainable production of second generation biofuels, arises mainly from the amorphous cell-wall matrix containing lignin and hemicellulose assembled into a complex supramolecular network that coats the cellulose fibrils. We employed the statistical-mechanical, 3D reference interaction site model with the Kovalenko-Hirata closure approximation (or 3D-RISM-KH molecular theory of solvation) to reveal the supramolecular interactions in this network and provide molecular-level insight into the effective lignin-lignin and lignin-hemicellulose thermodynamic interactions. We found that such interactions are hydrophobic and entropy-driven, and arise from the expelling of water from the mutual interaction surfaces. The molecular origin of these interactions is carbohydrate-π and π-π stacking forces, whose strengths are dependent on the lignin chemical composition. Methoxy substituents in the phenyl groups of lignin promote substantial entropic stabilization of the ligno-hemicellulosic matrix. Our results provide a detailed molecular view of the fundamental interactions within the secondary plant cell walls that lead to recalcitrance.

The influence of ArF excimer laser micromachining on physicochemical properties of bioresorbable poly(L-lactide)

NASA Astrophysics Data System (ADS)

Stepak, Bogusz D.; Antończak, Arkadiusz J.; Szustakiewicz, Konrad; Pezowicz, Celina; Abramski, Krzysztof M.

2016-03-01

The main advantage of laser processing is a non-contact character of material removal and high precision attainable thanks to low laser beam dimensions. This technique enables forming a complex, submillimeter geometrical shapes such as vascular stents which cannot be manufactured using traditional techniques e.g. injection moulding or mechanical treatment. In the domain of nanosecond laser sources, an ArF excimer laser appears as a good candidate for laser micromachining of bioresorbable polymers such as poly(L-lactide). Due to long pulse duration, however, there is a risk of heat diffusion and accumulation in the material. In addition, due to short wavelength (193 nm) photochemical process can modify the chemical composition of ablated surfaces. The motivation for this research was to evaluate the influence of laser micromachining on physicochemical properties of poly(L-lactide). We performed calorimetric analysis of laser machined samples by using differential scanning calorimetry (DSC). It allowed us to find the optimal process parameters for heat affected zone (HAZ) reduction. The chemical composition of the ablated surface was investigated by FTIR in attenuated total reflectance (ATR) mode.

Characterization of Satsuma mandarin (Citrus unshiu Marc.) nectar-to-honey transformation pathway using FTIR-ATR spectroscopy.

PubMed

Svečnjak, Lidija; Prđun, Saša; Rogina, Josip; Bubalo, Dragan; Jerković, Igor

2017-10-01

Samples of Satsuma mandarin (Citrus unshiu Marc.) nectar, honey sac content and honey were analyzed by FTIR-ATR spectroscopy and reference methods. The spectral analysis allowed detection of the major chemical constituents in C. unshiu nectar-to-honey transformation pathway thus providing information on the intensity and location of the compositional changes occurring during this process. The preliminary results showed that in average more than one-third of sugar-related nectar-to-honey conversion takes place directly in the honey sac; the average sugar content (w/w) was 17.93% (nectar), 47.03% (honey sac) and 79.63% (honey). FTIR-ATR results showed great spectral similarity of analyzed honey samples and small degree variations in both sugar and water content in nectar samples. The spectral data revealed distinctive differences in the chemical composition of individual honey sac contents with the most intensive and complex absorption envelope in the spectral region between 1175 and 950cm -1 (glucose, fructose and sucrose absorption bands). Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical composition and in vitro antioxidant activity of hydro-ethanolic extracts from Bauhinia forficata subsp. pruinosa and B. variegata.

PubMed

Sayago, Carla T M; Camargo, Vanessa B; Barbosa, F; Gularte, Cláudia; Pereira, Geovana; Miotto, Silvia; Cechinel Filho, V; Luiz Puntel, R; Folmer, V; Mendez, A

2013-03-01

Bauhinia species are known to have hypoglycemiant and antioxidant activities. Here, hydro-ethanolic leaf extracts from Bauhinia forficata subsp. pruinosa and Bauhinia variegata, collected in a Pampa biome region of Brazil, were investigated to characterize their chromatographic profile, flavonoid content and in vitro antioxidant activity (TBARS and DPH assays). The extracts were obtained from dried and fresh leaves. The total flavonoid content was assessed by spectrophotometric determination, and the results ranged between 572.08 and 1,102.99 μg mL-1. Moreover, flavonoids were more predominant in B. variegata than in B. forficata subsp. pruinosa. HPLC analysis detected a complex profile of phenolic compounds, being the flavonoid kaempferitrin founded B. forficata subsp. pruinosa; in addition, other kaempferol and quercetin derivatives were present. In vitro antioxidant assays demonstrated a different behavior depending on the species, leaf treatment and extract concentration. In general, B. variegata extracts obtained from fresh material presented higher antioxidant potential, which can be attributed to the predominance of flavonoids in their chemical composition.

High-resolution mass spectrometric analysis of biomass pyrolysis vapors

DOE PAGES

Christensen, Earl; Evans, Robert J.; Carpenter, Daniel

2017-01-19

Vapors generated from the pyrolysis of lignocellulosic biomass are made up of a complex mixture of oxygenated compounds. Direct analysis of these vapors provides insight into the mechanisms of depolymerization of cellulose, hemicellulose, and lignin as well as insight into reactions that may occur during condensation of pyrolysis vapors into bio-oil. Studies utilizing pyrolysis molecular beam mass spectrometry have provided valuable information regarding the chemical composition of pyrolysis vapors. Mass spectrometers generally employed with these instruments have low mass resolution of approximately a mass unit. The presence of chemical species with identical unit mass but differing elemental formulas cannot bemore » resolved with these instruments and are therefore detected as a single ion. In this study we analyzed the pyrolysis vapors of several biomass sources using a high-resolution double focusing mass spectrometer. High-resolution analysis of pyrolysis vapors allowed for speciation of several compounds that would be detected as a single ion with unit mass resolution. Lastly, these data not only provide greater detail into the composition of pyrolysis vapors but also highlight differences between vapors generated from multiple biomass feedstocks.« less

Impacts of the mixing state and chemical composition on the cloud condensation nuclei (CCN) activity in Beijing during winter, 2016

NASA Astrophysics Data System (ADS)

Ren, J.; Zhang, F.

2017-12-01

Abstract.Understanding aerosol chemical composition and mixing state on CCN activity in polluted urban area is crucial to determine NCCN accurately and thus to quantify aerosol indirect effects. Aerosol hrgroscopicity, size-resolved cloud condensation nuclei (CCN) concentration and chemical composition are measured under polluted and background conditions in Beijing based on the Air Pollution and Human Health (APHH) field campaign in winter 2016. The CCN number concentration (NCCN) is predicted by using κ-Köhler theory from the PNSD and five simplified of the mixing state and chemical composition. The assumption of EIS (sulfate, nitrate and SOA internally mixed, and POA and BC externally mixed with size-resolved chemical composition) shows the best closure to predict NCCN with the ratio of predicted to measured NCCN of 0.96-1.12 both in POL and BG conditions. Under BG conditions, IB (internal mixture with bulk chemical composition) scheme achieves the best CCN closure during any periods of a day. In polluted days, EIS and IS (internal mixture with size-resolved chemical composition) scheme may achieve better closure than IB scheme due to the heterogeneity in particles composition across different size. ES (external mixture with size-resolved chemical composition) and EB (external mixture with bulk chemical composition) scheme markedly underestimate the NCCN with the ratio of predicted to measured NCCN of 0.6-0.8. In addition, we note that assumptions of size-resolved composition (IS or ES) show very limited promotes by comparing with the assumptions of bulk composition (IB or EB), furthermore, the prediction becomes worse by using size-resolved assumption in clean days. The predicted NCCN during eve-rush periods shows the most sensitivity to the five different assumptions, with ratios of the predicted and measured NCCN ranging from 0.5 to 1.4, reflecting great impacts from evening traffic and cooking sources. The result from the sensitivity examination of predict NCCN to particles mixing state and organic volume fractions with the aging of organic particles suggests that the mixing state of particles plays a minor role when the κorg exceeds 0.1. Our study could provide new dataset to evaluate the CCN parameterization in models in those heavily polluted regions with large fraction of POA and BC.

Laboratory Inquiry for Determining the Chemical Composition of a Component in a Daily Use Detergent: Sodium Sesquicarbonate

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Kimura, Tomoyasu; Shigedomi, Kana

2011-01-01

An inquiry-based laboratory activity to determine the chemical composition of a component in alkaline detergents, sodium sesquicarbonate (SSC), is proposed. On the basis of introductory demonstrations by the instructor on the chemical properties and reactions of SSC, students propose the hypothetical composition of SSC and possible quantitative…

Chemical complexity and source of the White River Ash, Alaska and Yukon

USGS Publications Warehouse

Preece, S.J.; McGimsey, Robert G.; Westgate, J.A.; Pearce, N.J.G.; Hartmann, W.K.; Perkins, W.T.

2014-01-01

The White River Ash, a prominent stratigraphic marker bed in Alaska (USA) and Yukon (Canada), consists of multiple compositional units belonging to two geochemical groups. The compositional units are characterized using multiple criteria, with combined glass and ilmenite compositions being the best discriminators. Two compositional units compose the northern group (WRA-Na and WRA-Nb), and two units are present in the eastern group (WRA-Ea and the younger, WRA-Eb). In the proximal area, the ca. 1900 yr B.P. (Lerbekmo et al., 1975) WRA-Na displays reverse zoning in the glass phase and systematic changes in ilmenite composition and estimated oxygen fugacity from the base to the top of the unit. The eruption probably tapped different magma batches or bodies within the magma reservoir with limited mixing or mingling between them. The 1147 cal yr B.P. (calibrated years, approximately equivalent to calendric years) (Clague et al., 1995) WRA-Ea eruption is only weakly zoned, but pumices with different glass compositions are present, along with gray and white intermingled glass in individual pumice clasts, indicating the presence of multiple magmatic bodies or layers. All White River Ash products are high-silica adakites and are sourced from the Mount Churchill magmatic system.

Apatite U-Pb thermochronolgy applied to complex geological settings - insights from geo/thermochronology and geochemistry

NASA Astrophysics Data System (ADS)

Paul, Andre; Spikings, Richard; Ulyanov, Alexey; Chew, David

2016-04-01

Application of high temperature (>350oC) thermochronology is limited to the U-Pb system of accessory minerals, such as apatite, under the assumption that radiogenic lead is lost to thermally activated volume diffusion into an infinite reservoir. Cochrane et al. (2015) have demonstrated a working example from the northern Andes of South America. Predictions from volume diffusion theory were compared with measured single grain U-Pb date correlated to shortest diffusion radius and in-situ profiles measured by LA-ICP-MS. Results from both techniques were found to be in agreement with predictions from thermally activated, volume diffusion. However, outliers from the ID-TIMS data suggested some complexity, as grains were found to be too young relative to their diffusion radius. Interaction of multiple processes can be responsible for the alteration of apatite U-Pb dates such as: (1) metamorphic (over)growth, (2) fluid aided alteration/recrystallization and (3) metamictization and fracturing of the grain. Further, predictions from volume diffusion rely on the input parameters: (a) diffusivity, (b) activation energy and (c) shortest diffusion radius. Diffusivity and activation energy are potentially influenced by the chemical composition and subsequent changes in crystal structure. Currently there is one value for diffusion parameter and activation energy established for (Durango) apatite (Cherniak et al., 1991). Correlation between diffusivity/activation energy and composition has not been established. We investigate if correlations exist between diffusivity/activation energy and composition by obtaining single grain apatite U-Pb date and chemical compostion and correlating these to their diffusion radius. We test the consistency of apatite closure temperature, by comparing the apatite U-Pb dates with lower temperature thermochronometers such as white mica and K-feldspar Ar/Ar and by petrographic observations. We test if chemical information can be a proxy to identify metamorphic (over)growth and fluid aided alteration/recrystallization. We seek to evaluate if apatite U-Pb thermochronology can be applied to a broad range of rock types and geological environments or if limitations must be drawn.

Lithological, Chemical and Chronological Constraints on Melt Extraction from the Mantle Section of the ~492 Ma Shetland Ophiolite Complex, Scotland

NASA Astrophysics Data System (ADS)

O'Driscoll, B.; Walker, R. J.; Clay, P. L.; Day, J. M.; Ash, R. D.; Daly, J. S.

2015-12-01

The mantle sections of ophiolites offer a means of studying the composition and structure of the oceanic mantle. In particular, the relations between different lithologies can be established in the field, permitting an assessment of the relative timing of processes such as melt extraction and melt-rock reaction. The Shetland Ophiolite Complex (SOC) contains a well-preserved mantle section that is dominated by harzburgite (≥70 vol.%), with dominantly chondritic present-day 187Os/188Os compositions1. Melt extraction and melt-rock reaction is evident in the form of dunite and chromitite layers and lenses, with thicknesses ranging from millimetres-to-metres. These lithologies are characteristic of supra-subduction zone processing and are considered to relate to closure of the Iapetus Ocean at ~492 Ma1. However, evidence of much earlier melt extraction has been suggested for some SOC harzburgites, which have relatively unradiogenic 187Os/188Os compositions that yield TRD model ages as old as ~1.4 Ga1. In order to assess the scales at which such compositional heterogeneities are preserved in the mantle, a small (45 m2) area of the SOC mantle section was selected for detailed lithological mapping and sampling. A selection of harzburgites (n=8), dunites (n=6) and pyroxenites (n=2) from this area has been analysed for their Os isotope and highly-siderophile element (HSE) compositions. Six of the harzburgites and four of the dunites have relative HSE abundances and gOs values that are approximately chondritic, with gOs ranging only from -0.6 to +2.7 (n=10). Two dunites have more radiogenic gOs (up to +7.5), that is correlated with enhanced concentrations of accessory base-metal sulphides, suggesting formation via melt percolation and melt-rock reaction. The two remaining harzburgites have less radiogenic gOs (-3.5 and -4), yielding Mesoproterozoic TRD ages. The new data indicate that a comparable range of Os isotope compositions to that previously measured across the entire SOC mantle section is present in the mapped area, i.e., at the m2 scale, revealing the modest scale of isotopic and chemical heterogeneity in the oceanic mantle. 1O'Driscoll B, Day JMD, Walker RJ, Daly JS, McDonough WF, Piccoli PM (2012). Earth and Planetary Science Letters 333-334: 226-237.

Visualizing chemical functionality in plant cell walls

DOE PAGES

Zeng, Yining; Himmel, Michael E.; Ding, Shi-You

2017-11-30

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructivelymore » and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition - especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.« less

Visualizing chemical functionality in plant cell walls

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

Zeng, Yining; Himmel, Michael E.; Ding, Shi-You

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructivelymore » and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition - especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.« less

Visualizing chemical functionality in plant cell walls.

PubMed

Zeng, Yining; Himmel, Michael E; Ding, Shi-You

2017-01-01

Understanding plant cell wall cross-linking chemistry and polymeric architecture is key to the efficient utilization of biomass in all prospects from rational genetic modification to downstream chemical and biological conversion to produce fuels and value chemicals. In fact, the bulk properties of cell wall recalcitrance are collectively determined by its chemical features over a wide range of length scales from tissue, cellular to polymeric architectures. Microscopic visualization of cell walls from the nanometer to the micrometer scale offers an in situ approach to study their chemical functionality considering its spatial and chemical complexity, particularly the capabilities of characterizing biomass non-destructively and in real-time during conversion processes. Microscopic characterization has revealed heterogeneity in the distribution of chemical features, which would otherwise be hidden in bulk analysis. Key microscopic features include cell wall type, wall layering, and wall composition-especially cellulose and lignin distributions. Microscopic tools, such as atomic force microscopy, stimulated Raman scattering microscopy, and fluorescence microscopy, have been applied to investigations of cell wall structure and chemistry from the native wall to wall treated by thermal chemical pretreatment and enzymatic hydrolysis. While advancing our current understanding of plant cell wall recalcitrance and deconstruction, microscopic tools with improved spatial resolution will steadily enhance our fundamental understanding of cell wall function.

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

NASA Astrophysics Data System (ADS)

Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

2018-02-01

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in highly acidic brines is controlled by the distribution of dissolved chlorine species, which changes from Cl- to HClo dominance with the progressive pH decline. The Kawah Ijen lake acquired its extreme composition through influx of sulphur and halogen-rich magmatic gas components and extensive rock dissolution. If hyperacid brines with comparable chemical composition existed on Mars, evaporation processes up to the extent reported here (aH2O = 0.85), were likely accompanied by losses of gaseous HCl. The resulting changes in Cl isotope compositions, Br/Cl, S/Cl and other ratios in the residual brine might be potentially recorded in assemblages of halogen-bearing secondary evaporation minerals. Also, volcanic-hydrothermal brines as these would extend the stability of liquid water on the Martian surface down to a temperature of -90 °C.

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Shunyao; Ye, Jianhuai; Soong, Ronald; Wu, Bing; Yu, Legeng; Simpson, André J.; Chan, Arthur W. H.

2018-03-01

Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal-organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

Fibrous Growth of Chloride Minerals on Diatomite Saturated with a Brine

NASA Astrophysics Data System (ADS)

Toboła, Tomasz; Rembiś, Marek; Figarska-Warchoł, Beata; Stańczak, Grażyna

One of the fundamental characteristics of diatomites is their structural porosity as it controls specific properties of these rocks and their possible industrial applications. The authors examined the interaction between natural diatomites (not calcinated) from Polish Carpathian Flysch Belt and a brine composed of the mixture of NaCl, KCl and MgCl2*H2O with the concentration 100 g/L each for 5 days. Blocks of diatomites immersed in the brine showed an uprising boundary of a moisturised rock after a 2-4 h. Then, after about 24 h salt efflorescences began to grow on their surfaces. SEM-EDS analyses have revealed two types of fibres on the block surfaces. One group is formed by long and thin, often strongly bent fibres. In the cross-section they are rounded or flatten (ribbons) or have more complex shapes. Their chemical composition indicates sylvine but with a considerable amount of sodium. The crystals of the second type are shorter and thicker, and their chemical composition indicates halite but with high amounts of potassium. The magnesium minerals was not stated. Inside the lower parts of diatomite blocks, pores are almost completely filled with halite, but in the upper parts of the blocks sylvine is the precipitate found in the pores. The habit of the efflorescent salts seem to be influenced by the size and shape of the diatomite porous structure. The spatial distribution of both salt types and their chemical compositions seem to be associated with selective absorption of ions by silica that forms the diatomite framework.

A Study of Chemical Composition of δ Scuti-Type Stars Based on the Observations with the BTA and RTT-150

NASA Astrophysics Data System (ADS)

Galeev, A. I.; Berdnikova, V. M.; Ivanova, D. V.; Kudryavtsev, D. O.; Shimanskaya, N. N.; Shimansky, V. V.; Balashova, M. O.

2017-06-01

The results of a study of a sample of δ Scuti-type stars obtained from the observations with the BTA and RTT-150 are presented. Based on photometric data, we measured and analyzed the fundamental parameters of all the studied stars. For eight stars (for two of them for the first time), the fundamental parameters of the atmospheres (Teff, log g, [Fe/H]) and the chemical composition for 29 elements in the LTE-approximation are received using spectroscopic observations. The chemical composition analysis demonstrates both the solar abundances of chemical elements and the anomalies of chemical composition typical of Am stars in the studied sample of δ Scuti-type stars.

The use of computer-assisted image analysis in the evaluation of the effect of management systems on changes in the color, chemical composition and texture of m. longissimus dorsi in pigs.

PubMed

Zapotoczny, Piotr; Kozera, Wojciech; Karpiesiuk, Krzysztof; Pawłowski, Rodian

2014-08-01

The effect of management systems on selected physical properties and chemical composition of m. longissimus dorsi was studied in pigs. Muscle texture parameters were determined by computer-assisted image analysis, and the color of muscle samples was evaluated using a spectrophotometer. Highly significant correlations were observed between chemical composition and selected texture variables in the analyzed images. Chemical composition was not correlated with color or spectral distribution. Subject to the applied classification methods and groups of variables included in the classification model, the experimental groups were identified correctly in 35-95%. No significant differences in the chemical composition of m. longissimus dorsi were observed between experimental groups. Significant differences were noted in color lightness (L*) and redness (a*). Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermally emissive sensing materials for chemical spectroscopy analysis

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

Poole, Zsolt; Ohodnicki, Paul R.

A sensor using thermally emissive materials for chemical spectroscopy analysis includes an emissive material, wherein the emissive material includes the thermally emissive materials which emit electromagnetic radiation, wherein the electromagnetic radiation is modified due to chemical composition in an environment; and a detector adapted to detect the electromagnetic radiation, wherein the electromagnetic radiation is indicative of the chemical interaction changes and hence chemical composition and/or chemical composition changes of the environment. The emissive material can be utilized with an optical fiber sensor, with the optical fiber sensor operating without the emissive material probed with a light source external to themore » material.« less