On the anomalous adsorption of [Pd(edta)]2- at the water/Goethite interface: spectroscopic evidence for two types of surface complexes.

PubMed

Kaplun, Marina; Nordin, Agneta; Persson, Per

2008-01-15

The structure of palladium(II) ethylenediaminetetraacetate (edta) in aqueous solutions and its adsorption on the surface of goethite (alpha-FeOOH) were studied using extended X-ray absorption fine structure spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The obtained results show that in aqueous solutions, Pd-edta exists as a 1:1 complex, [Pd(edta)]2-, with edta acting as a quadridentate ligand. On the surface of goethite, [Pd(edta)]2- forms two different types of complexes over a pH range of 3.40-8.12. At pH < 5, [Pd(edta)]2- adsorbs as an outer-sphere species with possible hydrogen bonding. At higher pH values, the formation of inner-sphere complexes of the cation-type sets in after a cleavage of one glycinate ring and the formation of an (edta)Pd-O-Fe linkage.

Dynamics of Nanoparticle-Protein Corona Complex Formation: Analytical Results from Population Balance Equations

PubMed Central

Darabi Sahneh, Faryad; Scoglio, Caterina; Riviere, Jim

2013-01-01

Background Nanoparticle-protein corona complex formation involves absorption of protein molecules onto nanoparticle surfaces in a physiological environment. Understanding the corona formation process is crucial in predicting nanoparticle behavior in biological systems, including applications of nanotoxicology and development of nano drug delivery platforms. Method This paper extends the modeling work in to derive a mathematical model describing the dynamics of nanoparticle corona complex formation from population balance equations. We apply nonlinear dynamics techniques to derive analytical results for the composition of nanoparticle-protein corona complex, and validate our results through numerical simulations. Results The model presented in this paper exhibits two phases of corona complex dynamics. In the first phase, proteins rapidly bind to the free surface of nanoparticles, leading to a metastable composition. During the second phase, continuous association and dissociation of protein molecules with nanoparticles slowly changes the composition of the corona complex. Given sufficient time, composition of the corona complex reaches an equilibrium state of stable composition. We find analytical approximate formulae for metastable and stable compositions of corona complex. Our formulae are very well-structured to clearly identify important parameters determining corona composition. Conclusion The dynamics of biocorona formation constitute vital aspect of interactions between nanoparticles and living organisms. Our results further understanding of these dynamics through quantitation of experimental conditions, modeling results for in vitro systems to better predict behavior for in vivo systems. One potential application would involve a single cell culture medium related to a complex protein medium, such as blood or tissue fluid. PMID:23741371

Free Surface Flows and Extensional Rheology of Polymer Solutions

NASA Astrophysics Data System (ADS)

Dinic, Jelena; Jimenez, Leidy Nallely; Biagioli, Madeleine; Estrada, Alexandro; Sharma, Vivek

Free-surface flows - jetting, spraying, atomization during fuel injection, roller-coating, gravure printing, several microfluidic drop/particle formation techniques, and screen-printing - all involve the formation of axisymmetric fluid elements that spontaneously break into droplets by a surface-tension-driven instability. The growth of the capillary-driven instability and pinch-off dynamics are dictated by a complex interplay of inertial, viscous and capillary stresses for simple fluids. Additional contributions by elasticity, extensibility and extensional viscosity play a role for complex fluids. We show that visualization and analysis of capillary-driven thinning and pinch-off dynamics of the columnar neck in an asymmetric liquid bridge created by dripping-onto-substrate (DoS) can be used for characterizing the extensional rheology of complex fluids. Using a wide variety of complex fluids, we show the measurement of the extensional relaxation time, extensional viscosity, power-law index and shear viscosity. Lastly, we elucidate how polymer composition, flexibility, and molecular weight determine the thinning and pinch-off dynamics of polymeric complex fluids.

In vitro platelet activation, aggregation and platelet-granulocyte complex formation induced by surface modified single-walled carbon nanotubes.

PubMed

Fent, János; Bihari, Péter; Vippola, Minnamari; Sarlin, Essi; Lakatos, Susan

2015-08-01

Surface modification of single-walled carbon nanotubes (SWCNTs) such as carboxylation, amidation, hydroxylation and pegylation is used to reduce the nanotube toxicity and render them more suitable for biomedical applications than their pristine counterparts. Toxicity can be manifested in platelet activation as it has been shown for SWCNTs. However, the effect of various surface modifications on the platelet activating potential of SWCNTs has not been tested yet. In vitro platelet activation (CD62P) as well as the platelet-granulocyte complex formation (CD15/CD41 double positivity) in human whole blood were measured by flow cytometry in the presence of 0.1mg/ml of pristine or various surface modified SWCNTs. The effect of various SWCNTs was tested by whole blood impedance aggregometry, too. All tested SWCNTs but the hydroxylated ones activate platelets and promote platelet-granulocyte complex formation in vitro. Carboxylated, pegylated and pristine SWCNTs induce whole blood aggregation as well. Although pegylation is preferred from biomedical point of view, among the samples tested by us pegylated SWCNTs induced far the most prominent activation and a well detectable aggregation of platelets in whole blood. Copyright © 2015 Elsevier Ltd. All rights reserved.

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

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

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

DOE PAGES

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.; ...

2018-02-08

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Cellulose Microfibril Formation by Surface-Tethered Cellulose Synthase Enzymes.

PubMed

Basu, Snehasish; Omadjela, Okako; Gaddes, David; Tadigadapa, Srinivas; Zimmer, Jochen; Catchmark, Jeffrey M

2016-02-23

Cellulose microfibrils are pseudocrystalline arrays of cellulose chains that are synthesized by cellulose synthases. The enzymes are organized into large membrane-embedded complexes in which each enzyme likely synthesizes and secretes a β-(1→4) glucan. The relationship between the organization of the enzymes in these complexes and cellulose crystallization has not been explored. To better understand this relationship, we used atomic force microscopy to visualize cellulose microfibril formation from nickel-film-immobilized bacterial cellulose synthase enzymes (BcsA-Bs), which in standard solution only form amorphous cellulose from monomeric BcsA-B complexes. Fourier transform infrared spectroscopy and X-ray diffraction techniques show that surface-tethered BcsA-Bs synthesize highly crystalline cellulose II in the presence of UDP-Glc, the allosteric activator cyclic-di-GMP, as well as magnesium. The cellulose II cross section/diameter and the crystal size and crystallinity depend on the surface density of tethered enzymes as well as the overall concentration of substrates. Our results provide the correlation between cellulose microfibril formation and the spatial organization of cellulose synthases.

Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface

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

Peak, Derek

2008-06-09

Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO{sub 4}{sup 2-}) and selenite (SeO{sub 3}{sup 2-}) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum ({alpha}-Al{sub 2}O{sub 3}) was studied to determine if adsorption mechanisms change as the aluminum oxide surfacemore » structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and {alpha}-Me{sub 2}O{sub 3}.« less

[Mechanistic modelling allows to assess pathways of DNA lesion interactions underlying chromosome aberration formation].

PubMed

Eĭdel'man, Iu A; Slanina, S V; Sal'nikov, I V; Andreev, S G

2012-12-01

The knowledge of radiation-induced chromosomal aberration (CA) mechanisms is required in many fields of radiation genetics, radiation biology, biodosimetry, etc. However, these mechanisms are yet to be quantitatively characterised. One of the reasons is that the relationships between primary lesions of DNA/chromatin/chromosomes and dose-response curves for CA are unknown because the pathways of lesion interactions in an interphase nucleus are currently inaccessible for direct experimental observation. This article aims for the comparative analysis of two principally different scenarios of formation of simple and complex interchromosomal exchange aberrations: by lesion interactions at chromosome territories' surface vs. in the whole space of the nucleus. The analysis was based on quantitative mechanistic modelling of different levels of structures and processes involved in CA formation: chromosome structure in an interphase nucleus, induction, repair and interactions of DNA lesions. It was shown that the restricted diffusion of chromosomal loci, predicted by computational modelling of chromosome organization, results in lesion interactions in the whole space of the nucleus being impossible. At the same time, predicted features of subchromosomal dynamics agrees well with in vivo observations and does not contradict the mechanism of CA formation at the surface of chromosome territories. On the other hand, the "surface mechanism" of CA formation, despite having certain qualities, proved to be insufficient to explain high frequency of complex exchange aberrations observed by mFISH technique. The alternative mechanism, CA formation on nuclear centres is expected to be sufficient to explain frequent complex exchanges.

Mechanism of Benzene Tribopolymerization on the RuO2 (110) Surface

NASA Astrophysics Data System (ADS)

Yang, J.; Qi, Y.; Kim, H. D.; Rappe, A. M.

2018-04-01

A tribopolymer formed on the contacts of microelectromechanical and nanoelectromechanical system (MEMS-NEMS) devices is a major concern hampering their practical use in information technology. Conductive metal oxides, such as RuO2 and ReO3 , have been regarded as promising candidate materials for MEMS-NEMS contacts due to their conductivity, hardness, and relatively chemically inert surfaces. However, recent experimental works demonstrate that trace amounts of a polymer could still form on RuO2 surfaces. We demonstrate the mechanism of this class of unexpected tribopolymer formation by conducting density-functional-theory-based computational compression experiments with benzene as the contamination gas. First, mechanical force during compression changes the benzene molecules from slightly physisorbed to strongly chemisorbed. Further compression causes deformation and chemical linkage of the benzene molecules. Finally, the two contacts detach, with one having a complex organic molecule attached and the other a more reactive surface. The complex organic molecule, which has an oxabicyclic segment, can be viewed as the rudiment of a tribopolymer, and the more reactive surface can trigger the next adsorption-reaction-tribopolymer formation cycle. Based on these results, we also predict tribopolymer formation rates by using transition-state theory and the second-order rate law. We promote a deeper understanding of tribopolymer formation (especially on metal oxides) and provide strategies for suppressing tribopolymerization.

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

PubMed

Fernandes, M Marques; Scheinost, A C; Baeyens, B

2016-08-01

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of Surfaces on Amyloid Fibril Formation

PubMed Central

Moores, Bradley; Drolle, Elizabeth; Attwood, Simon J.; Simons, Janet; Leonenko, Zoya

2011-01-01

Using atomic force microscopy (AFM) we investigated the interaction of amyloid beta (Aβ) (1–42) peptide with chemically modified surfaces in order to better understand the mechanism of amyloid toxicity, which involves interaction of amyloid with cell membrane surfaces. We compared the structure and density of Aβ fibrils on positively and negatively charged as well as hydrophobic chemically-modified surfaces at physiologically relevant conditions. We report that due to the complex distribution of charge and hydrophobicity amyloid oligomers bind to all types of surfaces investigated (CH3, COOH, and NH2) although the charge and hydrophobicity of surfaces affected the structure and size of amyloid deposits as well as surface coverage. Hydrophobic surfaces promote formation of spherical amorphous clusters, while charged surfaces promote protofibril formation. We used the nonlinear Poisson-Boltzmann equation (PBE) approach to analyze the electrostatic interactions of amyloid monomers and oligomers with modified surfaces to complement our AFM data. PMID:22016789

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Thiol surface complexation on growing CdS clusters

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

Swayambunathan, V.; Hayes, D.; Schmidt, K.H.

1990-05-09

The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{supmore » {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.« less

Reactive Desorption and Radiative Association as Possible Drivers of Complex Molecule Formation in the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Vasyunin, A. I.; Herbst, Eric

2013-05-01

The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed "warm-up" scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

Multi-parametric surface plasmon resonance platform for studying liposome-serum interactions and protein corona formation.

PubMed

Kari, Otto K; Rojalin, Tatu; Salmaso, Stefano; Barattin, Michela; Jarva, Hanna; Meri, Seppo; Yliperttula, Marjo; Viitala, Tapani; Urtti, Arto

2017-04-01

When nanocarriers are administered into the blood circulation, a complex biomolecular layer known as the "protein corona" associates with their surface. Although the drivers of corona formation are not known, it is widely accepted that this layer mediates biological interactions of the nanocarrier with its surroundings. Label-free optical methods can be used to study protein corona formation without interfering with its dynamics. We demonstrate the proof-of-concept for a multi-parametric surface plasmon resonance (MP-SPR) technique in monitoring the formation of a protein corona on surface-immobilized liposomes subjected to flowing 100 % human serum. We observed the formation of formulation-dependent "hard" and "soft" coronas with distinct refractive indices, layer thicknesses, and surface mass densities. MP-SPR was also employed to determine the affinity (K D ) of a complement system molecule (C3b) with cationic liposomes with and without polyethylene glycol. Tendency to create a thick corona correlated with a higher affinity of opsonin C3b for the surface. The label-free platform provides a fast and robust preclinical tool for tuning nanocarrier surface architecture and composition to control protein corona formation.

IMPACTS OF BIOFILM FORMATION ON CELLULOSE FERMENTATION

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

Leschine, Susan

2009-10-31

This project addressed four major areas of investigation: i) characterization of formation of Cellulomonas uda biofilms on cellulose; ii) characterization of Clostridium phytofermentans biofilm development; colonization of cellulose and its regulation; iii) characterization of Thermobifida fusca biofilm development; colonization of cellulose and its regulation; and iii) description of the architecture of mature C. uda, C. phytofermentans, and T. fusca biofilms. This research is aimed at advancing understanding of biofilm formation and other complex processes involved in the degradation of the abundant cellulosic biomass, and the biology of the microbes involved. Information obtained from these studies is invaluable in the developmentmore » of practical applications, such as the single-step bioconversion of cellulose-containing residues to fuels and other bioproducts. Our results have clearly shown that cellulose-decomposing microbes rapidly colonize cellulose and form complex structures typical of biofilms. Furthermore, our observations suggest that, as cells multiply on nutritive surfaces during biofilms formation, dramatic cell morphological changes occur. We speculated that morphological changes, which involve a transition from rod-shaped cells to more rounded forms, might be more apparent in a filamentous microbe. In order to test this hypothesis, we included in our research a study of biofilm formation by T. fusca, a thermophilic cellulolytic actinomycete commonly found in compost. The cellulase system of T. fusca has been extensively detailed through the work of David Wilson and colleagues at Cornell, and also, genome sequence of a T. fusca strain has been determine by the DOE Joint Genome Institute. Thus, T. fusca is an excellent subject for studies of biofilm development and its potential impacts on cellulose degradation. We also completed a study of the chitinase system of C. uda. This work provided essential background information for understanding how C. uda colonizes and degrades insoluble substrates. Major accomplishments of the project include: • Development of media containing dialysis tubing (described by the manufacturer as “regenerated cellulose”) as sole carbon and energy source and a nutritive surface for the growth of cellulolytic bacteria, and development of various microscopic methods to image biofilms on dialysis tubing. • Demonstration that cultures of C. phytofermentans, an obligate anaerobe, C. uda, a facultative aerobe, and T. fusca, a filamentous aerobe, formed microbial communities on the surface of dialysis tubing, which possessed architectural features and functional characteristics typical of biofilms. • Demonstration that biofilm formation on the nutritive surface, cellulose, involves a complex developmental processes, including colonization of dialysis tubing, formation of cell clusters attached to the nutritive surface, cell morphological changes, formation of complex structures embedded in extracellular polymeric matrices, and dispersal of biofilm communities as the nutritive surface is degraded. • Determination of surface specificity and regulatory aspects of biofilm formation by C. phytofermentans, C. uda, and T. fusca. • Demonstration that biofilm formation by T. fusca forms an integral part of the life cycle of this filamentous cellulolytic bacterium, including studies on the role of mycelial pellet formation in the T. fusca life cycle and a comparison of mycelial pellets to surface-attached T. fusca biofilms. • Characterization of T. fusca biofilm EPS, including demonstration of a functional role for EPS constituents. • Correlation of T. fusca developmental life cycle and cellulase gene expression.« less

Formation of plasmon pulses in the cooperative decay of excitons of quantum dots near a metal surface

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

Shesterikov, A. B.; Gubin, M. Yu.; Gladush, M. G.

The formation of pulses of surface electromagnetic waves at a metal–dielectric boundary is considered in the process of cooperative decay of excitons of quantum dots distributed near a metal surface in a dielectric layer. It is shown that the efficiency of exciton energy transfer to excited plasmons can, in principle, be increased by selecting the dielectric material with specified values of the complex permittivity. It is found that in the mean field approximation, the semiclassical model of formation of plasmon pulses in the system under study is reduced to the pendulum equation with the additional term of nonlinear losses.

On the chemical ladder of esters. Detection and formation of ethyl formate in the W51 e2 hot molecular core

NASA Astrophysics Data System (ADS)

Rivilla, V. M.; Beltrán, M. T.; Martín-Pintado, J.; Fontani, F.; Caselli, P.; Cesaroni, R.

2017-03-01

Context. In recent years, the detection of organic molecules with increasing complexity and potential biological relevance is opening the possibility to understand the formation of the building blocks of life in the interstellar medium. One of the families of molecules of substantial astrobiological interest are the esters. The simplest ester, methyl formate (CH3OCHO), is rather abundant in star-forming regions. The next step in the chemical complexity of esters is ethyl formate, C2H5OCHO. Despite the increase in sensitivity of current telescopes, the detection of complex molecules with more than ten atoms such as C2H5OCHO is still a challenge. Only two detections of this species have been reported so far, which strongly limits our understanding of how complex molecules are formed in the interstellar medium. New detections towards additional sources with a wide range of physical conditions are crucial to differentiate between competing chemical models based on dust grain surface and gas-phase chemistry. Aims: We have searched for ethyl formate towards the W51 e2 hot molecular core, one of the most chemically rich sources in the Galaxy and one of the most promising regions to study prebiotic chemistry, especially after the recent discovery of the P-O bond, key in the formation of DNA. Methods: We have analyzed a spectral line survey towards the W51 e2 hot molecular core, which covers 44 GHz in the 1, 2 and 3 mm bands, carried out with the IRAM 30 m telescope. Results: We report the detection of the trans and gauche conformers of ethyl formate. A local thermodynamic equilibrium analysis indicates that the excitation temperature is 78 ± 10 K and that the two conformers have similar source-averaged column densities of (2.0 ± 0.3) × 10-16 cm-2 and an abundance of 10-8. We compare for the first time the observed molecular abundances of ethyl formate with different competing chemical models based on grain surface and gas-phase chemistry. Conclusions: We propose that grain-surface chemistry may have a dominant role in the formation of ethyl formate (and other complex organic molecules) in hot molecular cores, rather than reactions in the gas phase. Based on observations carried out with the IRAM 30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).

Electrostatics Explains the Position-Dependent Effect of G⋅U Wobble Base Pairs on the Affinity of RNA Kissing Complexes.

PubMed

Abi-Ghanem, Josephine; Rabin, Clémence; Porrini, Massimiliano; Dausse, Eric; Toulmé, Jean-Jacques; Gabelica, Valérie

2017-10-06

In the RNA realm, non-Watson-Crick base pairs are abundant and can affect both the RNA 3D structure and its function. Here, we investigated the formation of RNA kissing complexes in which the loop-loop interaction is modulated by non-Watson-Crick pairs. Mass spectrometry, surface plasmon resonance, and UV-melting experiments show that the G⋅U wobble base pair favors kissing complex formation only when placed at specific positions. We tried to rationalize this effect by molecular modeling, including molecular mechanics Poisson-Boltzmann surface area (MMPBSA) thermodynamics calculations and PBSA calculations of the electrostatic potential surfaces. Modeling reveals that the G⋅U stabilization is due to a specific electrostatic environment defined by the base pairs of the entire loop-loop region. The loop is not symmetric, and therefore the identity and position of each base pair matters. Predicting and visualizing the electrostatic environment created by a given sequence can help to design specific kissing complexes with high affinity, for potential therapeutic, nanotechnology or analytical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of Immune Complex Structure by Statistical Mechanics and Light Scattering Techniques.

NASA Astrophysics Data System (ADS)

Busch, Nathan Adams

1995-01-01

The size and structure of immune complexes determine their behavior in the immune system. The chemical physics of the complex formation is not well understood; this is due in part to inadequate characterization of the proteins involved, and in part by lack of sufficiently well developed theoretical techniques. Understanding the complex formation will permit rational design of strategies for inhibiting tissue deposition of the complexes. A statistical mechanical model of the proteins based upon the theory of associating fluids was developed. The multipole electrostatic potential for each protein used in this study was characterized for net protein charge, dipole moment magnitude, and dipole moment direction. The binding sites, between the model antigen and antibodies, were characterized for their net surface area, energy, and position relative to the dipole moment of the protein. The equilibrium binding graphs generated with the protein statistical mechanical model compares favorably with experimental data obtained from radioimmunoassay results. The isothermal compressibility predicted by the model agrees with results obtained from dynamic light scattering. The statistical mechanics model was used to investigate association between the model antigen and selected pairs of antibodies. It was found that, in accordance to expectations from thermodynamic arguments, the highest total binding energy yielded complex distributions which were skewed to higher complex size. From examination of the simulated formation of ring structures from linear chain complexes, and from the joint shape probability surfaces, it was found that ring configurations were formed by the "folding" of linear chains until the ends are within binding distance. By comparing the single antigen/two antibody system which differ only in their respective binding site locations, it was found that binding site location influences complex size and shape distributions only when ring formation occurs. The internal potential energy of a ring complex is considerably less than that of the non-associating system; therefore the ring complexes are quite stable and show no evidence of breaking, and collapsing into smaller complexes. The ring formation will occur only in systems where the total free energy of each complex may be minimized. Thus, ring formation will occur even though entropically unfavorable conformations result if the total free energy can be minimized by doing so.

Studying of kinetics of rear earth ion (REI) nanoscale complex formation by resonant energy transfer

NASA Astrophysics Data System (ADS)

Ignatova, Tetyana; Pristinski, Denis; Rotkin, Slava V.

2011-03-01

We observed formation of nanoscale complexes between multivalent REIs (Tb and Eu) and negatively charged DNA wrapped SWNTs, ionized in the water solution. Foerster Resonance Energy Transfer (FRET) was found to be an ideal method to confirm the complex formation. Because of its high sensitivity and non-destructive characterization approach FRET can be used to trace the kinetics of the complex formation. Strong dependence of SWNT photoluminescence (PL) on the REI concentration was detected and interpreted as a competition between the REI absorption on the SWNTs and subsequent FRET enhanced PL and the SWNT agglomeration followed by PL quenching. We measured the distance between REI and SWNT which appears to be much shorter than the one from their relative concentration in solution. We speculate that Manning condensation of the REIs on the SWNT/DNA surface happens thereby significantly reducing their spacing and making FRET possible.

The Formation of Formaldehyde on Interstellar Carbonaceous Grain Analogs by O/H Atom Addition

NASA Astrophysics Data System (ADS)

Potapov, Alexey; Jäger, Cornelia; Henning, Thomas; Jonusas, Mindaugas; Krim, Lahouari

2017-09-01

An understanding of possible scenarios for the formation of astrophysically relevant molecules, particularly complex organic molecules, will bring us one step closer to the understanding of our astrochemical heritage. In this context, formaldehyde is an important molecule as a precursor of methanol, which in turn is a starting point for the formation of more complex organic species. In the present experiments, for the first time, following the synthesis of CO, formaldehyde has been produced on the surface of interstellar grain analogs, hydrogenated fullerene-like carbon grains, by O and H atom bombardment. The formation of H2CO is an indication for a possible methanol formation route in such systems.

Prediction of Protein-Protein Interaction Sites Using Electrostatic Desolvation Profiles

PubMed Central

Fiorucci, Sébastien; Zacharias, Martin

2010-01-01

Abstract Protein-protein complex formation involves removal of water from the interface region. Surface regions with a small free energy penalty for water removal or desolvation may correspond to preferred interaction sites. A method to calculate the electrostatic free energy of placing a neutral low-dielectric probe at various protein surface positions has been designed and applied to characterize putative interaction sites. Based on solutions of the finite-difference Poisson equation, this method also includes long-range electrostatic contributions and the protein solvent boundary shape in contrast to accessible-surface-area-based solvation energies. Calculations on a large set of proteins indicate that in many cases (>90%), the known binding site overlaps with one of the six regions of lowest electrostatic desolvation penalty (overlap with the lowest desolvation region for 48% of proteins). Since the onset of electrostatic desolvation occurs even before direct protein-protein contact formation, it may help guide proteins toward the binding region in the final stage of complex formation. It is interesting that the probe desolvation properties associated with residue types were found to depend to some degree on whether the residue was outside of or part of a binding site. The probe desolvation penalty was on average smaller if the residue was part of a binding site compared to other surface locations. Applications to several antigen-antibody complexes demonstrated that the approach might be useful not only to predict protein interaction sites in general but to map potential antigenic epitopes on protein surfaces. PMID:20441756

Monte Carlo kinetics simulations of ice-mantle formation on interstellar grains

NASA Astrophysics Data System (ADS)

Garrod, Robin

2015-08-01

The majority of interstellar dust-grain chemical kinetics models use rate equations, or alternative population-based simulation methods, to trace the time-dependent formation of grain-surface molecules and ice mantles. Such methods are efficient, but are incapable of considering explicitly the morphologies of the dust grains, the structure of the ices formed thereon, or the influence of local surface composition on the chemistry.A new Monte Carlo chemical kinetics model, MIMICK, is presented here, whose prototype results were published recently (Garrod 2013, ApJ, 778, 158). The model calculates the strengths and positions of the potential mimima on the surface, on the fly, according to the individual pair-wise (van der Waals) bonds between surface species, allowing the structure of the ice to build up naturally as surface diffusion and chemistry occur. The prototype model considered contributions to a surface particle's potential only from contiguous (or "bonded") neighbors; the full model considers contributions from surface constituents from short to long range. Simulations are conducted on a fully 3-D user-generated dust-grain with amorphous surface characteristics. The chemical network has also been extended from the simple water system previously published, and now includes 33 chemical species and 55 reactions. This allows the major interstellar ice components to be simulated, such as water, methane, ammonia and methanol, as well as a small selection of more complex molecules, including methyl formate (HCOOCH3).The new model results indicate that the porosity of interstellar ices are dependent on multiple variables, including gas density, the dust temperature, and the relative accretion rates of key gas-phase species. The results presented also have implications for the formation of complex organic molecules on dust-grain surfaces at very low temperatures.

Investigation of formation of cut off layers and productivity of screw milling process

NASA Astrophysics Data System (ADS)

Ambrosimov, S. K.; Morozova, A. V.

2018-03-01

The article presents studies of a new method for complex milling surfaces with a screw feed motion. Using the apparatus of algebra of logic, the process of formation of cut metal layers and processing capacity is presented.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

PubMed

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level < 2 ppmv. Tin redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

Self-assembly of metal nanostructures on binary alloy surfaces

PubMed Central

Duguet, T.; Han, Yong; Yuen, Chad; Jing, Dapeng; Ünal, Barış; Evans, J. W.; Thiel, P. A.

2011-01-01

Deposition of metals on binary alloy surfaces offers new possibilities for guiding the formation of functional metal nanostructures. This idea is explored with scanning tunneling microscopy studies and atomistic-level analysis and modeling of nonequilibrium island formation. For Au/NiAl(110), complex monolayer structures are found and compared with the simple fcc(110) bilayer structure recently observed for Ag/NiAl(110). We also consider a more complex codeposition system, (Ni + Al)/NiAl(110), which offers the opportunity for fundamental studies of self-growth of alloys including deviations for equilibrium ordering. A general multisite lattice-gas model framework enables analysis of structure selection and morphological evolution in these systems. PMID:21097706

Dual Effect of (LK)nL Peptides on the Onset of Insulin Amyloid Fiber Formation at Hydrophobic Surfaces.

PubMed

Chouchane, Karim; Vendrely, Charlotte; Amari, Myriam; Moreaux, Katie; Bruckert, Franz; Weidenhaupt, Marianne

2015-08-20

Soluble proteins are constantly in contact with material or cellular surfaces, which can trigger their aggregation and therefore have a serious impact on the development of stable therapeutic proteins. In contact with hydrophobic material surfaces, human insulin aggregates readily into amyloid fibers. The kinetics of this aggregation can be accelerated by small peptides, forming stable beta-sheets on hydrophobic surfaces. Using a series of (LK)nL peptides with varying length, we show that these peptides, at low, substoichiometric concentrations, have a positive, cooperative effect on insulin aggregation. This effect is based on a cooperative adsorption of (LK)nL peptides at hydrophobic surfaces, where they form complexes that help the formation of aggregation nuclei. At higher concentrations, they interfere with the formation of an aggregative nucleus. These effects are strictly dependent on the their adsorption on hydrophobic material surfaces and highlight the importance of the impact of materials on protein stability. (LK)nL peptides prove to be valuable tools to investigate the mechanism of HI aggregation nuclei formation on hydrophobic surfaces.

Using micro-patterned surfaces to inhibit settlement and biofilm formation by Bacillus subtilis.

PubMed

Chang, Siyuan; Chen, Xiaodong; Jiang, Shuo; Chen, Jinchun; Shi, Lin

2017-07-01

Biofilm is a biological complex caused by bacteria attachment to the substrates and their subsequent reproduction and secretion. This phenomenon reduces heat transfer efficiency and causes significant losses in treated sewage heat-recovering systems. This paper describes a physical approach to inhibit bacteria settlement and biofilm formation by Bacillus subtilis, which is the dominant species in treated sewage. Here, micro-patterned surfaces with different characteristics (stripe and cube) and dimensions (1-100 μm) were fabricated as surfaces of interest. Model sewage was prepared and a rotating coupon device was used to form the biofilms. Precision balance, scanning electron microscopy, and confocal laser scanning microscopy (CLSM) were employed to investigate the inhibitory effects and the mechanisms of the biofilm-surface interactions. The results have shown that surfaces with small pattern sizes (1 and 2 μm) all reduced biofilm formation significantly. Interestingly, the CLSM images showed that the surfaces do not play a role in "killing" the bacteria. These findings are useful for future development of new process surfaces on which bacteria settlement and biofilm formation can be inhibited or minimized.

Energetic basis for selective recognition of T*G mismatched base pairs in DNA by imidazole-rich polyamides.

PubMed

Lacy, Eilyn R; Nguyen, Binh; Le, Minh; Cox, Kari K; OHare, Caroline; Hartley, John A; Lee, Moses; Wilson, W David

2004-01-01

To complement available structure and binding results and to develop a detailed understanding of the basis for selective molecular recognition of T.G mismatches in DNA by imidazole containing polyamides, a full thermodynamic profile for formation of the T.G-polyamide complex has been determined. The amide-linked heterocycles f-ImImIm and f-PyImIm (where f is formamido group, Im is imidazole and Py is pyrrole) were studied by using biosensor-surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC) with a T.G mismatch containing DNA hairpin duplex and a similar DNA with only Watson-Crick base pairs. Large negative binding enthalpies for all of the polyamide-DNA complexes indicate that the interactions are enthalpically driven. SPR results show slower complex formation and stronger binding of f-ImImIm to the T.G than to the match site. The thermodynamic analysis indicates that the enhanced binding to the T.G site is the result of better entropic contributions. Negative heat capacity changes for the complex are correlated with calculated solvent accessible surface area changes and indicate hydrophobic contributions to complex formation. DNase I footprinting analysis in a long DNA sequence provided supporting evidence that f-ImImIm binds selectively to T.G mismatch sites.

Energetic basis for selective recognition of T·G mismatched base pairs in DNA by imidazole-rich polyamides

PubMed Central

Lacy, Eilyn R.; Nguyen, Binh; Le, Minh; Cox, Kari K.; O'Hare, Caroline; Hartley, John A.; Lee, Moses; Wilson, W. David

2004-01-01

To complement available structure and binding results and to develop a detailed understanding of the basis for selective molecular recognition of T·G mismatches in DNA by imidazole containing polyamides, a full thermodynamic profile for formation of the T·G–polyamide complex has been determined. The amide-linked heterocycles f-ImImIm and f-PyImIm (where f is formamido group, Im is imidazole and Py is pyrrole) were studied by using biosensor-surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC) with a T·G mismatch containing DNA hairpin duplex and a similar DNA with only Watson–Crick base pairs. Large negative binding enthalpies for all of the polyamide–DNA complexes indicate that the interactions are enthalpically driven. SPR results show slower complex formation and stronger binding of f-ImImIm to the T·G than to the match site. The thermodynamic analysis indicates that the enhanced binding to the T·G site is the result of better entropic contributions. Negative heat capacity changes for the complex are correlated with calculated solvent accessible surface area changes and indicate hydrophobic contributions to complex formation. DNase I footprinting analysis in a long DNA sequence provided supporting evidence that f-ImImIm binds selectively to T·G mismatch sites. PMID:15064359

Amyloidogenic Regions and Interaction Surfaces Overlap in Globular Proteins Related to Conformational Diseases

PubMed Central

Castillo, Virginia; Ventura, Salvador

2009-01-01

Protein aggregation underlies a wide range of human disorders. The polypeptides involved in these pathologies might be intrinsically unstructured or display a defined 3D-structure. Little is known about how globular proteins aggregate into toxic assemblies under physiological conditions, where they display an initially folded conformation. Protein aggregation is, however, always initiated by the establishment of anomalous protein-protein interactions. Therefore, in the present work, we have explored the extent to which protein interaction surfaces and aggregation-prone regions overlap in globular proteins associated with conformational diseases. Computational analysis of the native complexes formed by these proteins shows that aggregation-prone regions do frequently overlap with protein interfaces. The spatial coincidence of interaction sites and aggregating regions suggests that the formation of functional complexes and the aggregation of their individual subunits might compete in the cell. Accordingly, single mutations affecting complex interface or stability usually result in the formation of toxic aggregates. It is suggested that the stabilization of existing interfaces in multimeric proteins or the formation of new complexes in monomeric polypeptides might become effective strategies to prevent disease-linked aggregation of globular proteins. PMID:19696882

Tensorial Minkowski functionals of triply periodic minimal surfaces

PubMed Central

Mickel, Walter; Schröder-Turk, Gerd E.; Mecke, Klaus

2012-01-01

A fundamental understanding of the formation and properties of a complex spatial structure relies on robust quantitative tools to characterize morphology. A systematic approach to the characterization of average properties of anisotropic complex interfacial geometries is provided by integral geometry which furnishes a family of morphological descriptors known as tensorial Minkowski functionals. These functionals are curvature-weighted integrals of tensor products of position vectors and surface normal vectors over the interfacial surface. We here demonstrate their use by application to non-cubic triply periodic minimal surface model geometries, whose Weierstrass parametrizations allow for accurate numerical computation of the Minkowski tensors. PMID:24098847

Surface modification of biomedical and dental implants and the processes of inflammation, wound healing and bone formation.

PubMed

Stanford, Clark M

2010-01-25

Bone adaptation or integration of an implant is characterized by a series of biological reactions that start with bone turnover at the interface (a process of localized necrosis), followed by rapid repair. The wound healing response is guided by a complex activation of macrophages leading to tissue turnover and new osteoblast differentiation on the implant surface. The complex role of implant surface topography and impact on healing response plays a role in biological criteria that can guide the design and development of future tissue-implant surface interfaces.

The role of Proteus mirabilis cell wall features in biofilm formation.

PubMed

Czerwonka, Grzegorz; Guzy, Anna; Kałuża, Klaudia; Grosicka, Michalina; Dańczuk, Magdalena; Lechowicz, Łukasz; Gmiter, Dawid; Kowalczyk, Paweł; Kaca, Wiesław

2016-11-01

Biofilms formed by Proteus mirabilis strains are a serious medical problem, especially in the case of urinary tract infections. Early stages of biofilm formation, such as reversible and irreversible adhesion, are essential for bacteria to form biofilm and avoid eradication by antibiotic therapy. Adhesion to solid surfaces is a complex process where numerous factors play a role, where hydrophobic and electrostatic interactions with solid surface seem to be substantial. Cell surface hydrophobicity and electrokinetic potential of bacterial cells depend on their surface composition and structure, where lipopolysaccharide, in Gram-negative bacteria, is prevailing. Our studies focused on clinical and laboratory P. mirabilis strains, where laboratory strains have determined LPS structures. Adherence and biofilm formation tests revealed significant differences between strains adhered in early stages of biofilm formation. Amounts of formed biofilm were expressed by the absorption of crystal violet. Higher biofilm amounts were formed by the strains with more negative values of zeta potential. In contrast, high cell surface hydrophobicity correlated with low biofilm amount.

Surface-confined Ullmann coupling of thiophene substituted porphyrins

NASA Astrophysics Data System (ADS)

Beggan, J. P.; Boyle, N. M.; Pryce, M. T.; Cafolla, A. A.

2015-09-01

The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ˜423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins.

The Formation of Formaldehyde on Interstellar Carbonaceous Grain Analogs by O/H Atom Addition

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

Potapov, Alexey; Jäger, Cornelia; Henning, Thomas

An understanding of possible scenarios for the formation of astrophysically relevant molecules, particularly complex organic molecules, will bring us one step closer to the understanding of our astrochemical heritage. In this context, formaldehyde is an important molecule as a precursor of methanol, which in turn is a starting point for the formation of more complex organic species. In the present experiments, for the first time, following the synthesis of CO, formaldehyde has been produced on the surface of interstellar grain analogs, hydrogenated fullerene-like carbon grains, by O and H atom bombardment. The formation of H{sub 2}CO is an indication formore » a possible methanol formation route in such systems.« less

Formation of complex bacterial colonies via self-generated vortices

NASA Astrophysics Data System (ADS)

Czirók, András; Ben-Jacob, Eshel; Cohen, Inon; Vicsek, Tamás

1996-08-01

Depending on the environmental conditions bacterial colonies growing on agar surfaces can exhibit complex colony formation and various types of collective motion. Experimental results are presented concerning the hydrodynamics (vortices, migration of bacteria in clusters) and colony formation of a morphotype of Bacillus subtilis. Some of these features are not specific to this morphotype but also have been observed in several other bacterial strains, suggesting the presence of universal effects. A simple model of self-propelled particles is proposed, which is capable of describing the hydrodynamics on the intermediate level, including the experimentally observed rotating disks of bacteria. The colony formation is captured by a complex generic model taking into account nutrient diffusion, reproduction, and sporulation of bacteria, extracellular slime deposition, chemoregulation, and inhomogeneous population. Our model also sheds light on some possible biological benefits of this ``multicellular behavior.''

Theoretical studies of charge transfer and proton transfer complex formation between 3,5-dinitrobenzic acid and 1,2-dimethylimidazole

NASA Astrophysics Data System (ADS)

Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-05-01

Natural atomic charge analysis and molecular electrostatic potential (MEP) surface analysis of hydrogen bonded charge transfer (HBCT) and proton transfer (PT) complex of 3,5-dinitrobenzoic acid (DNBA) and 1,2-dimethylimidazole (DMI) have been investigated by theoretical modelling using widely employed DFT/B3LYP/6-311G(d,p) level of theory. Along with this analysis, Hirshfeld surface study of the intermolecular interactions and associated 2D finger plot for reported PT complex between DNBA and DMI have been explored.

The soluble extracellular domain of E-cadherin interferes with EPEC adherence via interaction with the Tir:intimin complex.

PubMed

Login, Frédéric H; Jensen, Helene H; Pedersen, Gitte A; Amieva, Manuel R; Nejsum, Lene N

2018-06-19

Enteropathogenic Escherichia coli (EPEC) causes watery diarrhea when colonizing the surface of enterocytes. The translocated intimin receptor (Tir):intimin receptor complex facilitates tight adherence to epithelial cells and formation of actin pedestals beneath EPEC. We found that the host cell adherens junction protein E-cadherin (Ecad) was recruited to EPEC microcolonies. Live-cell and confocal imaging revealed that Ecad recruitment depends on, and occurs after, formation of the Tir:intimin complex. Combinatorial binding experiments using wild-type EPEC, isogenic mutants lacking Tir or intimin, and E. coli expressing intimin showed that the extracellular domain of Ecad binds the bacterial surface in a Tir:intimin-dependent manner. Finally, addition of the soluble extracellular domain of Ecad to the infection medium or depletion of Ecad extracellular domain from the cell surface reduced EPEC adhesion to host cells. Thus, the soluble extracellular domain of Ecad may be used in the design of intervention strategies targeting EPEC adherence to host cells.-Login, F. H., Jensen, H. H., Pedersen, G. A., Amieva, M. R., Nejsum, L. N. The soluble extracellular domain of E-cadherin interferes with EPEC adherence via interaction with the Tir:intimin complex.

Prediction of protein-protein interaction sites using electrostatic desolvation profiles.

PubMed

Fiorucci, Sébastien; Zacharias, Martin

2010-05-19

Protein-protein complex formation involves removal of water from the interface region. Surface regions with a small free energy penalty for water removal or desolvation may correspond to preferred interaction sites. A method to calculate the electrostatic free energy of placing a neutral low-dielectric probe at various protein surface positions has been designed and applied to characterize putative interaction sites. Based on solutions of the finite-difference Poisson equation, this method also includes long-range electrostatic contributions and the protein solvent boundary shape in contrast to accessible-surface-area-based solvation energies. Calculations on a large set of proteins indicate that in many cases (>90%), the known binding site overlaps with one of the six regions of lowest electrostatic desolvation penalty (overlap with the lowest desolvation region for 48% of proteins). Since the onset of electrostatic desolvation occurs even before direct protein-protein contact formation, it may help guide proteins toward the binding region in the final stage of complex formation. It is interesting that the probe desolvation properties associated with residue types were found to depend to some degree on whether the residue was outside of or part of a binding site. The probe desolvation penalty was on average smaller if the residue was part of a binding site compared to other surface locations. Applications to several antigen-antibody complexes demonstrated that the approach might be useful not only to predict protein interaction sites in general but to map potential antigenic epitopes on protein surfaces. Copyright (c) 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Surface reactions of iron - enriched smectites: adsorption and transformation of hydroxy fatty acids and phenolic acids

NASA Astrophysics Data System (ADS)

Polubesova, Tamara; Olshansky, Yaniv; Eldad, Shay; Chefetz, Benny

2014-05-01

Iron-enriched smectites play an important role in adsorption and transformation of soil organic components. Soil organo-clay complexes, and in particular humin contain hydroxy fatty acids, which are derived from plant biopolymer cutin. Phenolic acids belong to another major group of organic acids detected in soil. They participate in various soil processes, and are of concern due to their allelopathic activity. We studied the reactivity of iron-enriched smectites (Fe(III)-montmorillonite and nontronite) toward both groups of acids. We used fatty acids- 9(10),16-dihydroxypalmitic acid (diHPA), isolated from curtin, and 9,10,16-trihydroxypalmitic acid (triHPA); the following phenolic acids were used: ferulic, p-coumaric, syringic, and vanillic. Adsorption of both groups of acids was measured. The FTIR spectra of fatty acid-mineral complexes indicated inner-sphere complexation of fatty acids with iron-enriched smectites (versus outer-sphere complexation with Ca(II)-montmorillonite). The LC-MS results demonstrated enhanced esterification of fatty acids on the iron-enriched smectite surfaces (as compared to Ca(II)-montmorillonite). This study suggests that fatty acids can be esterified on the iron-enriched smectite surfaces, which results in the formation of stable organo-mineral complexes. These complexes may serve as a model for the study of natural soil organo-clay complexes and humin. The reaction of phenolic acids with Fe(III)-montmorillonite demonstrated their oxidative transformation by the mineral surfaces, which was affected by molecular structure of acids. The following order of their transformation was obtained: ferulic >syringic >p-coumaric >vanillic. The LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on the Fe(III)-motnomrillonite surface. Our study demonstrate the importance of iron-enriched minerals for the abiotic formation of humic materials and for the transformation of aromatic (phenolic) pollutants.

Tracing the Origins of Nitrogen Bearing Organics Toward Orion KL with Alma

NASA Astrophysics Data System (ADS)

Carroll, Brandon; Crockett, Nathan; Wilkins, Olivia H.; Bergin, Edwin; Blake, Geoffrey

2017-06-01

A comprehensive analysis of a broadband 1.2 THz wide spectral survey of the Orion Kleinmann-Low nebula (Orion KL) has shown that nitrogen bearing complex organics trace systematically hotter gas than O-bearing organics toward this source. The origin of this O/N dichotomy remains a mystery. If complex molecules originate from grain surfaces, N-bearing species may be more difficult to remove from grain surfaces than O-bearing organics. Theoretical studies, however, have shown that hot (T=300 K) gas phase chemistry can produce high abundances of N-bearing organics while suppressing the formation of O-bearing complex molecules. In order to distinguish these distinct formation pathways we have obtained extremely high angular resolution observations of methyl cyanide (CH_3CN) using the Atacama Large Millimeter/Submillimeter Array (ALMA) toward Orion KL. By simultaneously imaging ^{13}CH_3CN and CH_2DCN we map the temperature structure and D/H ratio of CH_3CN. We will present updated results of these observations and discuss their implications for the formation of N-bearing organics in the interstellar medium.

Tracing the Origins of Nitrogen Bearing Organics Toward Orion KL with Alma

NASA Astrophysics Data System (ADS)

Carroll, Brandon; Crockett, Nathan; Bergin, Edwin; Blake, Geoffrey

2016-06-01

A comprehensive analysis of a broadband 1.2 THz wide spectral survey of the Orion Kleinmann-Low nebula (Orion KL) from the Herschel Space Telescope has shown that nitrogen bearing complex organics trace systematically hotter gas than O-bearing organics toward this source. The origin of this O/N dichotomy remains a mystery. If complex molecules originate from grain surfaces, N-bearing species may be more difficult to remove from grain surfaces than O-bearing organics. Theoretical studies, however, have shown that hot (T=300 K) gas phase chemistry can produce high abundances of N-bearing organics while suppressing the formation of O-bearing complex molecules. In order to distinguish these distinct formation pathways we have obtained extremely high angular resolution observations of methyl cyanide (CH_3CN) using the Atacama Large Millimeter/Submillimeter Array (ALMA) toward Orion KL. By simultaneously imaging 13CH_3CN and CH_2DCN we map the temperature structure and D/H ratio of CH_3CN. We will present the initial results of these observations and discuss their implications for the formation of N-bearing organics in the interstellar medium.

Collective evolution of submicron hillocks during the early stages of anisotropic alkaline wet chemical etching of Si(1 0 0) surfaces

NASA Astrophysics Data System (ADS)

Sana, P.; Vázquez, Luis; Cuerno, Rodolfo; Sarkar, Subhendu

2017-11-01

We address experimentally the large-scale dynamics of Si(1 0 0) surfaces during the initial stages of anisotropic wet (KOH) chemical etching, which are characterized through atomic force microscopy. These systems are known to lead to the formation of characteristic pyramids, or hillocks, of typical sizes in the nanometric/micrometer scales, thus with the potential for a large number of applications that can benefit from the nanotexturing of Si surfaces. The present pattern formation process is very strongly disordered in space. We assess the space correlations in such a type of rough surface and elucidate the existence of a complex and rich morphological evolution, featuring at least three different regimes in just 10 min of etching. Such a complex time behavior cannot be consistently explained within a single formalism for dynamic scaling. The pyramidal structure reveals itself as the basic morphological motif of the surface throughout the dynamics. A detailed analysis of the surface slope distribution with etching time reveals that the texturing process induced by the KOH etching is rather gradual and progressive, which accounts for the dynamic complexity. The various stages of the morphological evolution can be accurately reproduced by computer-generated surfaces composed by uncorrelated pyramidal structures. To reach such an agreement, the key parameters are the average pyramid size, which increases with etching time, its distribution and the surface coverage by the pyramidal structures.

Screening of Small Molecule Interactor Library by Using In-Cell NMR Spectroscopy (SMILI-NMR)

PubMed Central

Xie, Jingjing; Thapa, Rajiv; Reverdatto, Sergey; Burz, David S.; Shekhtman, Alexander

2011-01-01

We developed an in-cell NMR assay for screening small molecule interactor libraries (SMILI-NMR) for compounds capable of disrupting or enhancing specific interactions between two or more components of a biomolecular complex. The method relies on the formation of a well-defined biocomplex and utilizes in-cell NMR spectroscopy to identify the molecular surfaces involved in the interaction at atomic scale resolution. Changes in the interaction surface caused by a small molecule interfering with complex formation are used as a read-out of the assay. The in-cell nature of the experimental protocol insures that the small molecule is capable of penetrating the cell membrane and specifically engaging the target molecule(s). Utility of the method was demonstrated by screening a small dipeptide library against the FKBP–FRB protein complex involved in cell cycle arrest. The dipeptide identified by SMILI-NMR showed biological activity in a functional assay in yeast. PMID:19422228

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

USGS Publications Warehouse

Waychunas, G.A.; Fuller, C.C.; Davis, J.A.

2002-01-01

"Two-line" ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10-5 to 10-3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(0.2) A?? and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) A?? and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) A?? in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior. Copyright ?? 2002 Elsevier Science Ltd.

Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment

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

Peng, Xing; Xi, Beidou; Zhao, Ying

Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbedmore » arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.« less

In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

PubMed

Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

2015-02-17

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Complex technology of vacuum-arc processing of structural material surface

NASA Astrophysics Data System (ADS)

Arustamov, V. N.; Ashurov, Kh. B.; Kadyrov, Kh. Kh.; Khudoikulov, I. Kh.

2015-08-01

The development of environmentally friendly and energy-resource-saving technologies based on vacuum arc discharge is a topical problem in science and engineering. In view of their unique properties, cathode spots of a vacuum arc induce cleaning of the surface of an article (cathode) from various contaminations and pulsed thermal action on the surface layers. These processes occur in complex with vacuum-arc deposition of coatings in the same technological cycle, which makes it possible to considerably increase the efficiency of methods for changing physical, mechanical, and chemical properties of the surface of steel articles, which considerably increase their service life. Analysis of the formation of the temperature regime of the surface during vacuum arc action and of the parameters of the deposited coating will make it possible to optimize the regimes of complex treatment of the surfaces of articles and is of considerable theoretical and practical importance.

Efficient surface formation route of interstellar hydroxylamine through NO hydrogenation. II. The multilayer regime in interstellar relevant ices

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Ioppolo, S.; Lamberts, T.; Zhen, J. F.; Cuppen, H. M.; Linnartz, H.

2012-08-01

Hydroxylamine (NH2OH) is one of the potential precursors of complex pre-biotic species in space. Here, we present a detailed experimental study of hydroxylamine formation through nitric oxide (NO) surface hydrogenation for astronomically relevant conditions. The aim of this work is to investigate hydroxylamine formation efficiencies in polar (water-rich) and non-polar (carbon monoxide-rich) interstellar ice analogues. A complex reaction network involving both final (N2O, NH2OH) and intermediate (HNO, NH2O., etc.) products is discussed. The main conclusion is that hydroxyl-amine formation takes place via a fast and barrierless mechanism and it is found to be even more abundantly formed in a water-rich environment at lower temperatures. In parallel, we experimentally verify the non-formation of hydroxylamine upon UV photolysis of NO ice at cryogenic temperatures as well as the non-detection of NC- and NCO-bond bearing species after UV processing of NO in carbon monoxide-rich ices. Our results are implemented into an astrochemical reaction model, which shows that NH2OH is abundant in the solid phase under dark molecular cloud conditions. Once NH2OH desorbs from the ice grains, it becomes available to form more complex species (e.g., glycine and β-alanine) in gas phase reaction schemes.

Evidence for a novel chemisorption bond: Formate (HCO/sub 2/) on Cu(100)

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

Stoehr, J.; Outka, D.A.; Madix, R.J.

1985-03-25

Surface extended-x-ray-absorption fine-structure measurements reveal that formate (HCO/sub 2/) groups on Cu(100) chemisorb via the two oxygen atoms in adjacent fourfold hollow sites with an average O-Cu nearest-neighbor bond length of 2.38 +- 0.03 A. This distance is sig- nificantly (approx.0.4 A) longer than typical O-Cu bonds in bulk compounds and all known surface complexes. The unusually large O-Cu distance is attributed to a steric effect involving the C atom in HCO/sub 2/ and the nearest-neighbor Cu surface atoms.

Effect of homogenisation in formation of thermally induced aggregates in a non- and low- fat milk model system with microparticulated whey proteins.

PubMed

Torres, Isabel Celigueta; Nieto, Gema; Nylander, Tommy; Simonsen, Adam Cohen; Tolkach, Alexander; Ipsen, Richard

2017-05-01

The objective of the research presented in this paper was to investigate how different characteristics of whey protein microparticles (MWP) added to milk as fat replacers influence intermolecular interactions occurring with other milk proteins during homogenisation and heating. These interactions are responsible for the formation of heat-induced aggregates that influence the texture and sensory characteristics of the final product. The formation of heat-induced complexes was studied in non- and low-fat milk model systems, where microparticulated whey protein (MWP) was used as fat replacer. Five MWP types with different particle characteristics were utilised and three heat treatments used: 85 °C for 15 min, 90 °C for 5 min and 95 °C for 2 min. Surface characteristics of the protein aggregates were expressed as the number of available thiol groups and the surface net charge. Intermolecular interactions involved in the formation of protein aggregates were studied by polyacrylamide gel electrophoresis and the final complexes visualised by darkfield microscopy. Homogenisation of non-fat milk systems led to partial adsorption of caseins onto microparticles, independently of the type of microparticle. On the contrary, homogenisation of low-fat milk resulted in preferential adsorption of caseins onto fat globules, rather than onto microparticles. Further heating of the milk, led to the formation of heat induced complexes with different sizes and characteristics depending on the type of MWP and the presence or not of fat. The results highlight the importance of controlling homogenisation and heat processing in yoghurt manufacture in order to induce desired changes in the surface reactivity of the microparticles and thereby promote effective protein interactions.

Formation of complex organic molecules in cold objects: the role of gas-phase reactions

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

2015-04-01

While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

The influence of projectile ion induced chemistry on surface pattern formation

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

Karmakar, Prasanta, E-mail: prasantak@vecc.gov.in; Satpati, Biswarup

We report the critical role of projectile induced chemical inhomogeneity on surface nanostructure formation. Experimental inconsistency is common for low energy ion beam induced nanostructure formation in the presence of uncontrolled and complex contamination. To explore the precise role of contamination on such structure formation during low energy ion bombardment, a simple and clean experimental study is performed by selecting mono-element semiconductors as the target and chemically inert or reactive ion beams as the projectile as well as the source of controlled contamination. It is shown by Atomic Force Microscopy, Cross-sectional Transmission Electron Microscopy, and Electron Energy Loss Spectroscopy measurementsmore » that bombardment of nitrogen-like reactive ions on Silicon and Germanium surfaces forms a chemical compound at impact zones. Continuous bombardment of the same ions generates surface instability due to unequal sputtering and non-uniform re-arrangement of the elemental atom and compound. This instability leads to ripple formation during ion bombardment. For Argon-like chemically inert ion bombardment, the chemical inhomogeneity induced boost is absent; as a result, no ripples are observed in the same ion energy and fluence.« less

Formation and biochemical characterization of tube/pelle death domain complexes: critical regulators of postreceptor signaling by the Drosophila toll receptor.

PubMed

Schiffmann, D A; White, J H; Cooper, A; Nutley, M A; Harding, S E; Jumel, K; Solari, R; Ray, K P; Gay, N J

1999-09-07

In Drosophila, the Toll receptor signaling pathway is required for embryonic dorso-ventral patterning and at later developmental stages for innate immune responses. It is thought that dimerization of the receptor by binding of the ligand spätzle causes the formation of a postreceptor activation complex at the cytoplasmic surface of the membrane. Two components of this complex are the adaptor tube and protein kinase pelle. These proteins both have "death domains", protein interaction motifs found in a number of signaling pathways, particularly those involved in apoptotic cell death. It is thought that pelle is bound by tube during formation of the activation complexes, and that this interaction is mediated by the death domains. In this paper, we show using the yeast two-hybrid system that the wild-type tube and pelle death domains bind together. Mutant tube proteins which do not support signaling in the embryo are also unable to bind pelle in the 2-hybrid assay. We have purified proteins corresponding to the death domains of tube and pelle and show that these form corresponding heterodimeric complexes in vitro. Partial proteolysis reveals a smaller core consisting of the minimal death domain sequences. We have studied the tube/pelle interaction with the techniques of surface plasmon resonance, analytical ultracentrifugation and isothermal titration calorimetry. These measurements produce a value of K(d) for the complex of about 0.5 microM.

Evidence for Escherichia coli Diguanylate Cyclase DgcZ Interlinking Surface Sensing and Adhesion via Multiple Regulatory Routes

PubMed Central

Lacanna, Egidio; Bigosch, Colette; Kaever, Volkhard; Boehm, Alex

2016-01-01

ABSTRACT DgcZ is the main cyclic dimeric GMP (c-di-GMP)-producing diguanylate cyclase (DGC) controlling biosynthesis of the exopolysaccharide poly-β-1,6-N-acetylglucosamine (poly-GlcNAc or PGA), which is essential for surface attachment of Escherichia coli. Although the complex regulation of DgcZ has previously been investigated, its primary role and the physiological conditions under which the protein is active are not fully understood. Transcription of dgcZ is regulated by the two-component system CpxAR activated by the lipoprotein NlpE in response to surface sensing. Here, we show that the negative effect of a cpxR mutation and the positive effect of nlpE overexpression on biofilm formation both depend on DgcZ. Coimmunoprecipitation data suggest several potential interaction partners of DgcZ. Interaction with FrdB, a subunit of the fumarate reductase complex (FRD) involved in anaerobic respiration and in control of flagellum assembly, was further supported by a bacterial-two-hybrid assay. Furthermore, the FRD complex was required for the increase in DgcZ-mediated biofilm formation upon induction of oxidative stress by addition of paraquat. A DgcZ-mVENUS fusion protein was found to localize at one bacterial cell pole in response to alkaline pH and carbon starvation. Based on our data and previous knowledge, an integrative role of DgcZ in regulation of surface attachment is proposed. We speculate that both DgcZ-stimulated PGA biosynthesis and interaction of DgcZ with the FRD complex contribute to impeding bacterial escape from the surface. IMPORTANCE Bacterial cells can grow by clonal expansion to surface-associated biofilms that are ubiquitous in the environment but also constitute a pervasive problem related to bacterial infections. Cyclic dimeric GMP (c-di-GMP) is a widespread bacterial second messenger involved in regulation of motility and biofilm formation, and plays a primary role in bacterial surface attachment. E. coli possesses a plethora of c-di-GMP-producing diguanylate cyclases, including DgcZ. Our study expands the knowledge on the role of DgcZ in regulation of surface attachment and suggests that it interconnects surface sensing and adhesion via multiple routes. PMID:27402625

Evidence for Escherichia coli Diguanylate Cyclase DgcZ Interlinking Surface Sensing and Adhesion via Multiple Regulatory Routes.

PubMed

Lacanna, Egidio; Bigosch, Colette; Kaever, Volkhard; Boehm, Alex; Becker, Anke

2016-09-15

DgcZ is the main cyclic dimeric GMP (c-di-GMP)-producing diguanylate cyclase (DGC) controlling biosynthesis of the exopolysaccharide poly-β-1,6-N-acetylglucosamine (poly-GlcNAc or PGA), which is essential for surface attachment of Escherichia coli Although the complex regulation of DgcZ has previously been investigated, its primary role and the physiological conditions under which the protein is active are not fully understood. Transcription of dgcZ is regulated by the two-component system CpxAR activated by the lipoprotein NlpE in response to surface sensing. Here, we show that the negative effect of a cpxR mutation and the positive effect of nlpE overexpression on biofilm formation both depend on DgcZ. Coimmunoprecipitation data suggest several potential interaction partners of DgcZ. Interaction with FrdB, a subunit of the fumarate reductase complex (FRD) involved in anaerobic respiration and in control of flagellum assembly, was further supported by a bacterial-two-hybrid assay. Furthermore, the FRD complex was required for the increase in DgcZ-mediated biofilm formation upon induction of oxidative stress by addition of paraquat. A DgcZ-mVENUS fusion protein was found to localize at one bacterial cell pole in response to alkaline pH and carbon starvation. Based on our data and previous knowledge, an integrative role of DgcZ in regulation of surface attachment is proposed. We speculate that both DgcZ-stimulated PGA biosynthesis and interaction of DgcZ with the FRD complex contribute to impeding bacterial escape from the surface. Bacterial cells can grow by clonal expansion to surface-associated biofilms that are ubiquitous in the environment but also constitute a pervasive problem related to bacterial infections. Cyclic dimeric GMP (c-di-GMP) is a widespread bacterial second messenger involved in regulation of motility and biofilm formation, and plays a primary role in bacterial surface attachment. E. coli possesses a plethora of c-di-GMP-producing diguanylate cyclases, including DgcZ. Our study expands the knowledge on the role of DgcZ in regulation of surface attachment and suggests that it interconnects surface sensing and adhesion via multiple routes. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Unified Microscopic-Macroscopic Monte Carlo Simulations of Complex Organic Molecule Chemistry in Cold Cores

NASA Astrophysics Data System (ADS)

Chang, Qiang; Herbst, Eric

2016-03-01

The recent discovery of methyl formate and dimethyl ether in the gas phase of cold cores with temperatures as cold as 10 K challenges our previous astrochemical models concerning the formation of complex organic molecules (COMs). The strong correlation between the abundances and distributions of methyl formate and dimethyl ether further shows that current astrochemical models may be missing important chemical processes in cold astronomical sources. We investigate a scenario in which COMs and the methoxy radical can be formed on dust grains via a so-called chain reaction mechanism, in a similar manner to CO2. A unified gas-grain microscopic-macroscopic Monte Carlo approach with both normal and interstitial sites for icy grain mantles is used to perform the chemical simulations. Reactive desorption with varying degrees of efficiency is included to enhance the nonthermal desorption of species formed on cold dust grains. In addition, varying degrees of efficiency for the surface formation of methoxy are also included. The observed abundances of a variety of organic molecules in cold cores can be reproduced in our models. The strong correlation between the abundances of methyl formate and dimethyl ether in cold cores can also be explained. Nondiffusive chemical reactions on dust grain surfaces may play a key role in the formation of some COMs.

Morphology and FT IR spectra of porous silicon

NASA Astrophysics Data System (ADS)

Kopani, Martin; Mikula, Milan; Kosnac, Daniel; Gregus, Jan; Pincik, Emil

2017-12-01

The morphology and chemical bods of p-type and n-type porous Si was compared. The surface of n-type sample is smooth, homogenous without any features. The surface of p-type sample reveals micrometer-sized islands. FTIR investigation reveals various distribution of SiOxHy complexes in both p-and n-type samples. From the conditions leading to porous silicon layer formation (the presence of holes) we suggest both SiOxHy and SiFxHy complexes in the layer.

Removal of basic nitrogen compounds from hydrocarbon liquids

DOEpatents

Givens, Edwin N.; Hoover, David S.

1985-01-01

A method is provided for reducing the concentration of basic nitrogen compounds in hydrocarbonaceous feedstock fluids used in the refining industry by providing a solid particulate carbonaceous adsorbent/fuel material such as coal having active basic nitrogen complexing sites on the surface thereof and the coal with a hydrocarbonaceous feedstock containing basic nitrogen compounds to facilitate attraction of the basic nitrogen compounds to the complexing sites and the formation of complexes thereof on the surface of the coal. The adsorbent coal material and the complexes formed thereon are from the feedstock fluid to provide a hydrocarbonaceous fluid of reduced basic nitrogen compound concentration. The coal can then be used as fuel for boilers and the like.

The Influence of Prior Modes of Growth, Temperature, Medium, and Substrate Surface on Biofilm Formation by Antibiotic-Resistant Campylobacter jejuni.

PubMed

Teh, Amy Huei Teen; Lee, Sui Mae; Dykes, Gary A

2016-12-01

Campylobacter jejuni is one of the most common causes of bacterial gastrointestinal food-borne infection worldwide. It has been suggested that biofilm formation may play a role in survival of these bacteria in the environment. In this study, the influence of prior modes of growth (planktonic or sessile), temperatures (37 and 42 °C), and nutrient conditions (nutrient broth and Mueller-Hinton broth) on biofilm formation by eight C. jejuni strains with different antibiotic resistance profiles was examined. The ability of these strains to form biofilm on different abiotic surfaces (stainless steel, glass, and polystyrene) as well as factors potentially associated with biofilm formation (bacterial surface hydrophobicity, auto-aggregation, and initial attachment) was also determined. The results showed that cells grown as sessile culture generally have a greater ability to form biofilm (P < 0.05) compared to their planktonic counterparts. Biofilm was also greater (P < 0.05) in lower nutrient media, while growth at different temperatures affects biofilm formation in a strain-dependent manner. The strains were able to attach and form biofilms on different abiotic surfaces, but none of them demonstrated strong, complex, or structured biofilm formation. There were no clear trends between the bacterial surface hydrophobicity, auto-aggregation, attachment, and biofilm formation by the strains. This finding suggests that environmental factors did affect biofilm formation by C. jejuni, and they are more likely to persist in the environment in the form of mixed-species rather than monospecies biofilms.

Metal Surface Modification for Obtaining Nano- and Sub-Nanostructured Protective Layers.

PubMed

Ledovskykh, Volodymyr; Vyshnevska, Yuliya; Brazhnyk, Igor; Levchenko, Sergiy

2017-12-01

Regularities of the phase protective layer formation in multicomponent systems involving inhibitors with different mechanism of protective action have been investigated. It was shown that optimization of the composition of the inhibition mixture allows to obtain higher protective efficiency owing to improved microstructure of the phase layer. It was found that mechanism of the film formation in the presence of NaNO 2 -PHMG is due to deposition of slightly soluble PHMG-Fe complexes on the metal surface. On the basis of the proposed mechanism, the advanced surface engineering methods for obtaining nanoscaled and sub-nanostructured functional coatings may be developed.

Metal Surface Modification for Obtaining Nano- and Sub-Nanostructured Protective Layers

NASA Astrophysics Data System (ADS)

Ledovskykh, Volodymyr; Vyshnevska, Yuliya; Brazhnyk, Igor; Levchenko, Sergiy

2017-03-01

Regularities of the phase protective layer formation in multicomponent systems involving inhibitors with different mechanism of protective action have been investigated. It was shown that optimization of the composition of the inhibition mixture allows to obtain higher protective efficiency owing to improved microstructure of the phase layer. It was found that mechanism of the film formation in the presence of NaNO2-PHMG is due to deposition of slightly soluble PHMG-Fe complexes on the metal surface. On the basis of the proposed mechanism, the advanced surface engineering methods for obtaining nanoscaled and sub-nanostructured functional coatings may be developed.

Impact of cleaning methods on the structural properties and morphology of SrTiO3 surface

NASA Astrophysics Data System (ADS)

Arnay, Iciar; Rubio-Zuazo, Juan; Castro, German R.

2018-01-01

SrTiO3 is a widely used substrate for the epitaxial growth of complex systems. Nevertheless, in order to get good quality interface and avoid the formation of defects in the adsorbed layer it is essential to prepare the surface of the substrate prior to the deposition. Thermal and chemical treatments are mostly used to eliminate superficial contamination and improve the surface quality. However, there is a lack of information regarding the impact of these treatments on the formation of structural defects at the SrTiO3 surface. In this work we present a detailed characterization of the SrTiO3 surface for the different cleaning methods paying special attention to the formation of oxygen vacancies, large surface mosaicity and roughness. We prove that thermal treatment induces large surface roughness and that chemical etching produces important structural defects at the surface. Our results show that mechanical polishing provided the best compromise in terms of large surface domains, low roughness, absence of oxygen vacancies and absence of atomic structure modification, although with the presence of low level of contaminants at the SrTiO3 surface.

Mineral Surface-Templated Self-Assembling Systems: Case Studies from Nanoscience and Surface Science towards Origins of Life Research.

PubMed

Gillams, Richard J; Jia, Tony Z

2018-05-08

An increasing body of evidence relates the wide range of benefits mineral surfaces offer for the development of early living systems, including adsorption of small molecules from the aqueous phase, formation of monomeric subunits and their subsequent polymerization, and supramolecular assembly of biopolymers and other biomolecules. Each of these processes was likely a necessary stage in the emergence of life on Earth. Here, we compile evidence that templating and enhancement of prebiotically-relevant self-assembling systems by mineral surfaces offers a route to increased structural, functional, and/or chemical complexity. This increase in complexity could have been achieved by early living systems before the advent of evolvable systems and would not have required the generally energetically unfavorable formation of covalent bonds such as phosphodiester or peptide bonds. In this review we will focus on various case studies of prebiotically-relevant mineral-templated self-assembling systems, including supramolecular assemblies of peptides and nucleic acids, from nanoscience and surface science. These fields contain valuable information that is not yet fully being utilized by the origins of life and astrobiology research communities. Some of the self-assemblies that we present can promote the formation of new mineral surfaces, similar to biomineralization, which can then catalyze more essential prebiotic reactions; this could have resulted in a symbiotic feedback loop by which geology and primitive pre-living systems were closely linked to one another even before life’s origin. We hope that the ideas presented herein will seed some interesting discussions and new collaborations between nanoscience/surface science researchers and origins of life/astrobiology researchers.

Exploring interaction of TNF and orthopoxviral CrmB protein by surface plasmon resonance and free energy calculation.

PubMed

Ivanisenko, Nikita V; Tregubchak, Tatiana V; Saik, Olga V; Ivanisenko, Vladimir A; Shchelkunov, Sergei N

2014-01-01

Inhibition of the activity of the tumor necrosis factor (TNF) has become the main strategy for treating inflammatory diseases. The orthopoxvirus TNF-binding proteins can bind and efficiently neutralize TNF. To analyze the mechanisms of the interaction between human (hTNF) or mouse (mTNF) TNF and the cowpox virus N-terminal binding domain (TNFBD-CPXV), also the variola virus N-terminal binding domain (TNFBD-VARV) and to define the amino acids most importantly involved in the formation of complexes, computer models, derived from the X-ray structure of a homologous hTNF/TNFRII complex, were used together with experiments. The hTNF/TNFBD-CPXV, hTNF/TNFBD-VARV, mTNF/TNFBD-CPXV, and mTNF/TNFBD-VARV complexes were used in the molecular dynamics (MD) simulations and MM/GBSA free energy calculations. The complexes were ordered as hTNF/TNFBD-CPXV, hTNF/TNFBD-VARV, mTNF/TNFBD-CPXV and mTNF/TNFBD-VARV according to increase in the binding affinity. The calculations were in agreement with surface plasmon resonance (SPR) measurements of the binding constants. Key residues involved in complex formation were identified.

Complex Organic Parents during Star-Forming Infall

NASA Astrophysics Data System (ADS)

Drozdovskaya, Maria; Walsh, Catherine; Visser, Ruud; Harsono, Daniel; van Dishoeck, Ewine

2013-07-01

Stars are born upon the gravitation infall of clumps in molecular clouds. Complex organic compounds have been observed to accompany star formation and are also believed to be the simplest ingredients to life. Therefore understanding complex organics under star forming conditions is fundamentally interesting. This work models the formation and distribution of several potential parent species for complex organic compounds, such as formaldehyde (H2CO) and methanol (CH3OH), along trajectories of matter parcels, as they undergo infall from the cold outer envelope towards the hot core region and eventually onto the disk. The code from Visser et al. (2009, 2011) serves as the basis for this research. The gas-phase chemistry network has now been expanded with grain-surface reactions to form CH3OH and, ultimately, larger organics such as methyl formate (HCOOCH3) and dimethyl ether (CH3OCH3). The intention behind this work is to obtain information on complex organic parents in the star formation scenario by means of a physically and chemically robust model. The availability of complex organic compounds will vary depending on where the parent species are abundant, such as in the pre-stellar stage, hot-core, or only in the disk; and where they are available for a sufficient amount of time for the complexity enhancement. Such model-based conclusions can then be used in order to explain the observational data on complex organic compounds.

Mycobacterial biofilms: a greasy way to hold it together.

PubMed

Zambrano, María Mercedes; Kolter, Roberto

2005-12-02

Microorganisms growing on surfaces can form biofilms under certain conditions. In this issue of Cell, Ojha et al. (2005) investigate biofilm formation in mycobacteria. They identify new cell-wall components that are required for the formation of architecturally complex mature biofilms in these bacteria and the surprising involvement of a chaperone protein in this process.

Investigate the complex process in particle-fluid based surface generation technology using reactive molecular dynamics method

NASA Astrophysics Data System (ADS)

Han, Xuesong; Li, Haiyan; Zhao, Fu

2017-07-01

Particle-fluid based surface generation process has already become one of the most important materials processing technology for many advanced materials such as optical crystal, ceramics and so on. Most of the particle-fluid based surface generation technology involves two key process: chemical reaction which is responsible for surface softening; physical behavior which is responsible for materials removal/deformation. Presently, researchers cannot give a reasonable explanation about the complex process in the particle-fluid based surface generation technology because of the small temporal-spatial scale and the concurrent influence of physical-chemical process. Molecular dynamics (MD) method has already been proved to be a promising approach for constructing effective model of atomic scale phenomenon and can serve as a predicting simulation tool in analyzing the complex surface generation mechanism and is employed in this research to study the essence of surface generation. The deformation and piles of water molecule is induced with the feeding of abrasive particle which justifies the property mutation of water at nanometer scale. There are little silica molecule aggregation or materials removal because the water-layer greatly reduce the strength of mechanical interaction between particle and materials surface and minimize the stress concentration. Furthermore, chemical effect is also observed at the interface: stable chemical bond is generated between water and silica which lead to the formation of silconl and the reaction rate changes with the amount of water molecules in the local environment. Novel ring structure is observed in the silica surface and it is justified to be favored of chemical reaction with water molecule. The siloxane bond formation process quickly strengthened across the interface with the feeding of abrasive particle because of the compressive stress resulted by the impacting behavior.

Effect of lattice-gas atoms on the adsorption behaviour of thioether molecules.

PubMed

Pan, Yi; Yang, Bing; Hulot, Catherine; Blechert, Siegfried; Nilius, Niklas; Freund, Hans-Joachim

2012-08-21

Using STM topographic imaging and spectroscopy, we have investigated the adsorption of two thioether molecules, 1,2-bis(phenylthio)benzene and (bis(3-phenylthio)-phenyl)sulfane, on noble and transition metal surfaces. The two substrates show nearly antipodal behaviour. Whereas complexes with one or two protruding centres are observed on Au(111), only flat and uniform ad-structures are found on NiAl(110). The difference is ascribed to the possibility of the thioethers to form metal-organic complexes by coordinating lattice-gas atoms on the Au(111), while only the pristine molecules adsorb on the alloy surface. The metal coordination in the first case is driven by the formation of strong Au-S bonds and enables the formation of characteristic monomer, dimer and chain-like structures of the thioethers, using the Au atoms as linkers. A similar mechanism is not available on the NiAl, because no lattice gas develops at this surface at room temperature. Our work demonstrates how surface properties, i.e. the availability of mobile ad-species, determine the interaction of organic molecules with metallic substrates.

Poly(allyl methacrylate) functionalized hydroxyapatite nanocrystals via the combination of surface-initiated RAFT polymerization and thiol-ene protocol: a potential anticancer drug nanocarrier.

PubMed

Bach, Long Giang; Islam, Md Rafiqul; Vo, Thanh-Sang; Kim, Se-Kwon; Lim, Kwon Taek

2013-03-15

Hydroxyapatite nanocrystals (HAP NCs) were encapsulated by poly(allyl methacrylate) (PolyAMA) employing controlled surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization of allyl methacrylate to afford HAP-PolyAMA nanohybrids. The subsequent thiol-ene coupling of nanohybrids with 2-mercaptosuccinic acid resulted HAP-Poly(AMA-COOH) possessing multicarboxyl group. The formation of the nanohybrids was confirmed by FT-IR and EDS analyses. The TGA and FE-SEM investigation were further suggested the grafting of PolyAMA onto HAP NCs. The utility of the HAP-PolyAMA nanohybrid as drug carrier was also explored. The pendant carboxyl groups on the external layers of nanohybrids were conjugated with anticancer drug cisplatin to afford HAP-Poly(AMA-COOH)/Pt complex. The formation of the complex was confirmed by FT-IR, XPS, and FE-SEM. In vitro evaluation of the synthesized complex as nanomedicine revealed its potential chemotherapeutic efficacy against cancer cell lines. Copyright © 2012 Elsevier Inc. All rights reserved.

Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes

PubMed Central

Paulo Coelho, Joao; Osío Barcina, José; Aicart, Emilio; Tardajos, Gloria; Cruz-Gil, Pablo; Salgado, Cástor; Díaz-Núñez, Pablo

2018-01-01

Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays. PMID:29547539

Characterization of surface complexes in enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Roy, D.; Furtak, T. E.

1984-11-01

An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

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

Loring, John S.; Chen, Jeffrey; Benezeth, Pascale

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM,more » TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.« less

Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

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

Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale

Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM,more » TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.« less

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Ehrenfreund, P.; Kuan, Y. J.

2001-01-01

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

A theoretical investigation into the strength of N-NO2 bonds, ring strain and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX.

PubMed

Wang, Bao-Guo; Ren, Fu-de; Shi, Wen-Jing

2015-11-01

Changes in N-NO2 bond strength, ring strain energy and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX were investigated using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. Analysis of electron density shifts was also carried out. The results indicate that H-bonding energy correlates well with the increment of ring strain energy. Upon complex formation, the strength of the N-NO2 trigger-bond is enhanced, suggesting reduced sensitivity, while judged by the increased ring strain energy, sensitivity is increased. However, some features of the molecular surface electrostatic potential, such as a local maximum above the N-NO2 bond and ring, σ + (2) and electrostatic balance parameter ν, remain essentially unchanged upon complex formation, and only a small change in the impact sensitivity h 50 is suggested. It is not sufficient to determine sensitivity solely on the basis of trigger bond or ring strain; as a global feature of a molecule, the molecular surface electrostatic potential is available to help judge the change of sensitivity in H-bonded complexes. Graphical Abstract The strengthened N-NO2 bond suggests reduced sensitivity, while it is reverse by theincreased ring strain energy upon the complex formation. However, the molecular surfaceelectrostatic potential (V S) shows the little change of h 50. The V S should be taken into accountin the analysis of explosive sensitivity in the H-bonded complex.

Categorized Crater Counts on Martian Lobate Debris Aprons

NASA Astrophysics Data System (ADS)

Berman, D. C.; Crown, D. A.; Joseph, E. C.

2015-05-01

We have developed a new approach for analyzing crater size-frequency distributions designed to interpret formation and modification ages from complex geologic surfaces, such as those of ice-rich debris aprons.

Complex conductivity of organic-rich shales

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.; Torres-Verdin, C.

2013-12-01

We can accurately determine the intrinsic anisotropy and material properties in the laboratory, providing empirical evidence of transverse isotropy and the polarization of the organic and metallic fractions in saturated and unsaturated shales. We develop two distinct approaches to obtain the complex conductivity tensor from spectral induced polarization (SIP) measurements. Experimental results indicate clear anisotropy, and characterize the effects of thermal maturation, TOC, and pyrite, aiding in the calibration and interpretation of geophysical data. SIP is a non-intrusive measurement, sensitive to the surface conductance of mineral grains, frequency-dependent polarization of the electrical double layer, and bulk conductivity of the pore water. The in-phase and quadrature components depend upon parameters of principal importance in unconventional shale formation evaluation (e.g., the distribution of pore throat sizes, formation factor, permeability, salinity and cation exchange capacity (CEC), fluid saturation and wettability). In addition to the contribution of the electrical double layer of non-conducting minerals to surface conductivity, we have observed a clear relaxation associated with kerogen pyrolysis, pyrite distribution, and evidence that the CEC of the kerogen fraction may also contribute, depending on thermal maturation history. We utilize a recent model for anisotropic complex conductivity, and rigorous experimental protocols to quantify the role of kerogen and pyrolysis on surface and quadrature conductivity in mudrocks. The complex conductivity tensor σ* describes the directional dependence of electrical conduction in a porous medium, and accounts for both conduction and polarization. The complex-valued tensor components are given as σ*ij , where σ'ij represents in-phase and σ"ij denotes quadrature conductivities. The directional dependence of the complex conductivity tensor is relegated to the textural properties of the material. The components of the formation factor and connectivity (tortuosity) tensors Fij and Tij (affecting the bulk and surface conductivity, respectively) are correlated as Fij=TijΦ. Both conductivity and connectivity tensors share the same eigenvectors; the anisotropy ratio is equivalent in TI media. At high pore water salinity, surface and quadrature conductivity share the same bulk tortuosity; when surface conductivity dominates (low salinity), conductivity is controlled by the surface conductance, and the tortuosity of electrical current along mineral surfaces usually higher than that of the pore water. We developed two distinct SIP measurement protocols to obtain the tensor: (1) azimuthal sampling and inversion of phasor potentials through the full-field solution of the Laplace equation; (2) direct measurement of complex conductivity eigenvalues by polarized, single-component stimulus current. Experiments also include unsaturated and saturated measurements with three brines of known salinity and pH, at log-distributed frequencies ranging 1 mHz to 45 kHz. Both azimuthal spectra and eigenvalue spectra validate the theoretical model and illustrate the effectiveness of the protocols themselves. We obtain the textural tensors and invert key parameters including Archie exponents and CEC, and characterize the relaxation phenomena associated with kerogen content and maturity for multiphase fluid systems.

Heat capacity changes in carbohydrates and protein-carbohydrate complexes.

PubMed

Chavelas, Eneas A; García-Hernández, Enrique

2009-05-13

Carbohydrates are crucial for living cells, playing myriads of functional roles that range from being structural or energy-storage devices to molecular labels that, through non-covalent interaction with proteins, impart exquisite selectivity in processes such as molecular trafficking and cellular recognition. The molecular bases that govern the recognition between carbohydrates and proteins have not been fully understood yet. In the present study, we have obtained a surface-area-based model for the formation heat capacity of protein-carbohydrate complexes, which includes separate terms for the contributions of the two molecular types. The carbohydrate model, which was calibrated using carbohydrate dissolution data, indicates that the heat capacity contribution of a given group surface depends on its position in the saccharide molecule, a picture that is consistent with previous experimental and theoretical studies showing that the high abundance of hydroxy groups in carbohydrates yields particular solvation properties. This model was used to estimate the carbohydrate's contribution in the formation of a protein-carbohydrate complex, which in turn was used to obtain the heat capacity change associated with the protein's binding site. The model is able to account for protein-carbohydrate complexes that cannot be explained using a previous model that only considered the overall contribution of polar and apolar groups, while allowing a more detailed dissection of the elementary contributions that give rise to the formation heat capacity effects of these adducts.

Identification of Au–S complexes on Au(100)

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2016-01-25

In this study, using a combination of scanning tunneling microscopy and density functional theory (DFT) calculations, we have identified a set of related Au–S complexes that form on Au(100), when sulfur adsorbs and lifts the hexagonal surface reconstruction. The predominant complex is diamond-shaped with stoichiometry Au 4S 5. All of the complexes can be regarded as combinations of S–Au–S subunits. The complexes exist within, or at the edges of, p(2 × 2) sulfur islands that cover the unreconstructed Au regions, and are observed throughout the range of S coverage examined in this study, 0.009 to 0.12 monolayers. A qualitative modelmore » is developed which incorporates competitive formation of complexes, Au rafts, and p(2 × 2) sulfur islands, as Au atoms are released by the surface structure transformation.« less

Biofilm three-dimensional architecture influences in situ pH distribution pattern on the human enamel surface

PubMed Central

Xiao, Jin; Hara, Anderson T; Kim, Dongyeop; Zero, Domenick T; Koo, Hyun; Hwang, Geelsu

2017-01-01

To investigate how the biofilm three-dimensional (3D) architecture influences in situ pH distribution patterns on the enamel surface. Biofilms were formed on human tooth enamel in the presence of 1% sucrose or 0.5% glucose plus 0.5% fructose. At specific time points, biofilms were exposed to a neutral pH buffer to mimic the buffering of saliva and subsequently pulsed with 1% glucose to induce re-acidification. Simultaneous 3D pH mapping and architecture of intact biofilms was performed using two-photon confocal microscopy. The enamel surface and mineral content characteristics were examined successively via optical profilometry and microradiography analyses. Sucrose-mediated biofilm formation created spatial heterogeneities manifested by complex networks of bacterial clusters (microcolonies). Acidic regions (pH<5.5) were found only in the interior of microcolonies, which impedes rapid neutralization (taking more than 120 min for neutralization). Glucose exposure rapidly re-created the acidic niches, indicating formation of diffusion barriers associated with microcolonies structure. Enamel demineralization (white spots), rougher surface, deeper lesion and more mineral loss appeared to be associated with the localization of these bacterial clusters at the biofilm-enamel interface. Similar 3D architecture was observed in plaque-biofilms formed in vivo in the presence of sucrose. The formation of complex 3D architectures creates spatially heterogeneous acidic microenvironments in close proximity of enamel surface, which might correlate with the localized pattern of the onset of carious lesions (white spot like) on teeth. PMID:28452377

Surface to Borehole Procedures

EPA Pesticide Factsheets

There is a progression in both complexity and benefits from check shot and synthetic seismogram to vertical seismic profiles (VSP), three‑component VSP, offset VSP, and extrapolation and description of lithologic parameters into the geologic formations.

eF-seek: prediction of the functional sites of proteins by searching for similar electrostatic potential and molecular surface shape.

PubMed

Kinoshita, Kengo; Murakami, Yoichi; Nakamura, Haruki

2007-07-01

We have developed a method to predict ligand-binding sites in a new protein structure by searching for similar binding sites in the Protein Data Bank (PDB). The similarities are measured according to the shapes of the molecular surfaces and their electrostatic potentials. A new web server, eF-seek, provides an interface to our search method. It simply requires a coordinate file in the PDB format, and generates a prediction result as a virtual complex structure, with the putative ligands in a PDB format file as the output. In addition, the predicted interacting interface is displayed to facilitate the examination of the virtual complex structure on our own applet viewer with the web browser (URL: http://eF-site.hgc.jp/eF-seek).

The adsorption interaction of a rutin-biopolymer complex with nanosized silica particles

NASA Astrophysics Data System (ADS)

Fedyanina, T. V.; Barvinchenko, V. N.; Lipkovskaya, N. A.; Pogorelyi, V. K.

2008-10-01

The influence of complex formation with biopolymers on the optical and acid properties of natural flavonoid rutin was studied. The adsorption interaction of biologically active flavonoids from officinal plants with the surface of nanosized silica particles was found to depend on the chemical nature of the biopolymer and adsorbate and solution properties.

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

DOE PAGES

Chen, Yongqiang; Xie, Quan; Sari, Ahmad; ...

2017-11-21

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

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

Chen, Yongqiang; Xie, Quan; Sari, Ahmad

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

Flo11p-Independent Control of “Mat” Formation by Hsp70 Molecular Chaperones and Nucleotide Exchange Factors in Yeast

PubMed Central

Martineau, Céline N.; Beckerich, Jean-Marie; Kabani, Mehdi

2007-01-01

The yeast Saccharomyces cerevisiae has been used as a model for fungal biofilm formation due to its ability to adhere to plastic surfaces and to form mats on low-density agar petri plates. Mats are complex multicellular structures composed of a network of cables that form a central hub from which emanate multiple radial spokes. This reproducible and elaborate pattern is indicative of a highly regulated developmental program that depends on specific transcriptional programming, environmental cues, and possibly cell–cell communication systems. While biofilm formation and sliding motility were shown to be strictly dependent on the cell-surface adhesin Flo11p, little is known about the cellular machinery that controls mat formation. Here we show that Hsp70 molecular chaperones play key roles in this process with the assistance of the nucleotide exchange factors Fes1p and Sse1p and the Hsp40 family member Ydj1p. The disruption of these cofactors completely abolished mat formation. Furthermore, complex interactions among SSA genes were observed: mat formation depended mostly on SSA1 while minor defects were observed upon loss of SSA2; additional mutations in SSA3 or SSA4 further enhanced these phenotypes. Importantly, these mutations did not compromise invasive growth or Flo11p expression, suggesting that Flo11p-independent pathways are necessary to form mats. PMID:17947402

Protein corona – from molecular adsorption to physiological complexity

PubMed Central

Docter, Dominic; Maskos, Michael

2015-01-01

Summary In biological environments, nanoparticles are enshrouded by a layer of biomolecules, predominantly proteins, mediating its subsequent interactions with cells. Detecting this protein corona, understanding its formation with regards to nanoparticle (NP) and protein properties, and elucidating its biological implications were central aims of bio-related nano-research throughout the past years. Here, we discuss the mechanistic parameters that are involved in the protein corona formation and the consequences of this corona formation for both, the particle, and the protein. We review consequences of corona formation for colloidal stability and discuss the role of functional groups and NP surface functionalities in shaping NP–protein interactions. We also elaborate the recent advances demonstrating the strong involvement of Coulomb-type interactions between NPs and charged patches on the protein surface. Moreover, we discuss novel aspects related to the complexity of the protein corona forming under physiological conditions in full serum. Specifically, we address the relation between particle size and corona composition and the latest findings that help to shed light on temporal evolution of the full serum corona for the first time. Finally, we discuss the most recent advances regarding the molecular-scale mechanistic role of the protein corona in cellular uptake of NPs. PMID:25977856

Protein corona - from molecular adsorption to physiological complexity.

PubMed

Treuel, Lennart; Docter, Dominic; Maskos, Michael; Stauber, Roland H

2015-01-01

In biological environments, nanoparticles are enshrouded by a layer of biomolecules, predominantly proteins, mediating its subsequent interactions with cells. Detecting this protein corona, understanding its formation with regards to nanoparticle (NP) and protein properties, and elucidating its biological implications were central aims of bio-related nano-research throughout the past years. Here, we discuss the mechanistic parameters that are involved in the protein corona formation and the consequences of this corona formation for both, the particle, and the protein. We review consequences of corona formation for colloidal stability and discuss the role of functional groups and NP surface functionalities in shaping NP-protein interactions. We also elaborate the recent advances demonstrating the strong involvement of Coulomb-type interactions between NPs and charged patches on the protein surface. Moreover, we discuss novel aspects related to the complexity of the protein corona forming under physiological conditions in full serum. Specifically, we address the relation between particle size and corona composition and the latest findings that help to shed light on temporal evolution of the full serum corona for the first time. Finally, we discuss the most recent advances regarding the molecular-scale mechanistic role of the protein corona in cellular uptake of NPs.

Biofilm formation and local electrostatic force characteristics of Escherichia coli O157:H7 observed by electrostatic force microscopy

NASA Astrophysics Data System (ADS)

Oh, Y. J.; Jo, W.; Yang, Y.; Park, S.

2007-04-01

The authors report growth media dependence of electrostatic force characteristics in Escherichia coli O157:H7 biofilm through local measurement by electrostatic force microscopy (EFM). The difference values of electrostatic interaction between the bacterial surface and the abiotic surface show an exponential decay behavior during biofilm development. In the EFM data, the biofilm in the low nutrient media shows a faster decay than the biofilm in the rich media. The surface potential in the bacterial cells was changed from 957to149mV. Local characterization of extracellular materials extracted from the bacteria reveals the progress of the biofilm formation and functional complexities.

Solution NMR structure of CsgE: Structural insights into a chaperone and regulator protein important for functional amyloid formation.

PubMed

Shu, Qin; Krezel, Andrzej M; Cusumano, Zachary T; Pinkner, Jerome S; Klein, Roger; Hultgren, Scott J; Frieden, Carl

2016-06-28

Curli, consisting primarily of major structural subunit CsgA, are functional amyloids produced on the surface of Escherichia coli, as well as many other enteric bacteria, and are involved in cell colonization and biofilm formation. CsgE is a periplasmic accessory protein that plays a crucial role in curli biogenesis. CsgE binds to both CsgA and the nonameric pore protein CsgG. The CsgG-CsgE complex is the curli secretion channel and is essential for the formation of the curli fibril in vivo. To better understand the role of CsgE in curli formation, we have determined the solution NMR structure of a double mutant of CsgE (W48A/F79A) that appears to be similar to the wild-type (WT) protein in overall structure and function but does not form mixed oligomers at NMR concentrations similar to the WT. The well-converged structure of this mutant has a core scaffold composed of a layer of two α-helices and a layer of three-stranded antiparallel β-sheet with flexible N and C termini. The structure of CsgE fits well into the cryoelectron microscopy density map of the CsgG-CsgE complex. We highlight a striking feature of the electrostatic potential surface in CsgE structure and present an assembly model of the CsgG-CsgE complex. We suggest a structural mechanism of the interaction between CsgE and CsgA. Understanding curli formation can provide the information necessary to develop treatments and therapeutic agents for biofilm-related infections and may benefit the prevention and treatment of amyloid diseases. CsgE could establish a paradigm for the regulation of amyloidogenesis because of its unique role in curli formation.

Formation mechanism of a silane-PVA/PVAc complex film on a glass fiber surface.

PubMed

Repovsky, Daniel; Jane, Eduard; Palszegi, Tibor; Slobodnik, Marek; Velic, Dusan

2013-10-21

Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si-O-Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non-silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value Sa represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm(2) if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL(-1), respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (Ha ) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL(-1), respectively. The pH-dependent zeta-potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non-silanized glass fiber surface and the silane film have similar zeta potentials ranging from -64 to -12 mV at pH's of 10.5 and 3, respectively. The zeta potentials for the PVA/PVAc microspheres on the glass fiber surface and within the silane film significantly decrease and range from -25 to -5 mV. The shapes of the pH-dependent zeta potentials are different in the cases of silane groups over a pH range from 7 to 4. A triple-layer model is used to fit the non-silanized glass surface and the silane film. The value of the surface-site density for Γ(Xglass) and Γ(Xsilane), in which X denotes the Al-O-Si group, differs by a factor of 10(-4), which suggests an effective coupling of the silane film. A soft-layer model is used to fit the silane-PVA/PVAc complex film, which is approximated as four layers. Such a simplification and compensation of the microsphere shape gives an approximation of the relevant widths of the layers as the follows: 1) the layer of the silane groups makes up 10% of the total length (27 nm), 2) the layer of the first PVA shell contributes 30% to the total length (81 nm), 3) the layer of the PVAc core contributes 30% to the total length (81 nm), and finally 4) the layer of the second PVA shell provides 30% of the total length (81 nm). The coverage simulation resulted in a value of 0.4, which corresponds with the assumption of low-order coverage, and is supported by the AFM scans. Correlating the results of the AFM scans, and the zeta potentials sheds some light on the formation mechanism of the silane-PVA/PVAc complex film. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The equilibrium constant of complex formation in solution: A study utilizing a dielectric constant method

NASA Astrophysics Data System (ADS)

Loh, C. W.

1980-03-01

A method was developed for determining equilibrium constants, heat of reaction, and change in free energy and entropy during a 1:1 complex formation in solutions. The measurements were carried out on ternary systems containing two interacting solutes in an inert solvent. The procedures was applied to the investigation of hydrogen bond complex formations in two mixtures systems, phenol and pyridine in carbon tetrachloride, and 4, 5, 6, 7-tetrachloro-2-trifluoromethylbenzimidazole (TTFB) and alkyl acetate in styrene. The first mixture system was studied in order to compare the results with those obtained by other methods. Results for the second mixture system indicated strong association between molecules of TTFB and alkyl acetate and suggested that the blocking of valinomycin-mediated bilayer membrane conductance by substituted benzimidazoles was due to competition for a limited number of adsorption sites on the membrane surface.

Spatial Complexity Due to Bulk Electronic Liquid Crystals in Superconducting Dy-Bi2212

NASA Astrophysics Data System (ADS)

Carlson, Erica; Phillabaum, Benjamin; Dahmen, Karin

2012-02-01

Surface probes such as scanning tunneling microscopy (STM) have detected complex electronic patterns at the nanoscale in many high temperature superconductors. In cuprates, the pattern formation is associated with the pseudogap phase, a precursor to the high temperature superconducting state. Rotational symmetry breaking of the host crystal (i.e. from C4 to C2) in the form of electronic nematicity has recently been proposed as a unifying theme of the pseudogap phase [Lawler Nature 2010]. However, the fundamental physics governing the nanoscale pattern formation has not yet been identified. Here we use universal cluster properties extracted from STM studies of cuprate superconductors to identify the funda- mental physics controlling the complex pattern formation. We find that due to a delicate balance between disorder, interactions, and material anisotropy, the rotational symmetry breaking is fractal in nature, and that the electronic liquid crystal extends throughout the bulk of the material.

Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

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

Fatimah, Is, E-mail: isfatimah@uii.ac.id; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particlemore » sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.« less

Green synthesis of ZnO nanoparticles via complex formation by using Curcuma longa extract

NASA Astrophysics Data System (ADS)

Fatimah, Is; Yudha, Septian P.; Mutiara, Nur Afisa Lintang

2016-02-01

Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which shows the particle sie at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation was also confirmed from fast chemical oxygen demand (COD) reduction.

Effect of humic acid on nickel(II) sorption to Ca-montmorillonite by batch and EXAFS techniques study.

PubMed

Hu, Jun; Tan, Xiaoli; Ren, Xuemei; Wang, Xiangke

2012-09-21

The influence of humic acid (HA) on Ni(II) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(II) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(II) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(II) consists of ∼6 O atoms at the interatomic distances of ∼2.04 Å in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(II) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(II), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(II) in the natural environment.

Adsorption of weak polyelectrolytes on charged nanoparticles. Impact of salt valency, pH, and nanoparticle charge density. Monte Carlo simulations.

PubMed

Carnal, Fabrice; Stoll, Serge

2011-10-27

Complex formation between a weak flexible polyelectrolyte chain and one positively charged nanoparticle in presence of explicit counterions and salt particles is investigated using Monte Carlo simulations. The influence of parameters such as the nanoparticle surface charge density, salt valency, and solution property such as the pH on the chain protonation/deprotonation process and monomer adsorption at the nanoparticle surface are systematically investigated. It is shown that the nanoparticle presence significantly modifies chain acid/base and polyelectrolyte conformational properties. The importance of the attractive electrostatic interactions between the chain and the nanoparticle clearly promotes the chain deprotonation leading, at high pH and nanoparticle charge density, to fully wrapped polyelectrolyte at the nanoparticle surface. When the nanoparticle bare charge is overcompensated by the polyelectrolyte charges, counterions and salt particles condense at the surface of the polyelectrolyte-nanoparticle complex to compensate for the excess of charges providing from the adsorbed polyelectrolyte chain. It is also shown that the complex formation is significantly affected by the salt valency. Indeed, with the presence of trivalent salt cations, competition is observed between the nanoparticle and the trivalent cations. As a result, the amount of adsorbed monomers is less important than in the monovalent and divalent case and chain conformations are different due to the collapse of polyelectrolyte segments around trivalent cations out of the nanoparticle adsorption layer.

Functionalized granular activated carbon and surface complexation with chromates and bi-chromates in wastewater.

PubMed

Singha, Somdutta; Sarkar, Ujjaini; Luharuka, Pallavi

2013-03-01

Cr(VI) is present in the aqueous medium as chromate (CrO4(2-)) and bi-chromate (HCrO4(-)). Functionalized granular activated carbons (FACs) are used as adsorbents in the treatment of wastewaters containing hexavalent chromium. The FACs are prepared by chemical modifications of granular activated carbons (GACs) using functionalizing agents like HNO3, HCl and HF. The Brunauer, Emmett and Teller surface areas of FAC-HCl (693.5m(2)/g), FAC-HNO3 (648.8m(2)/g) and FAC-HF (726.2m(2)/g) are comparable to the GAC (777.7m(2)/g). But, the adsorption capacity of each of the FAC-HNO3, FAC-HCl and FAC-HF is found to be higher than the GAC. The functional groups play an important role in the adsorption process and pH has practically no role in this specific case. The FACs have hydrophilic protonated external surfaces in particular, along with the functional surface sites capable to make complexes with the CrO4(2-) and HCrO4(-) present. Surface complex formation is maximized in the order FAC-HNO3>FAC-HF>FAC-HCl, in proportion to the total surface acidity. This is also confirmed by the well-known pseudo second-order kinetic model. Physi-sorption equilibrium isotherms are parameterized by using standard Freundlich and Langmuir models. Langmuir fits better. The formation of surface complexes with the functional groups and hexavalent chromium is also revealed in the images of field emission scanning electron micrograph; energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy analysis after adsorption. The intra-particle diffusion is not the only rate-controlling factor. The Boyd's film diffusion model fits very well with R(2) as high as 98.1% for FAC-HNO3. This result demonstrates that the functionalization of the GAC by acid treatments would increase the diffusion rate, predominantly with a boundary layer diffusion effect. Copyright © 2013 Elsevier B.V. All rights reserved.

Gallium(III) adsorption on carbonates and oxides: X-ray absorption fine structure spectroscopy study and surface complexation modeling.

PubMed

Pokrovsky, O S; Pokrovski, G S; Schott, J

2004-11-15

Adsorption of Ga on calcite, magnesite, amorphous silica, and manganese oxide as a function of pH and gallium concentration in solution was studied using a batch adsorption technique. Adsorbed complexes of Ga on calcite, magnesite, and delta-MnO2 were further characterized using XAFS spectroscopy. At high surface loadings from supersaturated solutions, Ga is likely to form a polymeric network at the surface (edge- and corner-sharing octahedra). At low surface loadings, Ga presents as isolated octahedra, probably attached to the Me-O sites on the surface, and coordinated by water molecules and hydroxide groups at 1.90-1.94 A. At pH>6, Ga therefore changes its coordination from 4 to 6 when adsorbing from solution (Ga(OH)(-)4(aq)) onto metal surface sites (MeOGa(OH)n(H2O)2-n(5-n), Me = Ca, Mg, or Mn, and n=1 and 2 for carbonate minerals and MnO2, respectively). Because the EXAFS is not capable of seeing hydrogen atoms, the protonation of surface complexes was determined by fitting the experimental pH-dependent Ga adsorption edge. A surface complexation model which assumes the constant capacitance of the electric double layer (CCM) and postulates the formation of positively charged, neutral and negatively charged surface complexes for carbonates, manganese oxide and silica, respectively, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Ga concentration.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Energetics of formic acid conversion to adsorbed formates on Pt(111) by transient calorimetry.

PubMed

Silbaugh, Trent L; Karp, Eric M; Campbell, Charles T

2014-03-12

Carboxylates adsorbed on solid surfaces are important in many technological applications, ranging from heterogeneous catalysis and surface organo-functionalization to medical implants. We report here the first experimentally determined enthalpy of formation of any surface bound carboxylate on any surface, formate on Pt(111). This was accomplished by studying the dissociative adsorption of formic acid on oxygen-presaturated (O-sat) Pt(111) to make adsorbed monodentate and bidentate formates using single-crystal adsorption calorimetry. The integral heat of molecular adsorption of formic acid on clean Pt(111) at 100 K is 62.5 kJ/mol at 0.25 monolayer (ML). On O-sat Pt(111), the integral heat of the dissociative adsorption of formic acid to make monodentate formate (HCOOmon,ad) plus the water-hydroxyl complex ((H2O-OH)ad) was found to be 76 kJ/mol at 3/8 ML and 100-150 K. Similarly, its integral heat of dissociative adsorption to make bidentate formate (HCOObi,ad) plus (H2O-OH)ad was 106 kJ/mol at 3/8 ML and 150 K. These heats give the standard enthalpies of formation of adsorbed monodentate and bidentate formate on Pt(111) to be -354 ± 5 and -384 ± 5 kJ/mol, respectively, and their net bond enthalpies to the Pt(111) surface to be 224 ± 13 and 254 ± 13 kJ/mol, respectively. Coverage-dependent enthalpies of formation were used to estimate the enthalpy of the elementary reaction HCOOHad → HCOObi,ad + Had to be -4 kJ/mol at zero coverage and +24 kJ/mol at 3/8 ML.

WNK4 inhibits plasma membrane targeting of NCC through regulation of syntaxin13 SNARE formation.

PubMed

Chung, Woo Young; Park, Hyun Woo; Han, Jung Woo; Lee, Min Goo; Kim, Joo Young

2013-12-01

WNK4, a serine/threonine kinase, plays a critical role in the expression of membrane proteins in the cell surface; however, the underlying mechanism of WNK4 is not clear. Here, we demonstrate that WNK4 inhibits the fusion of plasma membrane delivering vesicle with sorting/recycling endosome through disrupting SNARE formation of syntaxin13, an endosomal t-SNARE and VAMP2, the v-SNARE in plasma membrane delivering vesicle. Their interaction and co-localization were enhanced by hyperosmotic stimulation which is known for WNK4 activation. The kinase domain of WNK4 interacts with the transmembrane domain (TM) of syntaxin13 and this interaction was abolished when the TM was replaced with that of syntaxin16. Interestingly, cell fractionation using sucrose gradients revealed that WNK4 inhibited the formation of the syntaxin13/VAMP2 SNARE complex in the endosomal compartment, but not syntaxin16/VAMP2 or syntaxin13/VAMP7. Syntaxin13 was not phosphorylated by WNK4 and WNK4KI also showed the same binding strength and similar inhibitory regulation on SNARE formation of syntaxin13. Physiological relevance of this mechanism was proved with the expression of NCC (Na(+) C1(-) co-transporter) in the cell surface. The inhibiting activity of WNK4 on surface expression of NCC was abolished by syntaxin13 siRNA transfection. These results suggest that WNK4 attenuates PM targeting of NCC proteins through regulation of syntaxin13 SNARE complex formation with VAMP2 in recycling and sorting endosome. © 2013.

The Death Valley turtlebacks reinterpreted as Miocene­ Pliocene folds of a major detachment surface

USGS Publications Warehouse

Holm, Daniel K.; Fleck, Robert J.; Lux, Daniel R.

1994-01-01

Determining the origin of extension parallel folds in metamorphic core complexes is fundamental to understanding the development of detachment faults. An excellent example of such a feature occurs in the Death Valley region of California where a major, undulatory, detachment fault is exposed along the well-known turtleback (antiformal) surfaces of the Black Mountains. In the hanging wall of this detachment fault are deformed strata of the Copper Canyon Formation. New age constraints indicate that the Copper Canyon Formation was deposited from ~6 to 3 Ma. The formation was folded during deposition into a SE-plunging syncline with an axial surface coplanar with that of a synform in the underlying detachment. This relation suggests the turtlebacks are a folded detachment surface formed during large-scale extension in an overall constrictional strain field. The present, more planar, Black Mountains frontal fault system may be the result of out-stepping of a normal fault system away from an older detachment fault that was deactivated by folding.

Gels of sodium alginate‒chitosan interpolyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Brovko, O. S.; Palamarchuk, I. A.; Val'chuk, N. A.; Chukhchin, D. G.; Bogolitsyn, K. G.; Boitsova, T. A.

2017-08-01

Aspects of the formation of gels of interpolyelectrolyte complexes (IPECs) based on sodium alginate (NaAlg) and chitosan are studied. The effect the conditions of synthesis and complex composition have on the morphological structure and functional properties of these complexes is examined. It is established that complexation in this system proceeds according to a mechanism of electrostatic interaction between the oppositely charged carboxylic groups of the L-hyaluronic acid pyranose cycles of NaAlg proximal polymer chains and chitosan's amino groups, along with a multitude of hydrogen bonds and dispersion forces. We show that the mechanism of IPEC formation is strongly influenced by the conformational state of a lyophilizing component that is present in the system in excess. The inner surfaces of cryogels based on NaAlg‒chitosan IPECs is found to be strongly influenced by the degree of conversion between the parental polyelectrolytes. The most developed mesoporous structure is obtained when a denser gel forms in the system.

Surface Segregation in Multicomponent Systems: Modeling of Surface Alloys and Alloy Surfaces

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Ferrante, John; Noebe, Ronald D.; Good, Brian; Honecy, Frank S.; Abel, Phillip

1999-01-01

The study of surface segregation, although of great technological importance, has been largely restricted to experimental work due to limitations associated with theoretical methods. However, recent improvements in both first-particle and semi-empirical methods are opening, the doors to an array of new possibilities for surface scientists. We apply one of these techniques, the Bozzolo, Ferrante and Smith (BFS) method for alloys, which is particularly suitable for complex systems, to several aspects of the computational modeling of surfaces and segregation, including alloy surface segregation, structure and composition of alloy surfaces, and the formation of surface alloys. We conclude with the study of complex NiAl-based binary, ternary and quaternary thin films (with Ti, Cr and Cu additions to NiAl). Differences and similarities between bulk and surface compositions are discussed, illustrated by the results of Monte Carlo simulations. For some binary and ternary cases, the theoretical predictions are compared to experimental results, highlighting the accuracy and value of this developing theoretical tool.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

2015-10-01

Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

An electrochemical label-free and sensitive thrombin aptasensor based on graphene oxide modified pencil graphite electrode.

PubMed

Ahour, F; Ahsani, M K

2016-12-15

In this work, we tactfully constructed a novel label-free electrochemical aptasensor for rapid and facile detection of thrombin using graphene oxide (GO) and thrombin binding aptamer (TBA). The strategy relies on the preferential adsorption of single-stranded DNA (ssDNA) to GO over aptamer-target complexes. The TBA-thrombin complex formation was monitored by differential pulse voltammetry (DPV) using the guanine oxidation signal. In the absence of thrombin, the aptamers adsorbed onto the surface of GO leading to a strong background guanine oxidation signal. Conversely, in the presence of thrombin, the conformational transformation of TBA after incubating with the thrombin solution and formation of the aptamer-thrombin complexes which had weak binding ability to GO, leads to the desorption of TBA-thrombin complex from electrode surface and significant oxidation signal decrease. The selectivity of the biosensor was studied using other biological substances. The biosensor's signal was proportional to the thrombin concentration from 0.1 to 10nM with a detection limit of 0.07nM. Particularly, the proposed method could be widely applied to the aptamer-based determination of other target analytes. Copyright © 2016 Elsevier B.V. All rights reserved.

Multifunctional Ultra-high Vacuum Apparatus for Studies of the Interactions of Chemical Warfare Agents on Complex Surfaces

DTIC Science & Technology

2014-01-02

of the formation of a hydrogen-bonded hydroxyl. Characteristic modes of the sarin molecule itself are also ob- served. These experimental results show...chemical warfare agent, surface science, uptake, decontamination, filtration , UHV, XPS, FTIR, TPD REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S...challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science

Effects of ultrasonic treatment on amylose-lipid complex formation and properties of sweet potato starch-based films.

PubMed

Liu, Pengfei; Wang, Rui; Kang, Xuemin; Cui, Bo; Yu, Bin

2018-06-01

To investigate the effect of ultrasonic treatment on the properties of sweet potato starch and sweet potato starch-based films, the complexing index, thermograms and diffractograms of the sweet potato starch-lauric acid composite were tested, and light transmission, microstructure, and mechanical and moisture barrier properties of the films were measured. The results indicated that the low power density ultrasound was beneficial to the formation of an inclusion complex. In thermograms, the gelatinization enthalpies of the ultrasonically treated starches were lower than those of the untreated sample. With the ultrasonic amplitude increased from 40% to 70%, the melting enthalpy (ΔH) of the inclusion complex gradually decreased. X-ray diffraction revealed that the diffraction intensity of the untreated samples was weaker than that of the ultrasonically treated samples. When the ultrasonic amplitude was above 40%, the diffraction intensity and relative crystallinity of inclusion complex gradually decreased. The scanning electronic microscope showed that the surface of the composite films became smooth after being treated by ultrasonication. Ultrasonication led to a reduction in film surface roughness under atomic force microscopy analysis. The films with ultrasonic treatment exhibited higher light transmission, lower elongation at break, higher tensile strength and better moisture barrier property than those without ultrasonic treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Soils as relative-age dating tools

USGS Publications Warehouse

Markewich, Helaine Walsh; Pavich, Milan J.; Wysocki, Douglas A.

2017-01-01

Soils develop at the earth's surface via multiple processes that act through time. Precluding burial or disturbance, soil genetic horizons form progressively and reflect the balance among formation processes, surface age, and original substrate composition. Soil morphology provides a key link between process and time (soil age), enabling soils to serve as both relative and numerical dating tools for geomorphic studies and landscape evolution. Five major factors define the contemporary state of all soils: climate, organisms, topography, parent material, and time. Soils developed on similar landforms and parent materials within a given landscape comprise what we term a soil/landform/substrate complex. Soils on such complexes that differ in development as a function of time represent a soil chronosequence. In a soil chronosequence, time constitutes the only independent formation factor; the other factors act through time. Time dictates the variations in soil development or properties (field or laboratory measured) on a soil/landform/substrate complex. Using a dataset within the chronosequence model, we can also formulate various soil development indices based upon one or a combination of soil properties, either for individual soil horizons or for an entire profile. When we evaluate soil data or soil indices mathematically, the resulting equation creates a chronofunction. Chronofunctions help quantify processes and mechanisms involved in soil development, and relate them mathematically to time. These rigorous kinds of comparisons among and within soil/landform complexes constitute an important tool for relative-age dating. After determining one or more absolute ages for a soil/landform complex, we can calculate quantitative soil formation, and or landform-development rates. Multiple dates for several complexes allow rate calculations for soil/landform-chronosequence development and soil-chronofunction calibration.

Extinguishing visible photoluminescence of porous silicon stimulated by antigen-antibody immunocomplex formation

NASA Astrophysics Data System (ADS)

Starodub, Nickolaj F.; Fedorenko, Leonid L.; Starodub, Valentyna M.; Dikiy, S. P.; Svechnikov, Sergey V.

1997-02-01

The photoluminescence of the porous silicon obtained by special procedure with the usage of the chemical and laser beam treatment of silicon crystal was investigated in water, buffer and solution containing sodium chloride. It was demonstrated that the intensity of the photoluminescence did not practically change at the above mentioned conditions as well as after antigen or antibody immobilization on the porous silicon surface. But this parameter of the photoluminescence dramatically decreased in case of specific immune complex formation on the silicon surface. The level of the photoluminescence extinguishing depended on duration and intensity of immune reaction. It is proposed to use discovered effect for creation of the immunosensors based on the direct registration of immunocomplex formation.

Evidence of extensive diversity in bacterial adherence mechanisms that exploit unanticipated stainless steel surface structural complexity for biofilm formation.

PubMed

Davis, Elisabeth M; Li, Dongyang; Shahrooei, Mohammad; Yu, Bin; Muruve, Daniel; Irvin, Randall T

2013-04-01

Three protease-resistant bioorganic 304 stainless steel surfaces were created through the reaction of synthetic peptides consisting of the D-enantiomeric isomer (D-K122-4), the retro-inverso D-enantiomeric isomer (RI-K122-4), and a combination of the two peptides (D+RI) of the Pseudomonas aeruginosa PilA receptor binding domain with steel surfaces. The peptides used to produce the new materials differ only in handedness of their three-dimensional structure, but they reacted with the steel to yield materials that differed in their surface electron work function (EWF) while displaying an identical chemical composition and equivalent surface adhesive force properties. These surfaces allowed for an assessment of the relative role of surface EWF in initial biofilm formation. We examined the ability of various bacteria (selected strains of Listeria monocytogenes, L. innocua, Staphylococcus aureus and S. epidermidis) to initiate biofilm formation. The D-K1224 generated surface displayed the lowest EWF (classically associated with greater molecular interactions and more extensive biofilm formation) but was observed to be least effectively colonized by bacteria (>50% decrease in bacterial adherence of all strains). The highest surface EWF with the lowest surface free energy (RI-K122-4 generated) was more extensively colonized by bacteria, with the binding of some strains being equivalent to unmodified steel. The D+RI generated surface was least effective in minimizing biofilm formation, where some strains displayed enhanced bacterial colonization. Fluorescent microscopy revealed that the D and RI peptides displayed similar but clearly different binding patterns, suggesting that the peptides recognized different sites on the steel, and that differential binding of the peptides to the steel surfaces influences the binding of different bacterial strains and species. We have demonstrated that stainless steel surfaces can be easily modified by peptides to generate surfaces with new physiochemical properties. The D-K122-4-modified surface substantially decreases biofilm formation compared to the RI-K122-4 and D+RI surfaces. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Molecular self-assembly on surfaces

NASA Astrophysics Data System (ADS)

Mateo-Marti, E.; Pradier, C. M.

2012-09-01

The aim of the present research is to study the interaction of biomolecules, among them single amino acids, on metallic and mineral surfaces, and their chemical reactivity by means of powerful surface science techniques. Therefore, the use of simple biomolecules gives fundamental and significant information, including an adequate control of biomolecule-surface interactions, which will be unattainable to develop with more complex molecules. Furthermore, these studies are focussed on the catalytic properties of different surfaces that could be involved in molecular self-organization processes and the formation of prebiotic organic compounds.

Abiogenic synthesis of nucleotides on the surface of small space bodies with high energy particles

NASA Astrophysics Data System (ADS)

Simakov, M. B.; Kuzicheva, E. A.; Antropov, A. E.; Dodonova, N. Ya

Abiotic formation of such complex biochemical compounds as nucleotides and oligopeptides on the surface of interstellar and interplanetary dust particles (IDP) by cosmic radiation was examined. In order to study the formation of organic compounds on IDPs, solid films prepared from nucleososide and inorganic phosphate were irradiated with high energy protons. Irradiated products were analyzed with HPLC. The natural nucleotides were detected. The main products were 5' AMP (3.2%) and 2'3' cAMP (2.7%). The results were compared with others experiments on the action of ultraviolet radiation with different wavelengths, γ-radiation and heat on solid mixtures of biologically significant compounds. The experiment on abiogenic synthesis of nucleotides on board of space satellite "BION-11" was compared also. The present results suggest that a considerable amount of complex biochemical compounds formed in extraterrestrial environments could have been supplied to the primitive earth before the origin of life.

A geometric modeler based on a dual-geometry representation polyhedra and rational b-splines

NASA Technical Reports Server (NTRS)

Klosterman, A. L.

1984-01-01

For speed and data base reasons, solid geometric modeling of large complex practical systems is usually approximated by a polyhedra representation. Precise parametric surface and implicit algebraic modelers are available but it is not yet practical to model the same level of system complexity with these precise modelers. In response to this contrast the GEOMOD geometric modeling system was built so that a polyhedra abstraction of the geometry would be available for interactive modeling without losing the precise definition of the geometry. Part of the reason that polyhedra modelers are effective is that all bounded surfaces can be represented in a single canonical format (i.e., sets of planar polygons). This permits a very simple and compact data structure. Nonuniform rational B-splines are currently the best representation to describe a very large class of geometry precisely with one canonical format. The specific capabilities of the modeler are described.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

Discrete structural features among interface residue-level classes.

PubMed

Sowmya, Gopichandran; Ranganathan, Shoba

2015-01-01

Protein-protein interaction (PPI) is essential for molecular functions in biological cells. Investigation on protein interfaces of known complexes is an important step towards deciphering the driving forces of PPIs. Each PPI complex is specific, sensitive and selective to binding. Therefore, we have estimated the relative difference in percentage of polar residues between surface and the interface for each complex in a non-redundant heterodimer dataset of 278 complexes to understand the predominant forces driving binding. Our analysis showed ~60% of protein complexes with surface polarity greater than interface polarity (designated as class A). However, a considerable number of complexes (~40%) have interface polarity greater than surface polarity, (designated as class B), with a significantly different p-value of 1.66E-45 from class A. Comprehensive analyses of protein complexes show that interface features such as interface area, interface polarity abundance, solvation free energy gain upon interface formation, binding energy and the percentage of interface charged residue abundance distinguish among class A and class B complexes, while electrostatic visualization maps also help differentiate interface classes among complexes. Class A complexes are classical with abundant non-polar interactions at the interface; however class B complexes have abundant polar interactions at the interface, similar to protein surface characteristics. Five physicochemical interface features analyzed from the protein heterodimer dataset are discriminatory among the interface residue-level classes. These novel observations find application in developing residue-level models for protein-protein binding prediction, protein-protein docking studies and interface inhibitor design as drugs.

Discrete structural features among interface residue-level classes

PubMed Central

2015-01-01

Background Protein-protein interaction (PPI) is essential for molecular functions in biological cells. Investigation on protein interfaces of known complexes is an important step towards deciphering the driving forces of PPIs. Each PPI complex is specific, sensitive and selective to binding. Therefore, we have estimated the relative difference in percentage of polar residues between surface and the interface for each complex in a non-redundant heterodimer dataset of 278 complexes to understand the predominant forces driving binding. Results Our analysis showed ~60% of protein complexes with surface polarity greater than interface polarity (designated as class A). However, a considerable number of complexes (~40%) have interface polarity greater than surface polarity, (designated as class B), with a significantly different p-value of 1.66E-45 from class A. Comprehensive analyses of protein complexes show that interface features such as interface area, interface polarity abundance, solvation free energy gain upon interface formation, binding energy and the percentage of interface charged residue abundance distinguish among class A and class B complexes, while electrostatic visualization maps also help differentiate interface classes among complexes. Conclusions Class A complexes are classical with abundant non-polar interactions at the interface; however class B complexes have abundant polar interactions at the interface, similar to protein surface characteristics. Five physicochemical interface features analyzed from the protein heterodimer dataset are discriminatory among the interface residue-level classes. These novel observations find application in developing residue-level models for protein-protein binding prediction, protein-protein docking studies and interface inhibitor design as drugs. PMID:26679043

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

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

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

Characterizations of the Formation of Polydopamine-Coated Halloysite Nanotubes in Various pH Environments.

PubMed

Feng, Junran; Fan, Hailong; Zha, Dao-An; Wang, Le; Jin, Zhaoxia

2016-10-11

Recent studies demonstrated that polydopamine (PDA) coating is universal to nearly all substrates, and it endows substrates with biocompatibility, postfunctionality, and other useful properties. Surface chemistry of PDA coating is important for its postmodifications and applications. However, there is less understanding of the formation mechanism and surface functional groups of PDA layers generated in different conditions. Halloysite is a kind of clay mineral with tubular nanostructure. Water-swellable halloysite has unique reactivity. In this study, we have investigated the reaction of dopamine in the presence of water-swellable halloysite. We have tracked the reaction progresses in different pH environments by using UV-vis spectroscopy and surface-enhanced Raman spectroscopy (SERS). The surface properties of PDA on halloysite were clarified by X-ray photoelectron spectroscopy (XPS), SERS, Fourier transform infrared (FTIR) characterizations, zeta potential, surface wettability, and morphological characterizations. We noticed that the interaction between halloysite surface and dopamine strongly influences the surface functionality of coated PDA. In addition, pH condition further modulates surface functional groups, resulting in less content of secondary/aromatic amine in PDA generated in weak acidic environment. This study demonstrates that the formation mechanism of polydopamine becomes complex in the presence of inorganic nanomaterials. Substrate property and reaction condition dominate the functionality of obtained PDA together.

Herschel Observations of Extraordinary Sources: Analysi sof the HIFI 1.2 THz Wide Spectral Survey toward Orion KL II. Chemical Implications

NASA Astrophysics Data System (ADS)

Crockett, N. R.; Bergin, E. A.; Neill, J. L.; Favre, C.; Blake, G. A.; Herbst, E.; Anderson, D. E.; Hassel, G. E.

2015-06-01

We present chemical implications arising from spectral models fit to the Herschel/HIFI spectral survey toward the Orion Kleinmann-Low nebula (Orion KL). We focus our discussion on the eight complex organics detected within the HIFI survey utilizing a novel technique to identify those molecules emitting in the hottest gas. In particular, we find the complex nitrogen bearing species CH3CN, C2H3CN, C2H5CN, and NH2CHO systematically trace hotter gas than the oxygen bearing organics CH3OH, C2H5OH, CH3OCH3, and CH3OCHO, which do not contain nitrogen. If these complex species form predominantly on grain surfaces, this may indicate N-bearing organics are more difficult to remove from grain surfaces than O-bearing species. Another possibility is that hot (Tkin ∼ 300 K) gas phase chemistry naturally produces higher complex cyanide abundances while suppressing the formation of O-bearing complex organics. We compare our derived rotation temperatures and molecular abundances to chemical models, which include gas-phase and grain surface pathways. Abundances for a majority of the detected complex organics can be reproduced over timescales ≳105 years, with several species being underpredicted by less than 3σ. Derived rotation temperatures for most organics, furthermore, agree reasonably well with the predicted temperatures at peak abundance. We also find that sulfur bearing molecules that also contain oxygen (i.e., SO, SO2, and OCS) tend to probe the hottest gas toward Orion KL, indicating the formation pathways for these species are most efficient at high temperatures. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Formation of VP-Zn complexes in bulk InP(Zn) by migration of P vacancies from the (110) surface

NASA Astrophysics Data System (ADS)

Slotte, J.; Saarinen, K.; Ebert, Ph.

2006-05-01

We apply a combination of positron annihilation spectroscopy and scanning tunneling microscopy to show that thermally generated P vacancies diffuse from the InP surface toward the bulk. The defect observed in the bulk can be identified as a complex consisting of a P vacancy and a Zn impurity. We infer that this pair is formed when the diffusing positive P vacancy is trapped at the Zn dopant. A rough estimate for the migration energy of the P vacancy results in a value of 1.3eV .

CO2 hydrate nucleation kinetics enhanced by an organo-mineral complex formed at the montmorillonite-water interface.

PubMed

Kyung, Daeseung; Lim, Hyung-Kyu; Kim, Hyungjun; Lee, Woojin

2015-01-20

In this study, we investigated experimentally and computationally the effect of organo-mineral complexes on the nucleation kinetics of CO2 hydrate. These complexes formed via adsorption of zwitter-ionic glycine (Gly-zw) onto the surface of sodium montmorillonite (Na-MMT). The electrostatic attraction between the −NH3(+) group of Gly-zw, and the negatively charged Na-MMT surface, provides the thermodynamic driving force for the organo-mineral complexation. We suggest that the complexation of Gly-zw on the Na-MMT surface accelerates CO2 hydrate nucleation kinetics by increasing the mineral–water interfacial area (thus increasing the number of effective hydrate-nucleation sites), and also by suppressing the thermal fluctuation of solvated Na(+) (a well-known hydrate formation inhibitor) in the vicinity of the mineral surface by coordinating with the −COO(–) groups of Gly-zw. We further confirmed that the local density of hydrate-forming molecules (i.e., reactants of CO2 and water) at the mineral surface (regardless of the presence of Gly-zw) becomes greater than that of bulk phase. This is expected to promote the hydrate nucleation kinetics at the surface. Our study sheds new light on CO2 hydrate nucleation kinetics in heterogeneous marine environments, and could provide knowledge fundamental to successful CO2 sequestration under seabed sediments.

Drosophila Chitinase 2 is expressed in chitin producing organs for cuticle formation.

PubMed

Pesch, Yanina-Yasmin; Riedel, Dietmar; Behr, Matthias

2017-01-01

The architecture of the outer body wall cuticle is fundamental to protect arthropods against invading pathogens and numerous other harmful stresses. Such robust cuticles are formed by parallel running chitin microfibrils. Molting and also local wounding leads to dynamic assembly and disassembly of the chitin-matrix throughout development. However, the underlying molecular mechanisms that organize proper chitin-matrix formation are poorly known. Recently we identified a key region for cuticle thickening at the apical cell surface, the cuticle assembly zone, where Obstructor-A (Obst-A) coordinates the formation of the chitin-matrix. Obst-A binds chitin and the deacetylase Serpentine (Serp) in a core complex, which is required for chitin-matrix maturation and preservation. Here we present evidence that Chitinase 2 (Cht2) could be essential for this molecular machinery. We show that Cht2 is expressed in the chitin-matrix of epidermis, trachea, and the digestive system. There, Cht2 is enriched at the apical cell surface and the dense chitin-matrix. We further show that in Cht2 knockdown larvae the assembly zone is rudimentary, preventing normal cuticle formation and pore canal organization. As sequence similarities of Cht2 and the core complex proteins indicate evolutionarily conserved molecular mechanisms, our findings suggest that Cht2 is involved in chitin formation also in other insects. Copyright © 2016 Elsevier Ltd. All rights reserved.

Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

PubMed

Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

2009-05-01

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

Passive film growth on titanium alloys: physicochemical and biologic considerations.

PubMed

Eliades, T

1997-01-01

The role of reactive oxygen derivatives (hydroxy peroxide, hydroxyl radical, and singlet oxygen) on the precipitation of inorganic and organic complexes onto the surface of titanium implant alloys is discussed in this review. In addition, the effect of possible implication of several biologic entities surrounding the implant on the implant-tissue interface constituents is described. Evidence from relevant studies suggests that local microenvironmental byproducts and factors associated with the inflammatory response resulting from the implant-induced tissue insult may enhance the expressivity of the inherent, clinically important property of titanium to form oxides. Growth of titanium oxide may be explained through several processes derived from biologic, thermodynamic, and electrochemical approaches. The models proposed to interpret this phenomenon are often contradictory, demonstrating inward or outward from the bulk material passive film growth, with increasing or self-limiting levels of oxide formation as a function of time. However, in vivo observations are consistent with aging-induced thickening of the complexes precipitated on the implant material surface. This review attempts to clarify several critical issues pertaining to passive film formation and kinetics on titanium-alloy surfaces.

Structure and functional properties of TiNiZr surface layers obtained by high-velocity oxygen fuel spraying

NASA Astrophysics Data System (ADS)

Rusinov, P. O.; Blednova, Zh M.; Borovets, O. I.

2017-05-01

The authors studied a complex method of surface modification of steels for materials with shape memory effect (SME) Ti-Ni-Zr with a high-velocity oxygen-fuel spraying (HVOF) of mechanically activated (MA) powder in a protective medium. We assessed the functional properties and X-ray diffraction studies, which showed that the formation of surface layers according to the developed technology ensures the manifestation of the shape memory effect.

Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase

NASA Astrophysics Data System (ADS)

Choi, Tae Su; Ko, Jae Yoon; Heo, Sung Woo; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I.

2012-10-01

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular SN2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular SN2 reaction of haloacetate, which correlate well with the experimental observation.

Induced polarization of volcanic rocks - 1. Surface versus quadrature conductivity

NASA Astrophysics Data System (ADS)

Revil, A.; Le Breton, M.; Niu, Q.; Wallin, E.; Haskins, E.; Thomas, D. M.

2017-02-01

We performed complex conductivity measurements on 28 core samples from the hole drilled for the Humu'ula Groundwater Research Project (Hawai'i Island, HI, USA). The complex conductivity measurements were performed at 4 different pore water conductivities (0.07, 0.5, 1.0 or 2.0, and 10 S m-1 prepared with NaCl) over the frequency range 1 mHz to 45 kHz at 22 ± 1 °C. The in-phase conductivity data are plotted against the pore water conductivity to determine, sample by sample, the intrinsic formation factor and the surface conductivity. The intrinsic formation factor is related to porosity by Archie's law with an average value of the cementation exponent m of 2.45, indicating that only a small fraction of the connected pore space controls the transport properties. Both the surface and quadrature conductivities are found to be linearly related to the cation exchange capacity of the material, which was measured with the cobalt hexamine chloride method. Surface and quadrature conductivities are found to be proportional to each other like for sedimentary siliclastic rocks. A Stern layer polarization model is used to explain these experimental results. Despite the fact that the samples contain some magnetite (up to 5 per cent wt.), we were not able to identify the effect of this mineral on the complex conductivity spectra. These results are very encouraging in showing that galvanometric induced polarization measurements can be used in volcanic areas to separate the bulk from the surface conductivity and therefore to define some alteration attributes. Such a goal cannot be achieved with resistivity alone.

Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.

PubMed

Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana

2016-12-01

Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

Nano- to Formation-Scale Estimates of Mineral-Specific Reactive Surface Area

NASA Astrophysics Data System (ADS)

Cole, D. R.; Swift, A.; Sheets, J.; Anovitz, L. M.

2017-12-01

Predictions of changes in fluid composition, coupled with the evolution of the solid matrix, include the generation and testing of reactive transport models. However, translating a heterogeneous natural system into physical and chemical model parameters, including the critical but poorly-constrained metric of fluid-accessible surface area, continues to challenge Earth scientists. Studies of carbon storage capacity, permeability, rock strain due to mineral dissolution and precipitation, or the prediction of rock evolution through diagenesis and weathering each consider macroscale outcomes of processes that often are critically impacted by rock surface geometry at the nanoscale. The approach taken here is to consider the whole vertical extent of a saline reservoir and then to address two questions. First, what is the accessible surface area for each major mineral, and for all adjacent pore sizes from <2 nm on up, within each major lithofacies in that formation? Second, with the formation thus divided into units of analysis, parameterized, and placed into geologic context, what constraints can be placed on reactive surface area as a function of mineral composition? A complex sandstone covering a substantial fraction of the quartz-K-feldspar-illite ternary is selected and mineral-specific surface area quantified using neutron scattering, nitrogen and mercury porosimetry, multi-signal high-resolution mineral mapping, and other techniques. For neutron scattering, scale-specific pore geometries enable more accurate translation of volume into surface area. By applying this workflow to all end-member lithologies of this reservoir formation, equations and maps of surface area as a function of position on a quartz-feldspar-clay ternary plot are developed for each major mineral. Results from this work therefore advance our ability to parameterize models not just for the particular formation studied, but for similar geologic units as well.

New insights on molecular regulation of biofilm formation in plant-associated bacteria.

PubMed

Castiblanco, Luisa F; Sundin, George W

2016-04-01

Biofilms are complex bacterial assemblages with a defined three-dimensional architecture, attached to solid surfaces, and surrounded by a self-produced matrix generally composed of exopolysaccharides, proteins, lipids and extracellular DNA. Biofilm formation has evolved as an adaptive strategy of bacteria to cope with harsh environmental conditions as well as to establish antagonistic or beneficial interactions with their host. Plant-associated bacteria attach and form biofilms on different tissues including leaves, stems, vasculature, seeds and roots. In this review, we examine the formation of biofilms from the plant-associated bacterial perspective and detail the recently-described mechanisms of genetic regulation used by these organisms to orchestrate biofilm formation on plant surfaces. In addition, we describe plant host signals that bacterial pathogens recognize to activate the transition from a planktonic lifestyle to multicellular behavior. © 2015 Institute of Botany, Chinese Academy of Sciences.

SCRATCHING THE SURFACE: Expectations of USAFRICOM

DTIC Science & Technology

2008-04-28

approaches. In response, the U.S. is taking a different approach with the formation of the United States Africa Command (USAFRICOM). USAFRICOM has been...undertaking that requires much more than narrow military focused approaches. In response, the U.S. is taking a different approach with the formation of...complex and intricate problems. "[Africa is a] continent characterized by a high degree of income inequality and is prone to conflict,,2 internally

Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

NASA Astrophysics Data System (ADS)

Vlasova, N. N.; Severinovskaya, O. V.; Golovkova, L. P.

The formation of supramolecular complexes between bilirubin and primary micelles of bile salts has been studied. The association constants of bile salts and binding of bilirubin with these associates have been determined. The adsorption of bilirubin and bile salts from individual and mixed aqueous solutions onto hydrophobic silica surfaces has been investigated. The interaction of bilirubin with primary bile salt micelles and the strong retention in mixed micelles, which are supramolecular complexes, result in the adsorption of bilirubin in free state only.

Detection of Threat Materials Using Terahertz Waveguides and Long Pathlength Terahertz Spectroscopy

DTIC Science & Technology

2015-05-01

intramolecular modes. Therefore a complex spectrum is anticipated. In the range between 0.2 THz and 3.0 THz there have been several free space THz...narrowing. A more complex underlying spectrum is only suggested, but not resolved. A PETN layer was formed on an Au-coated PPWG surface by drop casting...structure of the analyte, or complex formation where metal ions incorporate into the lattice of the analyte. In each of these cases the resulting THz

Electron-molecule chemistry and charging processes on organic ices and Titan's icy aerosol surrogates

NASA Astrophysics Data System (ADS)

Pirim, C.; Gann, R. D.; McLain, J. L.; Orlando, T. M.

2015-09-01

Electron-induced polymerization processes and charging events that can occur within Titan's atmosphere or on its surface were simulated using electron irradiation and dissociative electron attachment (DEA) studies of nitrogen-containing organic condensates. The DEA studies probe the desorption of H- from hydrogen cyanide (HCN), acetonitrile (CH3CN), and aminoacetonitrile (NH2CH2CN) ices, as well as from synthesized tholin materials condensed or deposited onto a graphite substrate maintained at low temperature (90-130 K). The peak cross sections for H- desorption during low-energy (3-15 eV) electron irradiation were measured and range from 3 × 10-21 to 2 × 10-18 cm2. Chemical and structural transformations of HCN ice upon 2 keV electron irradiation were investigated using X-ray photoelectron and Fourier-transform infrared spectroscopy techniques. The electron-beam processed materials displayed optical properties very similar to tholins produced by conventional discharge methods. Electron and negative ion trapping lead to 1011 charges cm-2 on a flat surface which, assuming a radius of 0.05 μm for Titan aerosols, is ∼628 charges/radius (in μm). The facile charge trapping indicates that electron interactions with nitriles and complex tholin-like molecules could affect the conductivity of Titan's atmosphere due to the formation of large negative ion complexes. These negatively charged complexes can also precipitate onto Titan's surface and possibly contribute to surface reactions and the formation of dunes.

Lewis acid properties of alumina based catalysts: study by paramagnetic complexes of probe molecules

NASA Astrophysics Data System (ADS)

Fionov, Alexander V.

2002-06-01

Lewis acid properties of LiAl 5O 8/Al 2O 3 (2 wt.% Li) and MgAl 2O 4/Al 2O 3 (3 wt.% Mg) catalysts were studied by EPR of adsorbed probe molecules--anthraquinone and 2,2,6,6-tetramethylpiperidine- N-oxyl (TEMPO). The lesser (in comparison with γ-Al 2O 3) concentration and the strength of Lewis acid sites (LAS) formed on the surface of aluminate layer has been shown. The stability of this layer plays important role in the change of Lewis acid properties during the calcination of modified alumina. The lithium aluminate layer was stable at used calcination temperature, 773 K, meanwhile magnesium aluminate layer observed only at calcination temperature below 723 K. The increase of the calcination temperature to 773 K caused the segregation of MgAl 2O 4 on the surface resulted in the release of alumina surface and recovery of the Lewis acid properties. The differences in the LAS manifestations towards TEMPO and anthraquinone was discussed. The mechanism of the formation of anthraquinone paramagnetic complexes with LAS--three-coordinated aluminum ions--was proposed. This mechanism includes the formation of anthrasemiquinone, and then--anthrasemiquinone ion pair or triple ion. Fragments like -O-Al +-O- play the role of cations in these ion pairs and triple ions. Proposed mechanism can also be applied for the consideration of similar anthraquinone paramagnetic complexes on the surface of gallium oxide containing systems.

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

NASA Astrophysics Data System (ADS)

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; Davis, J. A.

2018-01-01

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonite edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites ('spillover' effect). A series of U(VI) - Na-montmorillonite batch adsorption experiments was conducted as a function of pH, with variable U(VI), Ca, and dissolved carbonate concentrations. Based on the experimental data, a new type of surface complexation model (SCM) was developed for montmorillonite, that specifically accounts for the spillover effect using the edge surface speciation model by Tournassat et al. (2016a). The SCM allows for a prediction of U(VI) adsorption under varying chemical conditions with a minimum number of fitting parameters, not only for our own experimental results, but also for a number of published data sets. The model agreed well with many of these datasets without introducing a second site type or including the formation of ternary U(VI)-carbonato surface complexes. The model predictions were greatly impacted by utilizing analytical measurements of dissolved inorganic carbon (DIC) concentrations in individual sample solutions rather than assuming solution equilibration with a specific partial pressure of CO2, even when the gas phase was laboratory air. Because of strong aqueous U(VI)-carbonate solution complexes, the measurement of DIC concentrations was even important for systems set up in the 'absence' of CO2, due to low levels of CO2 contamination during the experiment.

Formation of magnetic discontinuities through viscous relaxation

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

Kumar, Sanjay; Bhattacharyya, R.; Smolarkiewicz, P. K.

2014-05-15

According to Parker's magnetostatic theorem, tangential discontinuities in magnetic field, or current sheets (CSs), are generally unavoidable in an equilibrium magnetofluid with infinite electrical conductivity and complex magnetic topology. These CSs are due to a failure of a magnetic field in achieving force-balance everywhere and preserving its topology while remaining in a spatially continuous state. A recent work [Kumar, Bhattacharyya, and Smolarkiewicz, Phys. Plasmas 20, 112903 (2013)] demonstrated this CS formation utilizing numerical simulations in terms of the vector magnetic field. The magnetohydrodynamic simulations presented here complement the above work by demonstrating CS formation by employing a novel approach ofmore » describing the magnetofluid evolution in terms of magnetic flux surfaces instead of the vector magnetic field. The magnetic flux surfaces being the possible sites on which CSs develop, this approach provides a direct visualization of the CS formation, helpful in understanding the governing dynamics. The simulations confirm development of tangential discontinuities through a favorable contortion of magnetic flux surfaces, as the magnetofluid undergoes a topology-preserving viscous relaxation from an initial non-equilibrium state with twisted magnetic field. A crucial finding of this work is in its demonstration of CS formation at spatial locations away from the magnetic nulls.« less

Complementarity of stability patches at the interfaces of protein complexes: Implication for the structural organization of energetic hot spots.

PubMed

Kuttner, Yosef Y; Engel, Stanislav

2018-02-01

A rational design of protein complexes with defined functionalities and of drugs aimed at disrupting protein-protein interactions requires fundamental understanding of the mechanisms underlying the formation of specific protein complexes. Efforts to develop efficient small-molecule or protein-based binders often exploit energetic hot spots on protein surfaces, namely, the interfacial residues that provide most of the binding free energy in the complex. The molecular basis underlying the unusually high energy contribution of the hot spots remains obscure, and its elucidation would facilitate the design of interface-targeted drugs. To study the nature of the energetic hot spots, we analyzed the backbone dynamic properties of contact surfaces in several protein complexes. We demonstrate that, in most complexes, the backbone dynamic landscapes of interacting surfaces form complementary "stability patches," in which static areas from the opposing surfaces superimpose, and that these areas are predominantly located near the geometric center of the interface. We propose that a diminished enthalpy-entropy compensation effect augments the degree to which residues positioned within the complementary stability patches contribute to complex affinity, thereby giving rise to the energetic hot spots. These findings offer new insights into the nature of energetic hot spots and the role that backbone dynamics play in facilitating intermolecular recognition. Mapping the interfacial stability patches may provide guidance for protein engineering approaches aimed at improving the stability of protein complexes and could facilitate the design of ligands that target complex interfaces. © 2017 Wiley Periodicals, Inc.

Architectural elements and bounding surfaces in fluvial deposits: anatomy of the Kayenta formation (lower jurassic), Southwest Colorado

NASA Astrophysics Data System (ADS)

Miall, Andrew D.

1988-03-01

Three well-exposed outcrops in the Kayenta Formation (Lower Jurassic), near Dove Creek in southwestern Colorado, were studied using lateral profiles, in order to test recent regarding architectural-element analysis and the classification and interpretation of internal bounding surfaces. Examination of bounding surfaces within and between elements in the Kayenta outcrops raises problems in applying the three-fold classification of Allen (1983). Enlarging this classification to a six-fold hierarchy permits the discrimination of surfaces intermediate between Allen's second- and third-order types, corresponding to the upper bounding surfaces of macroforms, and internal erosional "reactivation" surfaces within the macroforms. Examples of the first five types of surface occur in the Kayenta outcrops at Dove Creek. The new classifications is offered as a general solution to the problem of description of complex, three-dimensional fluvial sandstone bodies. The Kayenta Formation at Dove Creek consists of a multistorey sandstone body, including the deposits of lateral- and downstream-accreted macroforms. The storeys show no internal cyclicity, neither within individual elements nor through the overall vertical thickness of the formation. Low paleocurrent variance indicates low sinuosity flow, whereas macroform geometry and orientation suggest low to moderate sinuosity. The many internal minor erosion surfaces draped with mud and followed by intraclast breccias imply frequent rapid stage fluctuation, consistent with variable (seasonal? monsonal? ephemmeral?) flow. The results suggest a fluvial architecture similar to that of the South Saskatchewan River, through with a three-dimensional geometry unlike that interpreted from surface studies of that river.

Network analysis reveals the recognition mechanism for complex formation of mannose-binding lectins

NASA Astrophysics Data System (ADS)

Jian, Yiren; Zhao, Yunjie; Zeng, Chen

The specific carbohydrate binding of lectin makes the protein a powerful molecular tool for various applications including cancer cell detection due to its glycoprotein profile on the cell surface. Most biologically active lectins are dimeric. To understand the structure-function relation of lectin complex, it is essential to elucidate the short- and long-range driving forces behind the dimer formation. Here we report our molecular dynamics simulations and associated dynamical network analysis on a particular lectin, i.e., the mannose-binding lectin from garlic. Our results, further supported by sequence coevolution analysis, shed light on how different parts of the complex communicate with each other. We propose a general framework for deciphering the recognition mechanism underlying protein-protein interactions that may have potential applications in signaling pathways.

Experimental identification of nitrogen-vacancy complexes in nitrogen implanted silicon

NASA Astrophysics Data System (ADS)

Adam, Lahir Shaik; Law, Mark E.; Szpala, Stanislaw; Simpson, P. J.; Lawther, Derek; Dokumaci, Omer; Hegde, Suri

2001-07-01

Nitrogen implantation is commonly used in multigate oxide thickness processing for mixed signal complementary metal-oxide-semiconductor and System on a Chip technologies. Current experiments and diffusion models indicate that upon annealing, implanted nitrogen diffuses towards the surface. The mechanism proposed for nitrogen diffusion is the formation of nitrogen-vacancy complexes in silicon, as indicated by ab initio studies by J. S. Nelson, P. A. Schultz, and A. F. Wright [Appl. Phys. Lett. 73, 247 (1998)]. However, to date, there does not exist any experimental evidence of nitrogen-vacancy formation in silicon. This letter provides experimental evidence through positron annihilation spectroscopy that nitrogen-vacancy complexes indeed form in nitrogen implanted silicon, and compares the experimental results to the ab initio studies, providing qualitative support for the same.

Formation mechanism of dot-line square superlattice pattern in dielectric barrier discharge

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

Liu, Weibo; Dong, Lifang, E-mail: donglfhbu@163.com, E-mail: pyy1616@163.com; Wang, Yongjie

We investigate the formation mechanism of the dot-line square superlattice pattern (DLSSP) in dielectric barrier discharge. The spatio-temporal structure studied by using the intensified-charge coupled device camera shows that the DLSSP is an interleaving of three different subpatterns in one half voltage cycle. The dot square lattice discharges first and, then, the two kinds of line square lattices, which form square grid structures discharge twice. When the gas pressure is varied, DLSSP can transform from square superlattice pattern (SSP). The spectral line profile method is used to compare the electron densities, which represent the amounts of surface charges qualitatively. Itmore » is found that the amount of surface charges accumulated by the first discharge of DLSSP is less than that of SSP, leading to a bigger discharge area of the following discharge (lines of DLSSP instead of halos of SSP). The spatial distribution of the electric field of the surface charges is simulated to explain the formation of DLSSP. This paper may provide a deeper understanding for the formation mechanism of complex superlattice patterns in DBD.« less

Study on the mechanism of copper-ammonia complex decomposition in struvite formation process and enhanced ammonia and copper removal.

PubMed

Peng, Cong; Chai, Liyuan; Tang, Chongjian; Min, Xiaobo; Song, Yuxia; Duan, Chengshan; Yu, Cheng

2017-01-01

Heavy metals and ammonia are difficult to remove from wastewater, as they easily combine into refractory complexes. The struvite formation method (SFM) was applied for the complex decomposition and simultaneous removal of heavy metal and ammonia. The results indicated that ammonia deprivation by SFM was the key factor leading to the decomposition of the copper-ammonia complex ion. Ammonia was separated from solution as crystalline struvite, and the copper mainly co-precipitated as copper hydroxide together with struvite. Hydrogen bonding and electrostatic attraction were considered to be the main surface interactions between struvite and copper hydroxide. Hydrogen bonding was concluded to be the key factor leading to the co-precipitation. In addition, incorporation of copper ions into the struvite crystal also occurred during the treatment process. Copyright © 2016. Published by Elsevier B.V.

Actomyosin-dependent formation of the mechanosensitive talin–vinculin complex reinforces actin anchoring

PubMed Central

Ciobanasu, Corina; Faivre, Bruno; Le Clainche, Christophe

2014-01-01

The force generated by the actomyosin cytoskeleton controls focal adhesion dynamics during cell migration. This process is thought to involve the mechanical unfolding of talin to expose cryptic vinculin-binding sites. However, the ability of the actomyosin cytoskeleton to directly control the formation of a talin–vinculin complex and the resulting activity of the complex are not known. Here we develop a microscopy assay with pure proteins in which the self-assembly of actomyosin cables controls the association of vinculin to a talin-micropatterned surface in a reversible manner. Quantifications indicate that talin refolding is limited by vinculin dissociation and modulated by the actomyosin network stability. Finally, we show that the activation of vinculin by stretched talin induces a positive feedback that reinforces the actin–talin–vinculin association. This in vitro reconstitution reveals the mechanism by which a key molecular switch senses and controls the connection between adhesion complexes and the actomyosin cytoskeleton. PMID:24452080

Modeling topology formation during laser ablation

NASA Astrophysics Data System (ADS)

Hodapp, T. W.; Fleming, P. R.

1998-07-01

Micromachining high aspect-ratio structures can be accomplished through ablation of surfaces with high-powered lasers. Industrial manufacturers now use these methods to form complex and regular surfaces at the 10-1000 μm feature size range. Despite its increasingly wide acceptance on the manufacturing floor, the underlying photochemistry of the ablation mechanism, and hence the dynamics of the machining process, is still a question of considerable debate. We have constructed a computer model to investigate and predict the topological formation of ablated structures. Qualitative as well as quantitative agreement with excimer-laser machined polyimide substrates has been demonstrated. This model provides insights into the drilling process for high-aspect-ratio holes.

Geological History of the Tyre Region of Europa: A Regional Perspective on Europan Surface Features and Ice Thickness

NASA Technical Reports Server (NTRS)

Kadel, Steven D.; Chuang, Frank C.; Greeley, Ronald; Moore, Jeffrey M.

2000-01-01

Galileo images of the Tyre Macula region of Europa at regional (170 m/pixel) and local (approx. 40 m/pixel) scales allow mapping and understanding of surface processes and landforms. Ridged plains, doublet and complex ridges, shallow pits, domes, "chaos" areas. impact structures, tilted blocks and massifs, and young fracture systems indicate a complex history of surface deformation on Europa. Regional and local morphologies of the Tyre region of Europa suggest that an impactor penetrated through several kilometers of water ice tc a mobile layer below. The surface morphology was initially dominated by formation of ridged plains, followed by development of ridge bands and doublet ridges, with chaos and fracture formation dominating the latter part of the geologic history of the Tyre region. Two distinct types of chaos have been identified which, along with upwarped dome materials, appear to represent a continuum of features (domes-play chaos-knobby chaos) resulting from increasing degree of surface disruption associated with local lithospheric heating and thinning. Local and regional stratigraphic relationships, block heights, and the morphology of the Tyre impact structure suggest the presence of low-viscosity ice or liquid water beneath a thin (severa1 kilometers) surface ice shell at the time of the impact. The very low impact crater density on the surface of Europa suggests that this thin shell has either formed or been thoroughly resurfaced in the very recent past.

Procoagulant expression in platelets and defects leading to clinical disorders.

PubMed

Solum, N O

1999-12-01

Hemostasis is a result of interactions between fibrillar structures in the damaged vessel wall, soluble components in plasma, and cellular elements in blood represented mainly by platelets and platelet-derived material. During formation of a platelet plug at the damaged vessel wall, factors IXa and VIIIa form the "tenase" complex, leading to activation of factor X on the surface of activated platelets. Subsequently, factors Xa and Va form the "prothrombinase" complex, which catalyzes the formation of thrombin from prothrombin, leading to fibrin formation. An enhanced expression of negatively charged phosphatidylserine in the outer membrane leaflet resulting from a breakdown of the phospholipid asymmetry is essential for the formation of the procoagulant surface. An ATP-driven and inward-acting aminophospholipid "translocase" and a "floppase" counterbalancing this have been postulated to maintain the dynamic state of phospholipid asymmetry. A phospholipid-nonspecific "scramblase," believed to be responsible for the fast breakdown of the asymmetry during cell activation, has recently been isolated from erythrocytes, cloned, and characterized. An intracellular calcium-binding segment and one or more thioesterified fatty acids are probably of importance for calcium-induced activation of this transporter protein. Cytosolic calcium ions also activate the calcium-dependent protease calpain associated with shedding of microvesicles from the transformed platelet membrane. These are shed with a procoagulant surface and with surface-exposed P-selectin from the alpha-granules. Theoretically, therefore, microvesicles can be involved in both coagulation and inflammation. Scott syndrome is probably caused by a defect in the activation of an otherwise normal scramblase, resulting in a relatively severe bleeding tendency. In Stormorken syndrome, the patients demonstrate a spontaneous surface expression of aminophospholipids. Activated platelets and the presence of procoagulant microvesicles have been demonstrated in several clinical conditions, such as thrombotic and idiopathic thrombocytopenia, disseminated intravascular coagulation, and HIV-1 infection, and have been found to be associated with fibrin in thrombosis. Procoagulant microvesicles may also be formed from other cells as a result of apoptosis.

Single-Molecule Interactions of a Monoclonal Anti-DNA Antibody with DNA

PubMed Central

Nevzorova, Tatiana A.; Zhao, Qingze; Lomakin, Yakov A.; Ponomareva, Anastasia A.; Mukhitov, Alexander R.; Purohit, Prashant K.; Weisel, John W.; Litvinov, Rustem I.

2017-01-01

Interactions of DNA with proteins are essential for key biological processes and have both a fundamental and practical significance. In particular, DNA binding to anti-DNA antibodies is a pathogenic mechanism in autoimmune pathology, such as systemic lupus erythematosus. Here we measured at the single-molecule level binding and forced unbinding of surface-attached DNA and a monoclonal anti-DNA antibody MRL4 from a lupus erythematosus mouse. In optical trap-based force spectroscopy, a microscopic antibodycoated latex bead is trapped by a focused laser beam and repeatedly brought into contact with a DNA-coated surface. After careful discrimination of non-specific interactions, we showed that the DNA-antibody rupture force spectra had two regimes, reflecting formation of weaker (20–40 pN) and stronger (>40 pN) immune complexes that implies the existence of at least two bound states with different mechanical stability. The two-dimensional force-free off-rate for the DNA-antibody complexes was ~2.2 × 10−3 s−1, the transition state distance was ~0.94 nm, the apparent on-rate was ~5.26 s−1, and the stiffness of the DNA-antibody complex was characterized by a spring constant of 0.0021 pN/nm, suggesting that the DNA-antibody complex is a relatively stable, but soft and deformable macromolecular structure. The stretching elasticity of the DNA molecules was characteristic of single-stranded DNA, suggesting preferential binding of the MRL4 antibody to one strand of DNA. Collectively, the results provide fundamental characteristics of formation and forced dissociation of DNA-antibody complexes that help to understand principles of DNA-protein interactions and shed light on the molecular basis of autoimmune diseases accompanied by formation of anti-DNA antibodies. PMID:29104846

Preparation of microcapsules by complex coacervation of gum Arabic and chitosan.

PubMed

Butstraen, Chloé; Salaün, Fabien

2014-01-01

Gum Arabic-chitosan microcapsules containing a commercially available blend of triglycerides (Miglyol 812 N) as core phase were synthesized by complex coacervation. This study was conducted to clarify the influence of different parameters on the encapsulation process, i.e. during the emulsion formation steps and during the shell formation, using conductometry, zeta potential, surface and interface tension measurement and Fourier-transform infrared spectroscopy. By carefully analyzing the influencing factors including phase volume ratio, stirring rate and time, pH, reaction time, biopolymer ratio and crosslinking effect, the optimum synthetic conditions were found out. For the emulsion step, the optimum phase volume ratio chosen was 0.10 and an emulsion time of 15 min at 11,000 rpm was selected. The results also indicated that the optimum formation of these complexes appears at a pH value of 3.6 and a weight ratio of chitosan to gum Arabic mixtures of 0.25. Copyright © 2013 Elsevier Ltd. All rights reserved.

Vacancy clustering and its dissociation process in electroless deposited copper films studied by monoenergetic positron beams

NASA Astrophysics Data System (ADS)

Uedono, A.; Yamashita, Y.; Tsutsui, T.; Dordi, Y.; Li, S.; Oshima, N.; Suzuki, R.

2012-05-01

Positron annihilation was used to probe vacancy-type defects in electroless deposited copper films. For as-deposited films, two different types of vacancy-type defects were found to coexist; these were identified as vacancy aggregates (V3-V4) and larger vacancy clusters (˜V10). After annealing at about 200 °C, the defects started to diffuse toward the surface and aggregate. The same tendency has been observed for sulfur only, suggesting the formation of complexes between sulfur and vacancies. The defect concentration near the Cu/barrier-metal interface was high even after annealing above 600 °C, and this was attributed to an accumulation of vacancy-impurity complexes. The observed defect reactions were attributed to suppression of the vacancy diffusion to sinks through the formation of impurity-vacancy complexes. It was shown that electroless plating has a high potential to suppress the formation of voids/hillocks caused by defect migration.

Genesis of femtosecond-induced nanostructures on solid surfaces.

PubMed

Varlamova, Olga; Martens, Christian; Ratzke, Markus; Reif, Juergen

2014-11-01

The start and evolution of the formation of laser-induced periodic surface structures (LIPSS, ripples) are investigated. The important role of irradiation dose (fluence×number of pulses) for the properties of the generated structures is demonstrated. It is shown how, with an increasing dose, the structures evolve from random surface modification to regular sub-wavelength ripples, then coalesce to broader LIPSS and finally form more complex shapes when ablation produces deep craters. First experiments are presented following this evolution in one single irradiated spot.

Optical and thermal properties in ultrafast laser surface nanostructuring on biodegradable polymer

NASA Astrophysics Data System (ADS)

Yada, Shuhei; Terakawa, Mitsuhiro

2015-03-01

We investigate the effect of optical and thermal properties in laser-induced periodic surface structures (LIPSS) formation on a poly-L-lactic acid (PLLA), a biodegradable polymer. Surface properties of biomaterials are known to be one of the key factors in tissue engineering. Methods to process biomaterial surfaces have been studied widely to enhance cell adhesive and anisotropic properties. LIPSS formation has advantages in a dry processing which is able to process complex-shaped surfaces without using a toxic chemical component. LIPSS, however, was difficult to be formed on PLLA due to its thermal and optical properties compared to other polymers. To obtain new perspectives in effect of these properties above, LIPSS formation dependences on wavelength, pulse duration and repetition rate have been studied. At 800 nm of incident wavelength, high-spatial frequency LIPSS (HSFL) was formed after applying 10000 femtosecond pulses at 1.0 J/cm2 in laser fluence. At 400 nm of the wavelength, HSFL was formed at fluences higher than 0.20 J/cm2 with more than 3000 pulses. Since LIPSS was less formed with lower repetition rate, certain heat accumulation may be required for LIPSS formation. With the pulse duration of 2.0 ps, higher laser fluence as well as number of pulses compared to the case of 120 fs was necessary. This indicates that multiphoton absorption process is essential for LIPSS formation. Study on biodegradation modification was also performed.

Papillae formation on trichome cell walls requires the function of the mediator complex subunit Med25.

PubMed

Fornero, Christy; Suo, Bangxia; Zahde, Mais; Juveland, Katelyn; Kirik, Viktor

2017-11-01

Glassy Hair 1 (GLH1) gene that promotes papillae formation on trichome cell walls was identified as a subunit of the transcriptional mediator complex MED25. The MED25 gene is shown to be expressed in trichomes. The expression of the trichome development marker genes GLABRA2 (GL2) and Ethylene Receptor2 (ETR2) is not affected in the glh1 mutant. Presented data suggest that Arabidopsis MED25 mediator component is likely involved in the transcription of genes promoting papillae deposition in trichomes. The plant cell wall plays an important role in communication, defense, organization and support. The importance of each of these functions varies by cell type. Specialized cells, such as Arabidopsis trichomes, exhibit distinct cell wall characteristics including papillae. To better understand the molecular processes important for papillae deposition on the cell wall surface, we identified the GLASSY HAIR 1 (GLH1) gene, which is necessary for papillae formation. We found that a splice-site mutation in the component of the transcriptional mediator complex MED25 gene is responsible for the near papillae-less phenotype of the glh1 mutant. The MED25 gene is expressed in trichomes. Reporters for trichome developmental marker genes GLABRA2 (GL2) and Ethylene Receptor2 (ETR2) were not affected in the glh1 mutant. Collectively, the presented results show that MED25 is necessary for papillae formation on the cell wall surface of leaf trichomes and suggest that the Arabidopsis MED25 mediator component is likely involved in the transcription of a subset of genes that promote papillae deposition in trichomes.

Arsenate immobilization associated with microbial oxidation of ferrous ion in complex acid sulfate water.

PubMed

Ma, Yingqun; Lin, Chuxia

2012-05-30

Chemical, XRD, SEM, RS, FTIR and XPS techniques were used to investigate arsenate immobilization associated with microbial Fe(2+) oxidation in a complex acid sulfate water system consisting of a modified 9 K solution (pH 2.0) plus As, Cu, Cd, Pb, Zn and Mn. At a 1:12.5:70 molar ratio of As:Fe:S, schweretmannite formation was impeded. This was in contrast with the predominant presence of schwertmannite when the heavy metals were absent, suggesting that a schwertmannite binding model is not valid for explaining arsenate immobilization in the complex system. In this study, arsenate was initially immobilized through co-precipitation with non-Fe metals and phosphate. Subsequently when sufficient Fe(3+) was produced from Fe(2+) oxidation, formation of a mixed iron, arsenate and phosphate phase predominated. The last stage involved surface complexation of arsenate species. Pb appeared to play an insignificant role in arsenate immobilization due to its strong affinity for sulfate to form anglesite. Phosphate strongly competed with arsenate for the available binding sites. However, As exhibited an increased capacity to compete with P and S for available binding sites from the co-precipitation to surface complexation stage. Adsorbed As tended to be in HAsO(4)(2-) form. The scavenged arsenate species was relatively stable after 2464-h aging. Copyright © 2012 Elsevier B.V. All rights reserved.

Bacterial adherence and biofilm formation on medical implants: a review.

PubMed

Veerachamy, Suganthan; Yarlagadda, Tejasri; Manivasagam, Geetha; Yarlagadda, Prasad Kdv

2014-10-01

Biofilms are a complex group of microbial cells that adhere to the exopolysaccharide matrix present on the surface of medical devices. Biofilm-associated infections in the medical devices pose a serious problem to the public health and adversely affect the function of the device. Medical implants used in oral and orthopedic surgery are fabricated using alloys such as stainless steel and titanium. The biological behavior, such as osseointegration and its antibacterial activity, essentially depends on both the chemical composition and the morphology of the surface of the device. Surface treatment of medical implants by various physical and chemical techniques are attempted in order to improve their surface properties so as to facilitate bio-integration and prevent bacterial adhesion. The potential source of infection of the surrounding tissue and antimicrobial strategies are from bacteria adherent to or in a biofilm on the implant which should prevent both biofilm formation and tissue colonization. This article provides an overview of bacterial biofilm formation and methods adopted for the inhibition of bacterial adhesion on medical implants. © IMechE 2014.

Interpolymer complexation: comparisons of bulk and interfacial structures.

PubMed

Cattoz, Beatrice; de Vos, Wiebe M; Cosgrove, Terence; Crossman, Martin; Espidel, Youssef; Prescott, Stuart W

2015-04-14

The interactions between the strong polyelectrolyte sodium poly(styrenesulfonate), NaPSS, and the neutral polymer poly(vinylpyrrolidone), PVP, were investigated in bulk and at the silica/solution interface using a combination of diffusion nuclear magnetic resonance spectroscopy (NMR), small-angle neutron scattering (SANS), solvent relaxation NMR, and ellipsometry. We show for the first time that complex formation occurs between NaPSS and PVP in solution; the complexes formed were shown not to be influenced by pH variation, whereas increasing the ionic strength increases the complexation of NaPSS but does not influence the PVP directly. The complexes formed contained a large proportion of NaPSS. Study of these interactions at the silica interface demonstrated that complexes also form at the nanoparticle interface where PVP is added in the system prior to NaPSS. For a constant PVP concentration and varying NaPSS concentration, the system remains stable until NaPSS is added in excess, which leads to depletion flocculation. Surface complex formation using the layer-by-layer technique was also reported at a planar silica interface.

Unraveling the Pore-Forming Steps of Pneumolysin from Streptococcus pneumoniae.

PubMed

van Pee, Katharina; Mulvihill, Estefania; Müller, Daniel J; Yildiz, Özkan

2016-12-14

Pneumolysin (PLY) is the main virulence factor of Streptococcus pneumoniae that causes pneumonia, meningitis, and invasive pneumococcal infection. PLY is produced as monomers, which bind to cholesterol-containing membranes, where they oligomerize into large pores. To investigate the pore-forming mechanism, we determined the crystal structure of PLY at 2.4 Å and used it to design mutants on the surface of monomers. Electron microscopy of liposomes incubated with PLY mutants revealed that several mutations interfered with ring formation. Mutants that formed incomplete rings or linear arrays had strongly reduced hemolytic activity. By high-resolution time-lapse atomic force microscopy of wild-type PLY, we observed two different ring-shaped complexes. Most of the complexes protruded ∼8 nm above the membrane surface, while a smaller number protruded ∼11 nm or more. The lower complexes were identified as pores or prepores by the presence or absence of a lipid bilayer in their center. The taller complexes were side-by-side assemblies of monomers of soluble PLY that represent an early form of the prepore. Our observations suggest a four-step mechanism of membrane attachment and pore formation by PLY, which is discussed in the context of recent structural models. The functional separation of these steps is necessary for the understanding how cholesterol-dependent cytolysins form pores and lyse cells.

Mobile multiwave lidar

NASA Astrophysics Data System (ADS)

Gritsuta, A. N.; Klimkin, A. V.; Kokhanenko, G. P.; Kuryak, A. N.; Osipov, K. Y.; Ponomarev, Yu. N.; Simonova, G. V.

2018-04-01

The task that faced the authors was construction of a mobile lidar complex for detection and investigation of aerosol-gas formations in the atmosphere. The complex must be constructed of commercial industrially produced components as much as possible. Many of engineering solutions had been previously worked out by the authors when the first lidar of such type was developed. The complex is designed for study of capabilities of lidar sensing for remote investigation of aerosol-gas formations by their fluorescence and Raman scattering spectra, as well as topographyc objects by fluorescence spectra of their surfaces. The complex has been tested in 2016, and may be applied for atmospheric sensing, for detection of potentially hazardous and dangerous admixtures above the cities, industrial and agricultural emissions, including emissions after disclosures of agricultural animal burial sites. The complex is mounted on a motor vehicle chassis and is energy-independent, and that allow using it for remote sensing of different objects in different natural conditions. Probing distance: 30 000 meters in elastic scattering channel and 5 000 meters in fluorescence channel.

Nodulation outer proteins: double-edged swords of symbiotic rhizobia

USDA-ARS?s Scientific Manuscript database

Rhizobia are nitrogen-fixing bacteria that establish a nodule symbiosis with legumes. Nodule formation is the result of a complex bacterial infection process, which depends on signals and surface determinants produced by both symbiotic partners. Among them, rhizobial nodulation outer proteins (Nops)...

Impact of silica nanoparticle surface chemistry on protein corona formation and consequential interactions with biological cells.

PubMed

Kurtz-Chalot, Andréa; Villiers, Christian; Pourchez, Jérémie; Boudard, Delphine; Martini, Matteo; Marche, Patrice N; Cottier, Michèle; Forest, Valérie

2017-06-01

Nanoparticles (NP) physico-chemical features greatly influence NP/cell interactions. NP surface functionalization is often used to improve NP biocompatibility or to enhance cellular uptake. But in biological media, the formation of a protein corona adds a level of complexity. The aim of this study was to investigate in vitro the influence of NP surface functionalization on their cellular uptake and the biological response induced. 50nm fluorescent silica NP were functionalized either with amine or carboxylic groups, in presence or in absence of polyethylene glycol (PEG). NP were incubated with macrophages, cellular uptake and cellular response were assessed in terms of cytotoxicity, pro-inflammatory response and oxidative stress. The NP protein corona was also characterized by protein mass spectroscopy. Results showed that NP uptake was enhanced in absence of PEG, while NP adsorption at the cell membrane was fostered by an initial positively charged NP surface. NP toxicity was not correlated with NP uptake. NP surface functionalization also influenced the formation of the protein corona as the profile of protein binding differed among the NP types. Copyright © 2017 Elsevier B.V. All rights reserved.

Modeling of multiple equilibria in the self-aggregation of di-n-decyldimethylammonium chloride/octaethylene glycol monododecyl ether/cyclodextrin ternary systems.

PubMed

Leclercq, Loïc; Lubart, Quentin; Aubry, Jean-Marie; Nardello-Rataj, Véronique

2013-05-28

The surface tension equations of binary surfactant mixtures (di-n-decyldimethylammonium chloride and octaethylene glycol monododecyl ether) are established by combining the Szyszkowski equation of surfactant solutions, the ideal or nonideal mixing theory, and the phase separation model. For surfactant mixtures, the surface tension at the air-water interface is calculated using nonideal theory due to synergism between the two adsorbed surfactant types. The incorporation of cyclodextrin complexation model to the surface tension equations gives a robust model for the description of the surface tension isotherms of binary, ternary, and more complex systems involving numerous inclusion complexes. The surface tension data obtained experimentally shows excellent agreement with the theoretical model below and above the formation of micelles. The strong synergistic effect observed between the two surfactants is disrupted by the presence of CDs, leading to ideal behavior of ternary systems. Indeed, depending on the nature of the cyclodextrin (i.e., α, β, or γ), which allows a tuning of the cavity size, the binding constants with the surfactants are modified as well as the surface properties due to strong modification of equilibria involved in the ternary mixture.

Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

NASA Astrophysics Data System (ADS)

Frasconi, Marco; Mazzei, Franco

2009-07-01

This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

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

Spontaneous formation of linearly arranged microcraters on sol-gel-derived silica-poly(vinylpyrrolidone) hybrid films induced by Bénard-Marangoni convection.

PubMed

Uchiyama, Hiroaki; Mantani, Yuto; Kozuka, Hiromitsu

2012-07-10

Complex, sophisticated surface patterns on micrometer and nanometer scales are obtained when solvent evaporates from solutions containing nonvolatile solutes dropped on a solid substrate. Such evaporation-driven pattern formation has been utilized as a fabrication process of highly ordered patterns in thin films. Here, we suggested the spontaneous pattern formation induced by Bénard-Marangoni convection triggered by solvent evaporation as a novel patterning process of sol-gel-derived organic-inorganic hybrid films. Microcraters of 1.0-1.5 μm in height and of 100-200 μm in width were spontaneously formed on the surface of silica-poly(vinylpyrrolidone) hybrid films prepared via temperature-controlled dip-coating process, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. Such highly ordered micropatterns were achieved by Bénard-Marangoni convection activated at high temperatures and the unidirectional flow of the coating solution on the substrate during dip-coating.

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and on pH, electrostatic interactions, hydrogen bonding, and ternary surface complexation contribute in varying degrees to the adsorption process. Linear distribution coefficients K d between 8.7 and 60.5 L kg -1 (1 mmol L -1 initial PHCA concentration) indicate a considerable mineral surface affinity at very high pH, thus lowering the PHCA fraction available for the complexation of metal ions including radionuclides in solution and their subsequent mobilization.

Integration of Quartz Crystal Microbalance-Dissipation and Reflection-Mode Localized Surface Plasmon Resonance Sensors for Biomacromolecular Interaction Analysis.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Cho, Nam-Joon

2016-12-20

The combination of label-free, surface-sensitive measurement techniques based on different physical principles enables detailed characterization of biomacromolecular interactions at solid-liquid interfaces. To date, most combined measurement systems have involved experimental techniques with similar probing volumes, whereas the potential of utilizing techniques with different surface sensitivities remains largely unexplored, especially for data interpretation. Herein, we report a combined measurement approach that integrates a conventional quartz crystal microbalance-dissipation (QCM-D) setup with a reflection-mode localized surface plasmon (LSPR) sensor. Using this platform, we investigate vesicle adsorption on a titanium oxide-coated sensing substrate along with the amphipathic, α-helical (AH) peptide-induced structural transformation of surface-adsorbed lipid vesicles into a supported lipid bilayer (SLB) as a model biomacromolecular interaction. While the QCM-D and LSPR signals both detected mass uptake arising from vesicle adsorption, tracking the AH peptide-induced structural transformation revealed more complex measurement responses based on the different surface sensitivities of the two techniques. In particular, the LSPR signal recorded an increase in optical mass near the sensor surface which indicated SLB formation, whereas the QCM-D signals detected a significant loss in net acoustic mass due to excess lipid and coupled solvent leaving the probing volume. Importantly, these measurement capabilities allowed us to temporally distinguish the process of SLB formation at the sensor surface from the overall structural transformation process. Looking forward, these label-free measurement capabilities to simultaneously probe adsorbates at multiple length scales will provide new insights into complex biomacromolecular interactions.

Did Mineral Surface Chemistry and Toxicity Contribute to Evolution of Microbial Extracellular Polymeric Substances?

PubMed Central

Campbell, Jay M.; Zhang, Nianli; Hickey, William J.

2012-01-01

Abstract Modern ecological niches are teeming with an astonishing diversity of microbial life in biofilms closely associated with mineral surfaces, which highlights the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral–water interface. Biofilm formation capability likely evolved on early Earth because biofilms provide crucial cell survival functions. The potential toxicity of mineral surfaces toward cells and the complexities of the mineral–water–cell interface in determining the toxicity mechanisms, however, have not been fully appreciated. Here, we report a previously unrecognized role for extracellular polymeric substances (EPS), which form biofilms in shielding cells against the toxicity of mineral surfaces. Using colony plating and LIVE/DEAD staining methods in oxide suspensions versus oxide-free controls, we found greater viability of wild-type, EPS-producing strains of Pseudomonas aeruginosa PAO1 compared to their isogenic knockout mutant with defective biofilm-producing capacity. Oxide toxicity was specific to its surface charge and particle size. High resolution transmission electron microscopy (HRTEM) images and assays for highly reactive oxygen species (hROS) on mineral surfaces suggested that EPS shield via both physical and chemical mechanisms. Intriguingly, qualitative as well as quantitative measures of EPS production showed that toxic minerals induced EPS production in bacteria. By determining the specific toxicity mechanisms, we provide insight into the potential impact of mineral surfaces in promoting increased complexity of cell surfaces, including EPS and biofilm formation, on early Earth. Key Words: Mineral toxicity—Bacteria—EPS evolution—Biofilms—Cytotoxicity—Silica—Anatase—Alumina. Astrobiology 12, 785–798. PMID:22934560

Suppressing the formation of lipid raft-associated Rac1/PI3K/Akt signaling complexes by curcumin inhibits SDF-1α-induced invasion of human esophageal carcinoma cells.

PubMed

Lin, Meng-Liang; Lu, Yao-Cheng; Chen, Hung-Yi; Lee, Chuan-Chun; Chung, Jing-Gung; Chen, Shih-Shun

2014-05-01

Stromal cell-derived factor-1α (SDF-1α) is a ligand for C-X-C chemokine receptor type 4 (CXCR4), which contributes to the metastasis of cancer cells by promoting cell migration. Here, we show that the SDF-1α/CXCR4 axis can significantly increase invasion of esophageal carcinoma (EC) cells. We accomplished this by examining the effects of CXCR4 knockdown as well as treatment with a CXCR4-neutralizing antibody and the CXCR4-specific inhibitor AMD3100. Curcumin suppressed SDF-1α-induced cell invasion and matrix metalloproteinase-2 (MMP-2) promoter activity, cell surface localization of CXCR4 at lipid rafts, and lipid raft-associated ras-related C3 botulinum toxin substrate 1 (Rac1)/phosphatidylinositol 3-kinase (PI3K) p85α/Akt signaling. Curcumin inhibited SDF-1α-induced cell invasion by suppressing the Rac1-PI3K signaling complex at lipid rafts but did not abrogate lipid raft formation. We further demonstrate that the attenuation of lipid raft-associated Rac1 activity by curcumin was critical for the inhibition of SDF-1α-induced PI3K/Akt/NF-κB activation, cell surface localization of CXCR4 at lipid rafts, MMP-2 promoter activity, and cell invasion. Collectively, our results indicate that curcumin inhibits SDF-1α-induced EC cell invasion by suppressing the formation of the lipid raft-associated Rac1-PI3K-Akt signaling complex, the localization of CXCR4 with lipid rafts at the cell surface, and MMP-2 promoter activity, likely through the inhibition of Rac1 activity. © 2012 Wiley Periodicals, Inc.

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

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

Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesizedmore » that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).« less

Heterogeneous Ice Nucleation: Interplay of Surface Properties and Their Impact on Water Orientations.

PubMed

Glatz, Brittany; Sarupria, Sapna

2018-01-23

Ice is ubiquitous in nature, and heterogeneous ice nucleation is the most common pathway of ice formation. How surface properties affect the propensity to observe ice nucleation on that surface remains an open question. We present results of molecular dynamics studies of heterogeneous ice nucleation on model surfaces. The models surfaces considered emulate the chemistry of kaolinite, an abundant component of mineral dust. We investigate the interplay of surface lattice and hydrogen bonding properties in affecting ice nucleation. We find that lattice matching and hydrogen bonding are necessary but not sufficient conditions for observing ice nucleation at these surfaces. We correlate this behavior to the orientations sampled by the metastable supercooled water in contact with the surfaces. We find that ice is observed in cases where water molecules not only sample orientations favorable for bilayer formation but also do not sample unfavorable orientations. This distribution depends on both surface-water and water-water interactions and can change with subtle modifications to the surface properties. Our results provide insights into the diverse behavior of ice nucleation observed at different surfaces and highlight the complexity in elucidating heterogeneous ice nucleation.

Hierarchical star formation across the grand-design spiral NGC 1566

NASA Astrophysics Data System (ADS)

Gouliermis, Dimitrios A.; Elmegreen, Bruce G.; Elmegreen, Debra M.; Calzetti, Daniela; Cignoni, Michele; Gallagher, John S., III; Kennicutt, Robert C.; Klessen, Ralf S.; Sabbi, Elena; Thilker, David; Ubeda, Leonardo; Aloisi, Alessandra; Adamo, Angela; Cook, David O.; Dale, Daniel; Grasha, Kathryn; Grebel, Eva K.; Johnson, Kelsey E.; Sacchi, Elena; Shabani, Fayezeh; Smith, Linda J.; Wofford, Aida

2017-06-01

We investigate how star formation is spatially organized in the grand-design spiral NGC 1566 from deep Hubble Space Telescope photometry with the Legacy ExtraGalactic UV Survey. Our contour-based clustering analysis reveals 890 distinct stellar conglomerations at various levels of significance. These star-forming complexes are organized in a hierarchical fashion with the larger congregations consisting of smaller structures, which themselves fragment into even smaller and more compact stellar groupings. Their size distribution, covering a wide range in length-scales, shows a power law as expected from scale-free processes. We explain this shape with a simple 'fragmentation and enrichment' model. The hierarchical morphology of the complexes is confirmed by their mass-size relation that can be represented by a power law with a fractional exponent, analogous to that determined for fractal molecular clouds. The surface stellar density distribution of the complexes shows a lognormal shape similar to that for supersonic non-gravitating turbulent gas. Between 50 and 65 per cent of the recently formed stars, as well as about 90 per cent of the young star clusters, are found inside the stellar complexes, located along the spiral arms. We find an age difference between young stars inside the complexes and those in their direct vicinity in the arms of at least 10 Myr. This time-scale may relate to the minimum time for stellar evaporation, although we cannot exclude the in situ formation of stars. As expected, star formation preferentially occurs in spiral arms. Our findings reveal turbulent-driven hierarchical star formation along the arms of a grand-design galaxy.

Nanomechanical and thermophoretic analyses of the nucleotide-dependent interactions between the AAA + subunits of magnesium chelatase

DOE PAGES

Adams, Nathan B. P.; Vasilev, Cvetelin; Brindley, Amanda A.; ...

2016-04-30

In chlorophyll biosynthesis, the magnesium chelatase enzyme complex catalyzes the insertion of a Mg 2+ ion into protoporphyrin IX. Prior to this event, two of the three subunits, the AAA + proteins ChlI and ChlD, form a ChlID–MgATP complex. We used microscale thermophoresis to directly determine dissociation constants for the I-D subunits from Synechocystis, and to show that the formation of a ChlID–MgADP complex, mediated by the arginine finger and the sensor II domain on ChlD, is necessary for the assembly of the catalytically active ChlHID–MgATP complex. The N-terminal AAA + domain of ChlD is essential for complex formation, butmore » some stability is preserved in the absence of the C-terminal integrin domain of ChlD, particularly if the intervening polyproline linker region is retained. Single molecule force spectroscopy (SMFS) was used to determine the factors that stabilize formation of the ChlID–MgADP complex at the single molecule level; ChlD was attached to an atomic force microscope (AFM) probe in two different orientations, and the ChlI subunits were tethered to a silica surface; the probability of subunits interacting more than doubled in the presence of MgADP, and we show that the N-terminal AAA + domain of ChlD mediates this process, in agreement with the microscale thermophoresis data. Analysis of the unbinding data revealed a most probable interaction force of around 109 pN for formation of single ChlID–MgADP complexes. Finally, these experiments provide a quantitative basis for understanding the assembly and function of the Mg chelatase complex.« less

Electrostatic interactions lead to the formation of asymmetric collagen-phosphophoryn aggregates.

PubMed

Dahl, Thomas; Veis, Arthur

2003-01-01

In bone and dentin the formation and mineralization of the extra cellular matrix structure is a complex process highly dependent on intermolecular interactions. In dentin, the phosphophoryns (PP) and type I collagen (COL1) are the major constituents implicated in mineralization. Thus, as a first step in understanding the tissue organization, we have initiated a study of their interaction as a function of pH, ionic strength, and relative concentrations or mixing ratios. Complex formation has been analyzed by dynamic light scattering to detect aggregate formation and by rotary shadowing electron microscopy (EM) to determine aggregate shape. The EM data showed that at the pH values studied, the PP-COL1 interaction leads to the formation of large fibrillar aggregates in which the PP are present along the fibril surfaces. The quantitative phase distribution data showed a 1/1 molar equivalence at the maximum aggregation point, not at electrostatic PP-COL1 equivalence. As the ionic strength was raised, the PP-COL1 aggregates became smaller but the binding and asymmetric fibrillar aggregation persisted. In EM, the PP appear as dense spheres. Along the surfaces of the collagen aggregates, the PP are larger and more open or extended, suggesting that COL1-bound PP may undergo a conformational change, opening up so that a single PP molecule might interact with and electrostatically link several COL1 molecules. This might have important implications for dentin structure, stability, and mineralization.

The Inhibition of Escherichia coli Biofilm Formation by Gallium Nitrate-Modified Titanium.

PubMed

Zhu, Yuanyuan; Qiu, Yan; Chen, Ruiqi; Liao, Lianming

2015-08-01

Periprosthetic infections are notoriously difficult to treat due to biofilm formation. Previously, we reported that gallium-EDTA attached to PVC (polyvinyl chloride) surface could prevent bacterial colonization. Herein we examined the effect of this gallium-EDTA complex on Escherichia coli biofilm formation on titanium. It was clearly demonstrated that gallium nitrate significantly inhibited the growth and auto-aggregation of Escherichia coli. Furthermore, titanium with gallium-EDTA coating resisted bacterial colonization as indicated by crystal violet staining. When the chips were immersed in human serum and incubated at 37 °C, they demonstrated significant antimicrobial activity after more than 28 days of incubation. These findings indicate that gallium-EDTA coating of implants can result in a surface that can resist bacterial colonization. This technology holds great promise for the prevention and treatment of periprosthetic infections.

Programming While Construction of Engineering 3D Models of Complex Geometry

NASA Astrophysics Data System (ADS)

Kheyfets, A. L.

2017-11-01

The capabilities of geometrically accurate computational 3D models construction with the use of programming are presented. The construction of models of an architectural arch and a glo-boid worm gear is considered as an example. The models are designed in the AutoCAD pack-age. Three programs of construction are given. The first program is for designing a multi-section architectural arch. The control of the arch’s geometry by impacting its main parameters is shown. The second program is for designing and studying the working surface of a globoid gear’s worm. The article shows how to make the animation for this surface’s formation. The third program is for formation of a worm gear cavity surface. The cavity formation dynamics is studied. The programs are written in the AutoLisp programming language. The program texts are provided.

Double channel emission from a redox active single component quantum dot complex.

PubMed

Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

2015-01-13

Herein we report the generation and control of double channel emission from a single component system following a facile complexation reaction between a Mn(2+) doped ZnS colloidal quantum dot (Qdot) and an organic ligand (8-hydroxy quinoline; HQ). The double channel emission of the complexed quantum dot-called the quantum dot complex (QDC)-originates from two independent pathways: one from the complex (ZnQ2) formed on the surface of the Qdot and the other from the dopant Mn(2+) ions of the Qdot. Importantly, reaction of ZnQ2·2H2O with the Qdot resulted in the same QDC formation. The emission at 500 nm with an excitation maximum at 364 nm is assigned to the surface complex involving ZnQ2 and a dangling sulfide bond. On the other hand, the emission at 588 nm-with an excitation maximum at 330 nm-which is redox tunable, is ascribed to Mn(2+) dopant. The ZnQ2 complex while present in QDC has superior thermal stability in comparison to the bare complex. Interestingly, while the emission of Mn(2+) was quenched by an electron quencher (benzoquinone), that due to the surface complex remained unaffected. Further, excitation wavelength dependent tunability in chromaticity color coordinates makes the QDC a potential candidate for fabricating a light emitting device of desired color output.

Partially Glycosylated Dendrimers Block MD-2 and Prevent TLR4-MD-2-LPS Complex Mediated Cytokine Responses

PubMed Central

Barata, Teresa S.; Teo, Ian; Brocchini, Steve; Zloh, Mire; Shaunak, Sunil

2011-01-01

The crystal structure of the TLR4-MD-2-LPS complex responsible for triggering powerful pro-inflammatory cytokine responses has recently become available. Central to cell surface complex formation is binding of lipopolysaccharide (LPS) to soluble MD-2. We have previously shown, in biologically based experiments, that a generation 3.5 PAMAM dendrimer with 64 peripheral carboxylic acid groups acts as an antagonist of pro-inflammatory cytokine production after surface modification with 8 glucosamine molecules. We have also shown using molecular modelling approaches that this partially glycosylated dendrimer has the flexibility, cluster density, surface electrostatic charge, and hydrophilicity to make it a therapeutically useful antagonist of complex formation. These studies enabled the computational study of the interactions of the unmodified dendrimer, glucosamine, and of the partially glycosylated dendrimer with TLR4 and MD-2 using molecular docking and molecular dynamics techniques. They demonstrate that dendrimer glucosamine forms co-operative electrostatic interactions with residues lining the entrance to MD-2's hydrophobic pocket. Crucially, dendrimer glucosamine interferes with the electrostatic binding of: (i) the 4′phosphate on the di-glucosamine of LPS to Ser118 on MD-2; (ii) LPS to Lys91 on MD-2; (iii) the subsequent binding of TLR4 to Tyr102 on MD-2. This is followed by additional co-operative interactions between several of the dendrimer glucosamine's carboxylic acid branches and MD-2. Collectively, these interactions block the entry of the lipid chains of LPS into MD-2's hydrophobic pocket, and also prevent TLR4-MD-2-LPS complex formation. Our studies have therefore defined the first nonlipid-based synthetic MD-2 antagonist using both animal model-based studies of pro-inflammatory cytokine responses and molecular modelling studies of a whole dendrimer with its target protein. Using this approach, it should now be possible to computationally design additional macromolecular dendrimer based antagonists for other Toll Like Receptors. They could be useful for treating a spectrum of infectious, inflammatory and malignant diseases. PMID:21738462

Directed formation of micro- and nanoscale patterns of functional light-harvesting LH2 complexes.

PubMed

Reynolds, Nicholas P; Janusz, Stefan; Escalante-Marun, Maryana; Timney, John; Ducker, Robert E; Olsen, John D; Otto, Cees; Subramaniam, Vinod; Leggett, Graham J; Hunter, C Neil

2007-11-28

The precision placement of the desired protein components on a suitable substrate is an essential prelude to any hybrid "biochip" device, but a second and equally important condition must also be met: the retention of full biological activity. Here we demonstrate the selective binding of an optically active membrane protein, the light-harvesting LH2 complex from Rhodobacter sphaeroides, to patterned self-assembled monolayers at the micron scale and the fabrication of nanometer-scale patterns of these molecules using near-field photolithographic methods. In contrast to plasma proteins, which are reversibly adsorbed on many surfaces, the LH2 complex is readily patterned simply by spatial control of surface polarity. Near-field photolithography has yielded rows of light-harvesting complexes only 98 nm wide. Retention of the native optical properties of patterned LH2 molecules was demonstrated using in situ fluorescence emission spectroscopy.

Changes in the distribution of plastids and endoplasmic reticulum during cellular differentiation in root caps of Zea mays

NASA Technical Reports Server (NTRS)

Moore, R.; McClelen, C. E.

1985-01-01

In calyptrogen cells of Zea mays, proplastids are distributed randomly throughout the cell, and the endoplasmic reticulum (ER) is distributed parallel to the cell walls. The differentiation of calyptrogen cells into columella statocytes is characterized by the following sequential events: (1) formation of ER complexes at the distal and proximal ends of the cell, (2) differentiation of proplastids into amyloplasts, (3) sedimentation of amyloplasts onto the distal ER complex, (4) breakdown of the distal ER complex and sedimentation of amyloplasts to the bottom of the cell, and (5) formation of sheets of ER parallel to the longitudinal cell walls. Columella statocytes located in the centre of the cap each possess 4530 +/- 780 micrometers2 of ER surface area, an increase of 670 per cent over that of calyptrogen cells. The differentiation of peripheral cells correlates positively with (1) the ER becoming arranged in concentric sheets, (2) amyloplasts and ER becoming randomly distributed, and (3) a 280 per cent increase in ER surface area over that of columella statocytes. These results are discussed relative to graviperception and mucilage secretion, which are functions of columella and peripheral cells, respectively.

Self-templated formation of uniform NiCo2O4 hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors.

PubMed

Shen, Laifa; Yu, Le; Yu, Xin-Yao; Zhang, Xiaogang; Lou, Xiong Wen David

2015-02-02

Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template-based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed-metal-oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo2O4 hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo2O4 hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium-ion batteries and supercapacitors. This approach can be an efficient self-templated strategy for the preparation of mixed-metal-oxide hollow spheres with complex interior structures and functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction and formation mechanism of binary complex between zein and propylene glycol alginate.

PubMed

Sun, Cuixia; Dai, Lei; Gao, Yanxiang

2017-02-10

The anti-solvent co-precipitation method was used to fabricate the zein-propylene glycol alginate (PGA) binary complex with different mass ratios of zein to PGA (20:1, 10:1, 5:1, 2:1 and 1:1) at pH 4.0. Results showed that attractive electrostatic interaction between zein and PGA occurred and negatively charged binary complex with large size and high turbidity was formed due to the charge neutralization. Hydrogen bonding and hydrophobic effects were involved in the interactions between zein and PGA, leading to the changed secondary structure and improved thermal stability of zein. Aggregates in the irregular shape with large size were obviously observed in the AFM images. PGA alone exhibited a fine filamentous network structure, while zein-PGA binary complex showed a rough branch-like pattern and the surface of "branch" was closely adsorbed by lots of spherical zein particles. Q in zein-PGA binary complex dispersions presented the improved photochemical and thermal stability. The potential mechanism of a two-step process was proposed to explain the formation of zein-PGA binary complexes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tyrosine phosphorylation–dependent activation of TRPC6 regulated by PLC-γ1 and nephrin: effect of mutations associated with focal segmental glomerulosclerosis

PubMed Central

Kanda, Shoichiro; Harita, Yutaka; Shibagaki, Yoshio; Sekine, Takashi; Igarashi, Takashi; Inoue, Takafumi; Hattori, Seisuke

2011-01-01

Transient receptor potential canonicals (TRPCs) play important roles in the regulation of intracellular calcium concentration. Mutations in the TRPC6 gene are found in patients with focal segmental glomerulosclerosis (FSGS), a proteinuric disease characterized by dysregulated function of renal glomerular epithelial cells (podocytes). There is as yet no clear picture for the activation mechanism of TRPC6 at the molecular basis, however, and the association between its channel activity and pathogenesis remains unclear. We demonstrate here that tyrosine phosphorylation of TRPC6 induces a complex formation with phospholipase C (PLC)-γ1, which is prerequisite for TRPC6 surface expression. Furthermore, nephrin, an adhesion protein between the foot processes of podocytes, binds to phosphorylated TRPC6 via its cytoplasmic domain, competitively inhibiting TRPC6–PLC-γ1 complex formation, TRPC6 surface localization, and TRPC6 activation. Importantly, FSGS-associated mutations render the mutated TRPC6s insensitive to nephrin suppression, thereby promoting their surface expression and channel activation. These results delineate the mechanism of TRPC6 activation regulated by tyrosine phosphorylation, and imply the cell type–specific regulation, which correlates the FSGS mutations with deregulated TRPC6 channel activity. PMID:21471003

Nanoplasmonic sensing of metal-halide complex formation and the electric double layer capacitor.

PubMed

Dahlin, Andreas B; Zahn, Raphael; Vörös, Janos

2012-04-07

Many nanotechnological devices are based on implementing electrochemistry with plasmonic nanostructures, but these systems are challenging to understand. We present a detailed study of the influence of electrochemical potentials on plasmon resonances, in the absence of surface coatings and redox active molecules, by synchronized voltammetry and spectroscopy. The experiments are performed on gold nanodisks and nanohole arrays in thin gold films, which are fabricated by improved methods. New insights are provided by high resolution spectroscopy and variable scan rates. Furthermore, we introduce new analytical models in order to understand the spectral changes quantitatively. In contrast to most previous literature, we find that the plasmonic signal is caused almost entirely by the formation of ionic complexes on the metal surface, most likely gold chloride in this study. The refractometric sensing effect from the ions in the electric double layer can be fully neglected, and the charging of the metal gives a surprisingly small effect for these systems. Our conclusions are consistent for both localized nanoparticle plasmons and propagating surface plasmons. We consider the results in this work especially important in the context of combined electrochemical and optical sensors. This journal is © The Royal Society of Chemistry 2012

Advances in the production of freeform optical surfaces

NASA Astrophysics Data System (ADS)

Tohme, Yazid E.; Luniya, Suneet S.

2007-05-01

Recent market demands for free-form optics have challenged the industry to find new methods and techniques to manufacture free-form optical surfaces with a high level of accuracy and reliability. Production techniques are becoming a mix of multi-axis single point diamond machining centers or deterministic ultra precision grinding centers coupled with capable measurement systems to accomplish the task. It has been determined that a complex software tool is required to seamlessly integrate all aspects of the manufacturing process chain. Advances in computational power and improved performance of computer controlled precision machinery have driven the use of such software programs to measure, visualize, analyze, produce and re-validate the 3D free-form design thus making the process of manufacturing such complex surfaces a viable task. Consolidation of the entire production cycle in a comprehensive software tool that can interact with all systems in design, production and measurement phase will enable manufacturers to solve these complex challenges providing improved product quality, simplified processes, and enhanced performance. The work being presented describes the latest advancements in developing such software package for the entire fabrication process chain for aspheric and free-form shapes. It applies a rational B-spline based kernel to transform an optical design in the form of parametrical definition (optical equation), standard CAD format, or a cloud of points to a central format that drives the simulation. This software tool creates a closed loop for the fabrication process chain. It integrates surface analysis and compensation, tool path generation, and measurement analysis in one package.

Formation and Recondensation of Complex Organic Molecules During Protostellar Luminosity Outbursts

NASA Technical Reports Server (NTRS)

Taquet, Vianney; Wirstrom, Eva S.; Charnley, Steven B.

2016-01-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

NASA Astrophysics Data System (ADS)

Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

2016-04-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

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.

Contribution of coated humic acids calculated through their surface coverage on nano iron oxides for ofloxacin and norfloxacin sorption.

PubMed

Peng, Hongbo; Liang, Ni; Li, Hao; Chen, Fangyuan; Zhang, Di; Pan, Bo; Xing, Baoshan

2015-09-01

Sorption of organic contaminants on organo-mineral complexes has been investigated extensively, but the sorption contribution of mineral particles was not properly addressed before calculating KOC, especially for ionic organic contaminants. We measured the surface coverage of a humic acid (HA) on nano iron oxides (n-Fe2O3) in a series of synthesized organo-mineral complexes. The contribution of the coated HA to ofloxacin (OFL) and norfloxacin (NOR) sorption in HA-n-Fe2O3 complexes was over 80% of the total sorption with the surface coverage of 36% and fOC of 1.6%. All the coated HA showed higher sorption to NOR and OFL in comparison to the original HA, suggesting HA fractionation and/or physical re-conformation during organo-mineral complex formation. The decreased KOC with multilayer coating may suggest the importance of site-specific interactions for OFL sorption, while the increased KOC with multilayer coating may suggest the importance of partitioning in hydrophobic region for NOR sorption. Copyright © 2015 Elsevier Ltd. All rights reserved.

DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

PubMed

Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

2017-09-24

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

Understanding the spatial complexity of surface hoar from slope to range scale

NASA Astrophysics Data System (ADS)

Hendrikx, J.

2015-12-01

Surface hoar, once buried, is a common weak layer type in avalanche accidents in continental and intermountain snowpacks around the World. Despite this, there is still limited understanding of the spatial variability in both the formation of, and eventual burial of, surface hoar at spatial scales which are of critical importance to avalanche forecasters. While it is relatively well understood that aspect plays an important role in the spatial location of the formation, and burial of these grain forms, due to the unequal distribution of incoming radiation, this factor alone does not explain the complex and often confusing spatial pattern of these grains forms throughout the landscape at different spatial scales. In this paper we present additional data from a unique data set including over two hundred days of manual observations of surface hoar at sixteen locations on Pioneer Mountain at the Yellowstone Club in southwestern Montana. Using this wealth of observational data located on different aspects, elevations and exposures, coupled with detailed meteorological observations, and detailed slope scale observation, we examine the spatial variability of surface hoar at this scale, and examine the factors that control its spatial distribution. Our results further supports our preliminary work, which shows that small-scale slope conditions, meteorological differences, and local scale lapse rates, can greatly influence the spatial variability of surface hoar, over and above that which aspect alone can explain. These results highlight our incomplete understanding of the processes at both the slope and range scale, and are likely to have implications for both regional and local scale avalanche forecasting in environments where surface hoar cause ongoing instabilities.

Secondary instabilities modulate cortical complexity in the mammalian brain

NASA Astrophysics Data System (ADS)

Budday, Silvia; Steinmann, Paul; Kuhl, Ellen

2015-10-01

Disclosing the origin of convolutions in the mammalian brain remains a scientific challenge. Primary folds form before we are born: they are static, well defined and highly preserved across individuals. Secondary folds occur and disappear throughout our entire lifetime: they are dynamic, irregular and highly variable among individuals. While extensive research has improved our understanding of primary folding in the mammalian brain, secondary folding remains understudied and poorly understood. Here, we show that secondary instabilities can explain the increasing complexity of our brain surface as we age. Using the nonlinear field theories of mechanics supplemented by the theory of finite growth, we explore the critical conditions for secondary instabilities. We show that with continuing growth, our brain surface continues to bifurcate into increasingly complex morphologies. Our results suggest that even small geometric variations can have a significant impact on surface morphogenesis. Secondary bifurcations, and with them morphological changes during childhood and adolescence, are closely associated with the formation and loss of neuronal connections. Understanding the correlation between neuronal connectivity, cortical thickness, surface morphology and ultimately behaviour, could have important implications on the diagnostics, classification and treatment of neurological disorders.

Characterization of E coli biofim formations on baby spinach leaf surfaces using hyperspectral fluorescence imaging

NASA Astrophysics Data System (ADS)

Cho, Hyunjeong; Baek, Insuck; Oh, Mirae; Kim, Sungyoun; Lee, Hoonsoo; Kim, Moon S.

2017-05-01

Bacterial biofilm formed by pathogens on fresh produce surfaces is a food safety concern because the complex extracellular matrix in the biofilm structure reduces the reduction and removal efficacies of washing and sanitizing processes such as chemical or irradiation treatments. Therefore, a rapid and nondestructive method to identify pathogenic biofilm on produce surfaces is needed to ensure safe consumption of fresh, raw produce. This research aimed to evaluate the feasibility of hyperspectral fluorescence imaging for detecting Escherichia.coli (ATCC 25922) biofilms on baby spinach leaf surfaces. Samples of baby spinach leaves were immersed and inoculated with five different levels (from 2.6x104 to 2.6x108 CFU/mL) of E.coli and stored at 4°C for 24 h and 48 h to induce biofilm formation. Following the two treatment days, individual leaves were gently washed to remove excess liquid inoculums from the leaf surfaces and imaged with a hyperspectral fluorescence imaging system equipped with UV-A (365 nm) and violet (405 nm) excitation sources to evaluate a spectral-image-based method for biofilm detection. The imaging results with the UV-A excitation showed that leaves even at early stages of biofilm formations could be differentiated from the control leaf surfaces. This preliminary investigation demonstrated the potential of fluorescence imaging techniques for detection of biofilms on leafy green surfaces.

Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

2017-02-01

Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

Experimental study of electrostatic discharges of spacecraft solar array protective coatings under radiation

NASA Astrophysics Data System (ADS)

Khasanshin, Rashid; Novikov, Lev

Action of charged particles on low-conductive dielectrics causes formation of areas with a high charge density inside; their fields may give rise to development of electrostatic discharge between the charged area and the surface of the dielectric. Discharge channels are growing due to breakdown of dielectric and formation of a conducting phase. Generation of the channels is a complex stochastic process accompanied by such physical and chemical processes as ionization, gas formation, heating, and so on, which cause formation of conducting phase in a glass. That is why no quantitative theory describing formation of conductive channels has been formulated yet. The study of electrostatic discharges in dielectrics under radiation is essential both from a scientific point of view and for the solution of applied problems. In particular, interaction of a spacecraft with ambient plasma causes accumulation of electric charges on its surface producing, as a consequence, electric potential between the spacecraft surface and the plasma. For example, potentials on the surface of satellites operating on a geostationary orbit reach up to 20 kV. Elec-trostatic discharges caused by such potentials can produce not only the considerable electromag-netic interference, but also lead to the destruction of hardware components and structural ele-ments. Electrostatic charging due to electrons from the Earth’s radiation belts causes degradation of solar arrays as a result of surface and internal electrostatic discharges. In the work, surface of K-208 spacecraft solar array protective coatings irradiated by 20 and 40 keV electrons and protons has studied using by AFM methods. Traces of electrostatic dis-charges at different radiation flux densities were analyzed.

Raman spectroscopic studies of the interaction of oxalic acid and sodium oxalate used as corrosion inhibitors with copper

NASA Astrophysics Data System (ADS)

Jeziorowski, H.; Moser, B.

1985-09-01

The Raman spectra of the liquid-solid interface recorded in situ show the formation of a salt complex of the inhibitor molecules and the copper ions. This suggests that this chemisorbed surface species produces the protective layer.

Formation and mechanics of granular waves in gravity and shallow overland flow

USDA-ARS?s Scientific Manuscript database

Sediment transport in overland flow is a highly complex process involving many properties relative to the flow regime characteristics, soil surface conditions, and type of sediment. From a practical standpoint, most sediment transport studies are concerned with developing relationships of rates of s...

Dynamic complexity: plant receptor complexes at the plasma membrane.

PubMed

Burkart, Rebecca C; Stahl, Yvonne

2017-12-01

Plant receptor complexes at the cell surface perceive many different external and internal signalling molecules and relay these signals into the cell to regulate development, growth and immunity. Recent progress in the analyses of receptor complexes using different live cell imaging approaches have shown that receptor complex formation and composition are dynamic and take place at specific microdomains at the plasma membrane. In this review we focus on three prominent examples of Arabidopsis thaliana receptor complexes and how their dynamic spatio-temporal distribution at the PM has been studied recently. We will elaborate on the newly emerging concept of plasma membrane microdomains as potential hubs for specific receptor complex assembly and signalling outputs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

NASA Astrophysics Data System (ADS)

Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-12-01

Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

Formation of A Wrapped DNA-Protein Interface: Expermental Characterization and Analysis of the Large Contributions of Ions and Water to the Thermodynamics of Binding IHF to H′DNA

PubMed Central

Vander Meulen, Kirk A.; Saecker, Ruth M.; Record, M. Thomas

2008-01-01

To characterize driving forces and driven processes in formation of a large-interface, wrapped protein-DNA complex analogous to the nucleosome, we have investigated the thermodynamics of binding the 34 bp H′ DNA sequence to the E. coli DNA-remodeling protein Integration Host Factor (IHF). Isothermal titration calorimetry (ITC) and fluorescence resonance energy transfer (FRET) are applied to determine effects of salt concentration (KCl, KF, KGlutamate (KGlu)), and of the excluded solute glycine betaine, on the binding thermodynamics at 20°C. Both the binding constant Kobs and enthalpy ΔH°obs depend strongly on [salt] and anion identity. Formation of the wrapped complex is enthalpy-driven, especially at low [salt] (e.g. ΔH°obs = −20.2 kcal · mol−1 in 0.04 M KCl). ΔH°obs increases linearly with [salt] with a slope (dΔH°obs/d[salt]) which is much larger in KCl (38 ± 3 kcal · mol−1M−1) than in KF or KGlu (average 11 ± 2 kcal · mol−1M−1). At 0.33 M [salt], Kobs is approximately 30-fold larger in KGlu or KF than in KCl, and the [salt] derivative SKobs = dlnKobs/dln[salt] is almost twice as large in magnitude in KCl (−8.8 ± 0.7) as in KF or KGlu (average −4.7 ± 0.6). A novel analysis of the large effects of anion identity on Kobs, SKobs and on ΔH°obs dissects coulombic, Hofmeister and osmotic contributions to these quantities. This analysis attributes anion-specific differences in Kobs, SKobs and ΔH°obs to (i) displacement of a large number of waters of hydration (estimated to be 1.0 (± 0.2) × 103) from the 5340 Å2 of IHF and H′ DNA surface buried in complex formation, and (ii) significant local exclusion of F− and Glu− from this hydration water, relative to the situation with Cl−, which we propose is randomly distributed. To quantify net water release from anionic surface (22% of the surface buried in complexation, mostly from DNA phosphates), we determined the stabilizing effect of glycine betaine (GB) on Kobs: dlnKobs/d[GB] = 2.7 ± 0.4 at constant KCl activity, indicating the net release of 150 H2O from anionic surface. PMID:18237740

[Biofilm: set-up and organization of a bacterial community].

PubMed

Filloux, Alain; Vallet, Isabelle

2003-01-01

Bacterial attachment on various surfaces mostly takes place in the form of specialised bacterial communities, referred to as biofilm. The biofilm is formed through series of interactions between cells and adherence to surface, resulting in an organised structure. In this review we have been using Pseudomonas aeruginosa as a model microorganism to describe the series of events that occurred during this developmental process. P. aeruginosa is an opportunistic pathogen that has a wide variety of hosts and infectious sites. In addition to biofilm formation in certain tissues, inert surfaces, such as catheters, are also target for bacterial biofilm development. The use of convenient genetic screens has made possible the identification of numerous biofilm-defective mutants, which have been characterised further. These studies have allowed the proposal for a global model, in which key events are described for the different stages of biofilm formation. Briefly, flagellar mobility is crucial for approaching the surface, whereas type IV pili motility is preponderant for surface colonisation and microcolonies formation. These microcolonies are finally packed together and buried in an exopolysaccharide matrix to form the differentiated bio-film. It is obvious that the different stages of biofilm formation also involved perception of environmental stimuli. These stimuli, and their associated complex regulatory networks, have still to be fully characterised to understand the bacterial strategy, which initiates biofilm formation. One such regulatory system, called Quorum sensing, is one of the key player in the initial differentiation of biofilm. Finally, a better understanding, at the molecular level, of biofilm establishment and persistence should help for the design of antimicrobials that prevent bacterial infections.

Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

NASA Astrophysics Data System (ADS)

Lee, Seung-Mahn

2003-10-01

Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP removal rates were found to be in good agreement with the initial reaction kinetics as well as the mechanical properties of the chemically modified surface layer. In addition, the material removal model based on the micro- and nano-scale interactions, which were measured experimentally, has been developed.

Chemical shift changes provide evidence for overlapping single-stranded DNA- and XPA-binding sites on the 70 kDa subunit of human replication protein A.

PubMed

Daughdrill, Gary W; Buchko, Garry W; Botuyan, Maria V; Arrowsmith, Cheryl; Wold, Marc S; Kennedy, Michael A; Lowry, David F

2003-07-15

Replication protein A (RPA) is a heterotrimeric single-stranded DNA- (ssDNA) binding protein that can form a complex with the xeroderma pigmentosum group A protein (XPA). This complex can preferentially recognize UV-damaged DNA over undamaged DNA and has been implicated in the stabilization of open complex formation during nucleotide excision repair. In this report, nuclear magnetic resonance (NMR) spectroscopy was used to investigate the interaction between a fragment of the 70 kDa subunit of human RPA, residues 1-326 (hRPA70(1-326)), and a fragment of the human XPA protein, residues 98-219 (XPA-MBD). Intensity changes were observed for amide resonances in the (1)H-(15)N correlation spectrum of uniformly (15)N-labeled hRPA70(1-326) after the addition of unlabeled XPA-MBD. The intensity changes observed were restricted to an ssDNA-binding domain that is between residues 183 and 296 of the hRPA70(1-326) fragment. The hRPA70(1-326) residues with the largest resonance intensity reductions were mapped onto the structure of the ssDNA-binding domain to identify the binding surface with XPA-MBD. The XPA-MBD-binding surface showed significant overlap with an ssDNA-binding surface that was previously identified using NMR spectroscopy and X-ray crystallography. Overlapping XPA-MBD- and ssDNA-binding sites on hRPA70(1-326) suggests that a competitive binding mechanism mediates the formation of the RPA-XPA complex. To determine whether a ternary complex could form between hRPA70(1-326), XPA-MBD and ssDNA, a (1)H-(15)N correlation spectrum was acquired for uniformly (15)N-labeled hRPA70(1-326) after the simultaneous addition of unlabeled XPA-MBD and ssDNA. In this experiment, the same chemical shift perturbations were observed for hRPA70(1-326) in the presence of XPA-MBD and ssDNA as was previously observed in the presence of ssDNA alone. The ability of ssDNA to compete with XPA-MBD for an overlapping binding site on hRPA70(1-326) suggests that any complex formation between RPA and XPA that involves the interaction between XPA-MBD and hRPA70(1-326) may be modulated by ssDNA.

Chemical shift changes provide evidence for overlapping single-stranded DNA- and XPA-binding sites on the 70 kDa subunit of human replication protein A

PubMed Central

Daughdrill, Gary W.; Buchko, Garry W.; Botuyan, Maria V.; Arrowsmith, Cheryl; Wold, Marc S.; Kennedy, Michael A.; Lowry, David F.

2003-01-01

Replication protein A (RPA) is a heterotrimeric single-stranded DNA- (ssDNA) binding protein that can form a complex with the xeroderma pigmentosum group A protein (XPA). This complex can preferentially recognize UV-damaged DNA over undamaged DNA and has been implicated in the stabilization of open complex formation during nucleotide excision repair. In this report, nuclear magnetic resonance (NMR) spectroscopy was used to investigate the interaction between a fragment of the 70 kDa subunit of human RPA, residues 1–326 (hRPA701–326), and a fragment of the human XPA protein, residues 98–219 (XPA-MBD). Intensity changes were observed for amide resonances in the 1H–15N correlation spectrum of uniformly 15N-labeled hRPA701–326 after the addition of unlabeled XPA-MBD. The intensity changes observed were restricted to an ssDNA-binding domain that is between residues 183 and 296 of the hRPA701–326 fragment. The hRPA701–326 residues with the largest resonance intensity reductions were mapped onto the structure of the ssDNA-binding domain to identify the binding surface with XPA-MBD. The XPA-MBD-binding surface showed significant overlap with an ssDNA-binding surface that was previously identified using NMR spectroscopy and X-ray crystallography. Overlapping XPA-MBD- and ssDNA-binding sites on hRPA701–326 suggests that a competitive binding mechanism mediates the formation of the RPA–XPA complex. To determine whether a ternary complex could form between hRPA701–326, XPA-MBD and ssDNA, a 1H–15N correlation spectrum was acquired for uniformly 15N-labeled hRPA701–326 after the simultaneous addition of unlabeled XPA-MBD and ssDNA. In this experiment, the same chemical shift perturbations were observed for hRPA701–326 in the presence of XPA-MBD and ssDNA as was previously observed in the presence of ssDNA alone. The ability of ssDNA to compete with XPA-MBD for an overlapping binding site on hRPA701–326 suggests that any complex formation between RPA and XPA that involves the interaction between XPA-MBD and hRPA701–326 may be modulated by ssDNA. PMID:12853635

Effect of heparin and heparan sulphate on open promoter complex formation for a simple tandem gene model using ex situ atomic force microscopy.

PubMed

Chammas, Oliver; Bonass, William A; Thomson, Neil H

2017-05-01

The influence of heparin and heparan sulphate (HepS) on the appearance and analysis of open promoter complex (RP o ) formation by E. coli RNA polymerase (RNAP) holoenzyme (σ 70 RNAP) on linear DNA using ex situ imaging by atomic force microscopy (AFM) has been investigated. Introducing heparin or HepS into the reaction mix significantly reduces non-specific interactions of the σ 70 RNAP and RNAP after RP o formation allowing for better interpretation of complexes shown within AFM images, particularly on DNA templates containing more than one promoter. Previous expectation was that negatively charged polysaccharides, often used as competitive inhibitors of σRNAP binding and RP o formation, would also inhibit binding of the DNA template to the mica support surface and thereby lower the imaging yield of active RNAP-DNA complexes. We found that the reverse of this was true, and that the yield of RP o formation detected by AFM, for a simple tandem gene model containing two λ PR promoters, increased. Moreover and unexpectedly, HepS was more efficient than heparin, with both of them having a dispersive effect on the sample, minimising unwanted RNAP-RNAP interactions as well as non-specific interactions between the RNAP and DNA template. The success of this method relied on the observation that E. coli RNAP has the highest affinity for the mica surface of all the molecular components. For our system, the affinity of the three constituent biopolymers to muscovite mica was RNAP>Heparin or HepS>DNA. While we observed that heparin and HepS can inhibit DNA binding to the mica, the presence of E. coli RNAP overcomes this effect allowing a greater yield of RP o s for AFM analysis. This method can be extended to other DNA binding proteins and enzymes, which have an affinity to mica higher than DNA, to improve sample preparation for AFM studies. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Numerical simulation of colloidal self-assembly of super-hydrophobic arachnid cerotegument structures.

PubMed

Filippov, Alexander É; Wolff, Jonas O; Seiter, Michael; Gorb, Stanislav N

2017-10-07

Certain arachnids exhibit complex coatings of their exoskeleton, consisting of globular structures with complex surface features. This, so-called, cerotegument is formed by a multi-component colloidal secretion that self-assembles and cures on the body surface, and leads to high water repellency. Previous ultrastructural studies revealed the involvement of different glandular cells that contribute different components to the secretion mixture, but the overall process of self-assembly into the complex regular structures observed remained highly unclear. Here we study this process from a theoretical point of view, starting from the so-called Tammes-problem. We show that slight changes of simple parameters lead to a variety of morphologies that are highly similar to the ones observed in the species specific cerotegument structures of whip-spiders. These results are not only important for our understanding of the formation of globular hierarchical structures in nature, but also for the fabrication of novel surface coatings by colloidal lithography. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoporous Anodic Alumina Surface Modification by Electrostatic, Covalent, and Immune Complexation Binding Investigated by Capillary Filling.

PubMed

Eckstein, Chris; Acosta, Laura K; Pol, Laura; Xifré-Pérez, Elisabet; Pallares, Josep; Ferré-Borrull, Josep; Marsal, Lluis F

2018-03-28

The fluid imbibition-coupled laser interferometry (FICLI) technique has been applied to detect and quantify surface changes and pore dimension variations in nanoporous anodic alumina (NAA) structures. FICLI is a noninvasive optical technique that permits the determination of the NAA average pore radius with high accuracy. In this work, the technique is applied after each step of different surface modification paths of the NAA pores: (i) electrostatic immobilization of bovine serum albumin (BSA), (ii) covalent attachment of streptavidin via (3-aminipropyl)-triethoxysilane and glutaraldehyde grafting, and (iii) immune complexation. Results show that BSA attachment can be detected as a reduction in estimated radius from FICLI with high accuracy and reproducibility. In the case of the covalent attachment of streptavidin, FICLI is able to recognize a multilayer formation of the silane and the protein. For immune complexation, the technique is able to detect different antibody-antigen bindings and distinguish different dynamics among different immune species.

Complex Pattern Formation from Current-Driven Dynamics of Single-Layer Homoepitaxial Islands on Crystalline Conducting Substrates

NASA Astrophysics Data System (ADS)

Kumar, Ashish; Dasgupta, Dwaipayan; Maroudas, Dimitrios

2017-07-01

We report a systematic study of complex pattern formation resulting from the driven dynamics of single-layer homoepitaxial islands on surfaces of face-centered-cubic (fcc) crystalline conducting substrates under the action of an externally applied electric field. The analysis is based on an experimentally validated nonlinear model of mass transport via island edge atomic diffusion, which also accounts for edge diffusional anisotropy. We analyze the morphological stability and simulate the field-driven evolution of rounded islands for an electric field oriented along the fast edge diffusion direction. For larger-than-critical island sizes on {110 } and {100 } fcc substrates, we show that multiple necking instabilities generate complex island patterns, including not-simply-connected void-containing islands mediated by sequences of breakup and coalescence events and distributed symmetrically with respect to the electric field direction. We analyze the dependence of the formed patterns on the original island size and on the duration of application of the external field. Starting from a single large rounded island, we characterize the evolution of the number of daughter islands and their average size and uniformity. The evolution of the average island size follows a universal power-law scaling relation, and the evolution of the total edge length of the islands in the complex pattern follows Kolmogorov-Johnson-Mehl-Avrami kinetics. Our study makes a strong case for the use of electric fields, as precisely controlled macroscopic forcing, toward surface patterning involving complex nanoscale features.

Effect of alkali ions (Na+, K+, Cs+) on reaction mechanism of CZTS nano-particles synthesis

NASA Astrophysics Data System (ADS)

Kumar, Suresh; Altosaar, Mare; Grossberg, Maarja; Mikli, Valdek

2018-04-01

The control of morphology, elemental composition and phase composition of Cu2ZnSnS4 (CZTS) nano-crystals depends on the control of complex formation and surface stabilization of nano-particles in solution-based synthesis in oleylamine. At temperatures ≥280 °C, the control of nano-crystal's morphology and homogenous growth is difficult because of fast poly-nuclear growth occurring at higher temperatures. In the present work the effect of oleylamine complex formation with different alkali ions (Na+, K+ and Cs+) on nano-crystals growth at synthesis temperature of 280 °C was studied. It was found that nano-powders synthesized in the presence of Na+ and K+ ions showed the formation of crystals of different sizes - small nano-particles (18 nm-30 nm), large aggregated crystals (few nm to 1 μm) and large single crystals (1 μm - 4 μm). The presence of Cs+ ions in the nano-powder synthesis in oleylamine-metal precursor-CsOH solution promoted growth of nano-crystals of homogenous size. It is proposed that the formed oleylamine-Cs complexes a) enhance the formation and stabilization of oleylamine-metal (Cu, Zn and Sn) complexes before the injection of sulphur precursor into the oleylamine-metal precursor solution and b) after addition of sulphur stabilize the fast nucleated nano-particles and promote diffusion limited growth.

Electrochemical detection of sequence-specific DNA based on formation of G-quadruplex-hemin through continuous hybridization chain reaction.

PubMed

Sun, Xiaofan; Chen, Haohan; Wang, Shuling; Zhang, Yiping; Tian, Yaping; Zhou, Nandi

2018-08-27

A high-sensitive detection of sequence-specific DNA was established based on the formation of G-quadruplex-hemin complex through continuous hybridization chain reaction (HCR). Taking HIV DNA sequence as an example, a capture probe complementary to part of HIV DNA was firstly self-assembled onto the surface of Au electrode. Then a specially designed assistant probe with both terminals complementary to the target DNA and a G-quadruplex-forming sequence in the center was introduced into the detection solution. In the presence of both the target DNA and the assistant probe, the target DNA can be captured on the electrode surface and then a continuous HCR can be conducted due to the mutual recognition of the target DNA and the assistant probe, leading to the formation of a large number of G-quadruplex on the electrode surface. With the help of hemin, a pronounced electrochemical signal can be observed in differential pulse voltammetry (DPV), due to the formation of G-quadruplex-hemin complex. The peak current is linearly related with the logarithm of the concentration of the target DNA in the range from 10 fM to 10 pM. The electrochemical sensor has high selectivity to clearly discriminate single-base mismatched and three-base mismatched sequences from the original HIV DNA sequence. Moreover, the established DNA sensor was challenged by detection of HIV DNA in human serum samples, which showed the low detection limit of 6.3 fM. Thus it has great application prospect in the field of clinical diagnosis and environmental monitoring. Copyright © 2018 Elsevier B.V. All rights reserved.

Surface modification of zinc oxide nanoparticle by PMAA and its dispersion in aqueous system

NASA Astrophysics Data System (ADS)

Tang, Erjun; Cheng, Guoxiang; Ma, Xiaolu; Pang, Xingshou; Zhao, Qiang

2006-05-01

Commercial zinc oxide nanoparticles were modified by polymethacrylic acid (PMAA) in aqueous system. The hydroxyl groups of nano-ZnO particle surface can interact with carboxyl groups (COO-) of PMAA and form poly(zinc methacrylate) complex on the surface of nano-ZnO. The formation of poly(zinc methacrylate) complex was testified by Fourier-transform infrared spectra (FT-IR). Thermogravimetric analysis (TGA) indicated that PMAA molecules were absorbed or anchored on the surface of nano-ZnO particle, which facilitated to hinder the aggregation of nano-ZnO particles. Through particle size analysis and transmission electron micrograph (TEM) observation, it was found that PMAA enhanced the dispersibility of nano-ZnO particles in water. The dispersion stabilization of modified ZnO nanoparticles in aqueous system was significantly improved due to the introduction of grafted polymer on the surface of nanoparticles. The modification did not alter the crystalline structure of the ZnO nanoparticles according to the X-ray diffraction patterns.

Supramolecular structures on silica surfaces and their adsorptive properties.

PubMed

Belyakov, Vladimir N; Belyakova, Lyudmila A; Varvarin, Anatoly M; Khora, Olexandra V; Vasilyuk, Sergei L; Kazdobin, Konstantin A; Maltseva, Tetyana V; Kotvitskyy, Alexey G; Danil de Namor, Angela F

2005-05-01

The study of adsorptive and chemical immobilization of beta-cyclodextrin on a surface of hydroxylated silicas with various porous structure is described. Using IR spectroscopy, thermal gravimetrical analysis with a programmed heating, and chemical analysis of the silica surface, it is shown that the process of adsorption-desorption of beta-cyclodextrin depends on the porous structure of the silica. The reaction of esterification was used for chemical grafting of beta-cyclodextrin on the surface of hydroxylated silicas. Hydrolytic stability of silicas chemically modified by beta-cyclodextrin apparently is explained by simultaneous formation of chemical and hydrogen bonds between surface silanol groups and hydroxyl groups of beta-cyclodextrin. The uptake of the cations Cu(II), Cd(II), and Pb(II) and the anions Cr(VI) and As(V) by silicas modified with beta-cyclodextrin is investigated as a function of equilibrium ion concentrations. The increase of ion uptake and selectivity of ion extraction in comparison with starting silicas is established. It is due to the formation of surface inclusion complexes of the "host-guest" type in which one molecule of beta-cyclodextrin interacts simultaneously with several ions.

Electrochemical, photoelectrochemical, and surface plasmon resonance detection of cocaine using supramolecular aptamer complexes and metallic or semiconductor nanoparticles.

PubMed

Golub, Eyal; Pelossof, Gilad; Freeman, Ronit; Zhang, Hong; Willner, Itamar

2009-11-15

Metallic or semiconductor nanoparticles (NPs) are used as labels for the electrochemical, photoelectrochemical, or surface plasmon resonance (SPR) detection of cocaine using a common aptasensor configuration. The aptasensors are based on the use of two anticocaine aptamer subunits, where one subunit is assembled on a Au support, acting as an electrode or a SPR-active surface, and the second aptamer subunit is labeled with Pt-NPs, CdS-NPs, or Au-NPs. In the different aptasensor configurations, the addition of cocaine results in the formation of supramolecular complexes between the NPs-labeled aptamer subunits and cocaine on the metallic surface, allowing the quantitative analysis of cocaine. The supramolecular Pt-NPs-aptamer subunits-cocaine complex allows the detection of cocaine by the electrocatalyzed reduction of H(2)O(2). The photocurrents generated by the CdS-NPs-labeled aptamer subunits-cocaine complex, in the presence of triethanol amine as a hole scavenger, allows the photoelectrochemical detection of cocaine. The supramolecular Au-NPs-aptamer subunits-cocaine complex generated on the Au support allows the SPR detection of cocaine through the reflectance changes stimulated by the electronic coupling between the localized plasmon of the Au-NPs and the surface plasmon wave. All aptasensor configurations enable the analysis of cocaine with a detection limit in the range of 10(-6) to 10(-5) M. The major advantage of the sensing platform is the lack of background interfering signals.

A theoretical study on the electronic structure of Au-XO(0,-1,+1) (X=C, N, and O) complexes: effect of an external electric field.

PubMed

Tielens, Frederik; Gracia, Lourdes; Polo, Victor; Andrés, Juan

2007-12-20

A theoretical study on the nature of Au-XO(0,-1,+1) (X=C, N, O) interaction is carried out in order to provide a better understanding on the adsorption process of XO molecules on Au surfaces or Au-supported surfaces. The effect of the total charge as well as the presence of an external electric field on the formation processes of the Au-XO complex are analyzed and discussed using DFT (B3LYP) and high-level ab initio (CCSD(T)//MP2) methods employing a 6-311+G(3df) basis set for X and O atoms and Stuttgart pseudopotentials for Au atom. The presence of an electric field can increase the binding of O2 molecule to Au while weakening the formation of the Au-CO complex. These behaviors are discussed in the context of adsorption or deadsorption of these molecules on Au clusters. The formation of the Au-XO complex, the effect of addition/removal of one electron, and the role of the electric field are rationalized by studying the nature of the bonding interactions by means of the electron localization function (ELF) analysis. The net interaction between Au and XO fragments is governed by the interplay of three factors: (i) the amount of charge transfer from Au to XO, (ii) the sharing of the lone pair from X atom by the Au core (V(X, Au) basin), and (iii) the role of the lone pair of Au (V(Au) basin) mainly formed by 6s electrons. The total charge of the system and the applied electric field determine the population and orientation of the V(Au) basin and, subsequently, the degree of repulsion with the V(X, Au) basin.

Binding thermodynamics of synthetic dye Allura Red with bovine serum albumin.

PubMed

Lelis, Carini Aparecida; Hudson, Eliara Acipreste; Ferreira, Guilherme Max Dias; Ferreira, Gabriel Max Dias; da Silva, Luis Henrique Mendes; da Silva, Maria do Carmo Hespanhol; Pinto, Maximiliano Soares; Pires, Ana Clarissa Dos Santos

2017-02-15

The interaction between Allura Red and bovine serum albumin (BSA) was studied in vitro at pH 7.4. The fluorescence quenching was classified as static quenching due to the formation of AR-BSA complex, with binding constant (K) ranging from 3.26±0.09 to 8.08±0.0610(4)L.mol(-1), at the warfarin binding site of BSA. This complex formation was driven by increasing entropy. Isothermal titration calorimetric measurements also showed an enthalpic contribution. The Allura Red diffusion coefficient determined by the Taylor-Aris technique corroborated these results because it reduced with increasing BSA concentration. Interfacial tension measurements showed that the AR-BSA complex presented surface activity, since interfacial tension of the water-air interface decreased as the colorant concentration increased. This technique also provided a complexation stoichiometry similar to those obtained by fluorimetric experiments. This work contributes to the knowledge of interactions between BSA and azo colorants under physiological conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Myosin 7 and its adaptors link cadherins to actin.

PubMed

Yu, I-Mei; Planelles-Herrero, Vicente J; Sourigues, Yannick; Moussaoui, Dihia; Sirkia, Helena; Kikuti, Carlos; Stroebel, David; Titus, Margaret A; Houdusse, Anne

2017-06-29

Cadherin linkages between adjacent stereocilia and microvilli are essential for mechanotransduction and maintaining their organization. They are anchored to actin through interaction of their cytoplasmic domains with related tripartite complexes consisting of a class VII myosin and adaptor proteins: Myo7a/SANS/Harmonin in stereocilia and Myo7b/ANKS4B/Harmonin in microvilli. Here, we determine high-resolution structures of Myo7a and Myo7b C-terminal MyTH4-FERM domain (MF2) and unveil how they recognize harmonin using a novel binding mode. Systematic definition of interactions between domains of the tripartite complex elucidates how the complex assembles and prevents possible self-association of harmonin-a. Several Myo7a deafness mutants that map to the surface of MF2 disrupt harmonin binding, revealing the molecular basis for how they impact the formation of the tripartite complex and disrupt mechanotransduction. Our results also suggest how switching between different harmonin isoforms can regulate the formation of networks with Myo7a motors and coordinate force sensing in stereocilia.

Helical assembly in the MyD88-IRAK4-IRAK2 complex in TLR/IL-1R signalling

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

Lin, Su-Chang; Lo, Yu-Chih; Wu, Hao

2010-08-23

MyD88, IRAK4 and IRAK2 are critical signalling mediators of the TLR/IL1-R superfamily. Here we report the crystal structure of the MyD88-IRAK4-IRAK2 death domain (DD) complex, which surprisingly reveals a left-handed helical oligomer that consists of 6 MyD88, 4 IRAK4 and 4 IRAK2 DDs. Assembly of this helical signalling tower is hierarchical, in which MyD88 recruits IRAK4 and the MyD88-IRAK4 complex recruits the IRAK4 substrates IRAK2 or the related IRAK1. Formation of these Myddosome complexes brings the kinase domains of IRAKs into proximity for phosphorylation and activation. Composite binding sites are required for recruitment of the individual DDs in the complex,more » which are confirmed by mutagenesis and previously identified signalling mutations. Specificities in Myddosome formation are dictated by both molecular complementarity and correspondence of surface electrostatics. The MyD88-IRAK4-IRAK2 complex provides a template for Toll signalling in Drosophila and an elegant mechanism for versatile assembly and regulation of DD complexes in signal transduction.« less

Inhibition of the aggregation of lactoferrin and (-)-epigallocatechin gallate in the presence of polyphenols, oligosaccharides, and collagen peptide.

PubMed

Yang, Wei; Liu, Fuguo; Xu, Chenqi; Sun, Cuixia; Yuan, Fang; Gao, Yanxiang

2015-05-27

The aggregation of lactoferrin and (-)-epigallocatechin gallate (EGCG) was inhibited by polyphenols, oligosaccharides, and collagen peptide in this study. Polyphenols, oligosaccharides, or collagen peptide can effectively prevent the formation of lactoferrin-EGCG aggregates, respectively. The addition sequence of lactoferrin, polyphenols (oligosaccharides or collagen peptide) and EGCG can affect the turbidity and particle size of the ternary complexes in the buffer solution; however, it hardly affected the ζ-potential and fluorescence characteristics. With either positive or negative charge, polyphenols and collagen peptide disrupted the formation of lactoferrin-EGCG aggregate mainly through the mechanism of its competition with EGCG molecules which surrounded the lactoferrin molecule surface with weaker binding affinities, forming polyphenols or a collagen peptide-lactoferrin-EGCG ternary complex; for neutral oligosaccharides, the ternary complex was generated mainly through steric effects, accompanied by a change in the lactoferrin secondary structure induced by gallic acid, chlorogenic acid, and xylo-oligosaccharide. Polyphenols, oligosaccharides, or collagen peptide restraining the formation of lactoferrin-EGCG aggregate could be applied in the design of clear products in the food, pharmaceutical, and cosmetic industries.

Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

2017-08-01

Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O2 on ferrihydrite surfaces should include an electrochemical pathway, i.e., electron transfer (ET) in the Mn(II)-Conduction Band (CB)Ferrihydrite-O2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e., ET in the Mn(II)-Fe(II, III)-O2 complexes and direct ET in the Mn(II)-O2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments.

Direct electronic probing of biological complexes formation

NASA Astrophysics Data System (ADS)

Macchia, Eleonora; Magliulo, Maria; Manoli, Kyriaki; Giordano, Francesco; Palazzo, Gerardo; Torsi, Luisa

2014-10-01

Functional bio-interlayer organic field - effect transistors (FBI-OFET), embedding streptavidin, avidin and neutravidin as bio-recognition element, have been studied to probe the electronic properties of protein complexes. The threshold voltage control has been achieved modifying the SiO2 gate diaelectric surface by means of the deposition of an interlayer of bio-recognition elements. A threshold voltage shift with respect to the unmodified dielectric surface toward more negative potential values has been found for the three different proteins, in agreement with their isoelectric points. The relative responses in terms of source - drain current, mobility and threshold voltage upon exposure to biotin of the FBI-OFET devices have been compared for the three bio-recognition elements.

Factors Influencing Biofilm Formation in Streams: Bacterial Colonization, Detachment and Transport

NASA Astrophysics Data System (ADS)

Leff, L.

2005-05-01

Surfaces in aquatic systems develop biofilms containing microorganisms embedded in complex extracellular matrices. Properties of the surface, water, and colonizing organisms impact biofilm formation. Biofilm features, physical disturbance, and interactions between macro- and microscopic organisms, in turn, influence detachment. In spite of the importance of biofilms, much remains unknown about factors controlling biofilms in streams and other natural environments. Experiments were conducted in the laboratory and field to examine factors influencing surface colonization, and subsequent biofilm formation, and detachment. Microscopy methods, fluorescent in situ hybridization and confocal laser microscopy, were used to examine responses, including abundance of different taxa and biofilm depth. From these experiments, we determined that different taxa differ in their colonization ability based on properties like extracellular polysaccharide production and surface features, like hydrophobicity and that water chemistry, such as magnesium concentration, plays an important role. Moreover, detachment varies among taxa and with environmental conditions and may be enhanced by activities of macrofauna. Variation in detachment, in turn, influences bacterial transport and subsequent re-attachment. Overall, examination of attachment, detachment, and interactions in biofilms allows us to begin to understand how environmental conditions may impact the function of these communities in aquatic systems.

GDP-mannose-4,6-dehydratase (GMDS) Deficiency Renders Colon Cancer Cells Resistant to Tumor Necrosis Factor-related Apoptosis-inducing Ligand (TRAIL) Receptor- and CD95-mediated Apoptosis by Inhibiting Complex II Formation*

PubMed Central

Moriwaki, Kenta; Shinzaki, Shinichiro; Miyoshi, Eiji

2011-01-01

Tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) induces apoptosis through binding to TRAIL receptors, death receptor 4 (DR4), and DR5. TRAIL has potential therapeutic value against cancer because of its selective cytotoxic effects on several transformed cell types. Fucosylation of proteins and lipids on the cell surface is a very important posttranslational modification that is involved in many cellular events. Recently, we found that a deficiency in GDP-mannose-4,6-dehydratase (GMDS) rendered colon cancer cells resistant to TRAIL-induced apoptosis, resulting in tumor development and metastasis by escape from tumor immune surveillance. GMDS is an indispensable regulator of cellular fucosylation. In this study, we investigated the molecular mechanism of inhibition of TRAIL signaling by GMDS deficiency. DR4, but not DR5, was found to be fucosylated; however, GMDS deficiency inhibited both DR4- and DR5-mediated apoptosis despite the absence of fucosylation on DR5. In addition, GMDS deficiency also inhibited CD95-mediated apoptosis but not the intrinsic apoptosis pathway induced by anti-cancer drugs. Binding of TRAIL and CD95 ligand to their cognate receptors primarily leads to formation of a complex comprising the receptor, FADD, and caspase-8, referred to as the death-inducing signaling complex (DISC). GMDS deficiency did not affect formation of the primary DISC or recruitment to and activation of caspase-8 on the DISC. However, formation of secondary FADD-dependent complex II, comprising caspase-8 and cFLIP, was significantly inhibited by GMDS deficiency. These results indicate that GMDS regulates the formation of secondary complex II from the primary DISC independent of direct fucosylation of death receptors. PMID:22027835

The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

NASA Astrophysics Data System (ADS)

Enrique-Romero, J.; Rimola, A.; Ceccarelli, C.; Balucani, N.

2016-06-01

Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

Aniline chlorination by in situ formed Ag-Cl complexes under simulated solar light irradiation.

PubMed

Hu, Xuefeng; Wang, Xiaowen; Dong, Liuliu; Chang, Fei; Luo, Yongming

2015-01-01

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Spectroscopic identification of binary and ternary surface complexes of Np(V) on gibbsite.

PubMed

Gückel, Katharina; Rossberg, André; Müller, Katharina; Brendler, Vinzenz; Bernhard, Gert; Foerstendorf, Harald

2013-12-17

For the first time, detailed molecular information on the Np(V) sorption species on amorphous Al(OH)3 and crystalline gibbsite was obtained by in situ time-resolved Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The results consistently demonstrate the formation of mononuclear inner sphere complexes of the NpO2(+) ion irrespective of the prevailing atmospheric condition. The impact of the presence of atmospheric equivalent added carbonate on the speciation in solution and on the surfaces becomes evident from vibrational data. While the 1:1 aqueous carbonato species (NpO2CO3(-)) was found to become predominant in the circumneutral pH range, it is most likely that this species is sorbed onto the gibbsite surface as a ternary inner sphere surface complex where the NpO2(+) moiety is directly coordinated to the functional groups of the gibbsite's surface. These findings are corroborated by results obtained from EXAFS spectroscopy providing further evidence for a bidentate coordination of the Np(V) ion on amorphous Al(OH)3. The identification of the Np(V) surface species on gibbsite constitutes a basic finding for a comprehensive description of the dissemination of neptunium in groundwater systems.

Multiple pickering emulsions stabilized by microbowls.

PubMed

Nonomura, Yoshimune; Kobayashi, Naoto; Nakagawa, Naoki

2011-04-19

Some researchers have focused on the adsorption of solid particles at fluid-fluid interfaces and prepared emulsions and foams called "Pickering emulsions/foams". However, while several reports exist on simple spherical emulsions, few reports are available on the formation of more complex structures. Here, we show that holes on particle surfaces are a key factor in establishing the variety and complexity of mesoscale structures. Microbowls, which are hollow particles with holes on their surfaces, form multiple emulsions (water-in-oil-in-water and oil-in-water-in-oil emulsions) by simply mixing them with water and oil. Furthermore, stable potato-like or coffee-bean-like emulsions are also obtained, although nonspherical emulsions are usually unstable because of their larger interfacial energies. These findings are useful in designing the building blocks of complex supracolloidal systems for pharmaceutical, food, and cosmetic products. © 2011 American Chemical Society

Photoactivation of Diiodido-Pt(IV) Complexes Coupled to Upconverting Nanoparticles.

PubMed

Perfahl, Stefanie; Natile, Marta M; Mohamad, Heba S; Helm, Christiane A; Schulzke, Carola; Natile, Giovanni; Bednarski, Patrick J

2016-07-05

The preparation, characterization, and surface modification of upconverting lanthanide-doped hexagonal NaGdF4 nanocrystals attached to light sensitive diiodido-Pt(IV) complexes is presented. The evaluation for photoactivation and cytotoxicity of the novel carboxylated diiodido-Pt(IV) cytotoxic prodrugs by near-infrared (NIR) light (λ = 980 nm) is also reported. We attempted two different strategies for attachment of light-sensitive diiodido-Pt(IV) complexes to Yb,Er- and Yb,Tm-doped β-NaGdF4 upconverting nanoparticles (UCNPs) in order to provide nanohybrids, which offer unique opportunities for selective drug activation within the tumor cells and subsequent spatiotemporal controlled drug release by NIR-to-visible light-upconversion: (A) covalent attachment of the Pt(IV) complex via amide bond formation and (B) carboxylate exchange of oleate on the surface of the UCNPs with diiodido-Pt(IV) carboxylato complexes. Initial feasibility studies showed that NIR applied by a 980 nm laser had only a slight effect on the stability of the various diiodido-Pt(IV) complexes, but when UCNPs were present more rapid loss of the ligand-metal-charge transfer (LMCT) bands of the diiodido-Pt(IV) complexes was observed. Furthermore, Pt released from the Pt(IV) complexes platinated calf-thymus DNA (ct-DNA) more rapidly when NIR was applied compared to dark controls. Of the two attachment strategies, method A with the covalently attached diiodido-Pt(IV) carboxylates via amide bond formation proved to be the most effective method for generating UCNPs that release Pt when irradiated with NIR; the released Pt was also able to bind irreversibly to calf thymus DNA. Nonetheless, only ca. 20% of the Pt on the surface of the UCNPs was in the Pt(IV) oxidation state, the rest was Pt(II), indicating chemical reduction of the diiodido-Pt(IV) prodrug by the UCNPs. Cytotoxicity studies with the various UCNP-Pt conjugates and constructs, tested on human leukemia HL60 cells in culture, indicated a substantial increase in cytotoxicity when modified UCNPs were combined with five rounds of 30 min irradiation with NIR compared to dark controls, but NIR alone also had a significant cytotoxic effect at this duration.

Titan's atmosphere and climate

NASA Astrophysics Data System (ADS)

Hörst, S. M.

2017-03-01

Titan is the only moon with a substantial atmosphere, the only other thick N2 atmosphere besides Earth's, the site of extraordinarily complex atmospheric chemistry that far surpasses any other solar system atmosphere, and the only other solar system body with stable liquid currently on its surface. The connection between Titan's surface and atmosphere is also unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan's atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan's atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. The Cassini-Huygens mission to the Saturn system has provided a wealth of new information allowing for study of Titan as a complex system. Here I review our current understanding of Titan's atmosphere and climate forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I conclude with some of our remaining unanswered questions as the incredible era of exploration with Cassini-Huygens comes to an end.

Computer-aided molecular modeling techniques for predicting the stability of drug cyclodextrin inclusion complexes in aqueous solutions

NASA Astrophysics Data System (ADS)

Faucci, Maria Teresa; Melani, Fabrizio; Mura, Paola

2002-06-01

Molecular modeling was used to investigate factors influencing complex formation between cyclodextrins and guest molecules and predict their stability through a theoretical model based on the search for a correlation between experimental stability constants ( Ks) and some theoretical parameters describing complexation (docking energy, host-guest contact surfaces, intermolecular interaction fields) calculated from complex structures at a minimum conformational energy, obtained through stochastic methods based on molecular dynamic simulations. Naproxen, ibuprofen, ketoprofen and ibuproxam were used as model drug molecules. Multiple Regression Analysis allowed identification of the significant factors for the complex stability. A mathematical model ( r=0.897) related log Ks with complex docking energy and lipophilic molecular fields of cyclodextrin and drug.

Distinguishing Grenvillian basement from pre-Taconian cover rocks in the Northern Appalachians

USGS Publications Warehouse

Karabinos, P.; Aleinikoff, J.N.; Fanning, C.M.

1999-01-01

Distinguishing Grenvillian basement rocks from pre-Taconian cover sequences in the Appalachians is a first-order problem essential for accurate structural interpretations. The Cavendish Formation in southeastern Vermont presents a classic example of this problem. Doll and others (1961) showed the Cavendish Formation as younger than the Middle Proterozoic Mount Holly Complex but older than the lithologically similar Cambrian Tyson and Hoosac Formations. More recently, the name Cavendish Formation has been informally abandoned, and its metasedimentary units have been mapped as the Tyson and Hoosac Formations of Late Proterozoic to Cambrian age. In a radical departure from these interpretations, Ratcliffe and others (1997) reassigned metasedimentary rocks of the Cavendish Formation to the Mount Holly Complex based on an inferred intrusive relationship between them and a 1.42 Ga tonalite. This new age assignment, if correct, requires a completely new structural interpretation of the region. SHRIMP and Pb evaporation ages of detrital zircons extracted from a quartzite layer from Cavendish Gorge near the proposed intrusive contact with the tonalite constrain the time of deposition of the Cavendish Formation. Grain shapes of the zircons vary from euhedral to nearly spherical. Virtually all the grains have pitted surfaces and show at least some rounding of edges and terminations; grains exhibit oscillatory zoning typical of zircons that crystallized from a magma. Single-grain Pb evaporation analyses of ten zircons and SHRIMP analyses of 15 zircons all yield ages less than 1.42 Ga. Seven of the grains are consistent with derivation from the Bull Hill Gneiss that postdates the Grenville orogenic cycle and predates deposition of the Cavendish Formation. Thus, the metasedimentary units of the Cavendish Formation should not be assigned to the Mount Holly Complex.

A GAS-PHASE FORMATION ROUTE TO INTERSTELLAR TRANS-METHYL FORMATE

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

Cole, Callie A.; Wehres, Nadine; Yang Zhibo

2012-07-20

The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowingmore » afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 {+-} 0.39) Multiplication-Sign 10{sup -10} cm{sup 3} s{sup -1} ({+-} 1{sigma}) and an average branching fraction of 0.05 {+-} 0.04 for protonated trans-methyl formate and 0.95 {+-} 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.« less

Use of electrical imaging and distributed temperature sensing methods to characterize surface water–groundwater exchange regulating uranium transport at the Hanford 300 Area, Washington

USGS Publications Warehouse

Slater, Lee D.; Ntarlagiannis, Dimitrios; Day-Lewis, Frederick D.; Mwakanyamale, Kisa; Versteeg, Roelof J.; Ward, Andy; Strickland, Christopher; Johnson, Carole D.; Lane, John W.

2010-01-01

We explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber‐optic distributed temperature sensor (FO‐DTS) monitoring, to improve the conceptual model for uranium transport within the Columbia River corridor at the Hanford 300 Area, Washington. We first inverted resistivity and induced polarization CWEI data sets for distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units was reconstructed. Variations in the depth to the interface between the overlying coarse‐grained, high‐permeability Hanford Formation and the underlying finer‐grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, were resolved along ∼3 km of the river corridor centered on the 300 Area. Polarizability images were translated into lithologic images using established relationships between polarizability and surface area normalized to pore volume (Spor). The FO‐DTS data recorded along 1.5 km of cable with a 1 m spatial resolution and 5 min sampling interval revealed subreaches showing (1) temperature anomalies (relatively warm in winter and cool in summer) and (2) a strong correlation between temperature and river stage (negative in winter and positive in summer), both indicative of reaches of enhanced surface water–groundwater exchange. The FO‐DTS data sets confirm the hydrologic significance of the variability identified in the CWEI and reveal a pattern of highly focused exchange, concentrated at springs where the Hanford Formation is thickest. Our findings illustrate how the combination of CWEI and FO‐DTS technologies can characterize surface water–groundwater exchange in a complex, coupled river‐aquifer system.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

Mechanisms on the Impacts of Alkalinity, pH, and Chloride on Persulfate-Based Groundwater Remediation.

PubMed

Li, Wei; Orozco, Ruben; Camargos, Natalia; Liu, Haizhou

2017-04-04

Persulfate (S 2 O 8 2- )-based in situ chemical oxidation (ISCO) has gained more attention in recent years due to the generation of highly reactive and selective sulfate radical (SO 4 •- ). This study examined the effects of important groundwater chemical parameters, i.e., alkalinity, pH, and chloride on benzene degradation via heterogeneous persulfate activation by three Fe(III)- and Mn(IV)-containing aquifer minerals: ferrihydrite, goethite, and pyrolusite. A comprehensive kinetic model was established to elucidate the mechanisms of radical generation and mineral surface complexation. Results showed that an increase of alkalinity up to 10 meq/L decreased the rates of persulfate decomposition and benzene degradation, which was associated with the formation of unreactive surface carbonato complexes. An increase in pH generally accelerated persulfate decomposition due to enhanced formation of reactive surface hydroxo complexation. A change in the chloride level up to 5 mM had a negligibly effect on the reaction kinetics. Kinetics modeling also suggested that SO 4 •- was transformed to hydroxyl radical (HO • ) and carbonate radical (CO 3 •- ) at higher pHs. Furthermore, the yields of two major products of benzene oxidation, i.e., phenol and aldehyde, were positively correlated with the branching ratio of SO 4 •- reacting with benzene, but inversely correlated with that of HO • or CO 3 •- , indicating that SO 4 •- preferentially oxidized benzene via pathways involving fewer hydroxylation steps compared to HO • or CO 3 •- .

Charge-transfer complex formation between TiO2 nanoparticles and thiosalicylic acid: A comprehensive experimental and DFT study

NASA Astrophysics Data System (ADS)

Milićević, Bojana; Đorđević, Vesna; Lončarević, Davor; Dostanić, Jasmina M.; Ahrenkiel, S. Phillip; Dramićanin, Miroslav D.; Sredojević, Dušan; Švrakić, Nenad M.; Nedeljković, Jovan M.

2017-11-01

Under normal conditions, titanium dioxide does not absorb visible light photons due to large band gap. Nevertheless, when titanium dioxide nanoparticles (TiO2 NPs) are surface-modified with thiosalicylic acid (TSA), their optical properties are altered owing to the formation of charge transfer complex that initiates absorption in the visible spectral range. Colloidal and sol-gel techniques were used to synthesize uniform TiO2 NPs of different sizes (average diameters in the range 4-15 nm), and effects of their subsequent modification by TSA molecules were compared with effect of modification of commercial Degussa TiO2 powder. Thorough microstructural characterization of TiO2 nanoparticulates was performed including transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis, as well as nitrogen adsorption-desorption isotherms. Optical measurements revealed that all surface-modified TiO2 samples with TSA have similar spectral features independent of their morphological differences, and, more importantly, absorption onset of modified TiO2 samples was found to be red-shifted by 1.0 eV compared to the unmodified ones. The mode of binding between TSA and surface Ti atoms was analyzed by infrared spectroscopy. Finally, the quantum chemical calculations, based on density functional theory, were performed to support optical characterization of surface-modified TiO2 with TSA.

MicroCantilever (MC) based nanomechanical sensor for detection of molecular interactions

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

Kang, Kyung

Specific aims of this study are to investigate the mechanism governing surface stress generation associated with chemical or molecular binding on functionalized microcantilevers. Formation of affinity complexes on cantilever surfaces leads to charge redistribution, configurational change and steric hindrance between neighboring molecules resulting in surface stress change and measureable cantilever deformation. A novel interferometry technique employing two adjacent micromachined cantilevers (a sensing/reference pair) was utilized to measure the cantilever deformation. The sensing principle is that binding/reaction of specific chemical or biological species on the sensing cantilever transduces to mechanical deformation. The differential bending of the sensing cantilever respect to themore » reference cantilever ensures that measured response is insensitive to environmental disturbances. As a proof of principle for the measurement technique, surface stress changes associated with: self-assembly of alkanethiol, hybridization of ssDNA, and the formation of cocaine-aptamer complexes were measured. Dissociation constant (K d) for each molecular reaction was utilized to estimate the surface coverage of affinity complexes. In the cases of DNA hybridization and cocaine-aptamer binding, measured surface stress was found to be dependent on the surface coverage of the affinity complexes. In order to achieve a better sensitivity for DNA hybridization, immobilization of receptor molecules was modified to enhance the deformation of underlying surface. Single-stranded DNA (ssDNA) strands with thiol-modification on both 3-foot and 5-foot ends were immobilized on the gold surface such that both ends are attached to the gold surface. Immobilization condition was controlled to obtain similar receptor density as single-thiolated DNA strands. Hybridization of double-thiolated DNA strands leads to an almost two orders of magnitude increase in cantilever deformation. In both DNA hybridization and the conventional mode for cocaine detection, the lowest detectable concentration was determined by binding activity between the ligand and receptor molecules. In order to overcome this limitation for cocaine detection, a novel competition sensing mode that relies on rate of aptamers unbinding from the cantilever due to either diffusion or reaction with cocaine as target ligands in solution was investigated. The rate of unbinding is found to be dependent on the concentration of cocaine molecules. A model based on diffusion-reaction equation was developed to explain the experimental observation. Experimental results indicate that the competition mode reduces the lowest detectable threshold to 200 nM which is comparable to that achieved analytical techniques such as mass spectrometry.« less

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics.

PubMed

Dul, Maria; Paluch, Krzysztof J; Kelly, Hazel; Healy, Anne Marie; Sasse, Astrid; Tajber, Lidia

2015-06-05

The aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT. Copyright © 2015 Elsevier Ltd. All rights reserved.

Optimum hexametaphosphate concentration to inhibit efflorescence formation in dry fermented sausages.

PubMed

Walz, Felix H; Gibis, Monika; Fritz, Maren; Herrmann, Kurt; Hinrichs, Jörg; Weiss, Jochen

2018-05-01

The occurrence of efflorescences on the surface of dry fermented sausages represents a current issue for the meat processing industry. Preventing the efflorescence formation by the addition of sodium hexametaphosphate (SHMP) was shown to be promising in a previous study. The optimum SHMP addition was studied by adding SHMP (0.0, 1.0, 3.0, and 5.0g/kg) directly to the sausage batter. Visual and chemical analyses were conducted during 8weeks of storage under modified atmosphere. Visual analyses revealed significant lower amounts of efflorescences on the sausage surface after 8weeks when 1.0 (27.1%), 3.0 (9.0%), and 5.0g/kg SHMP (3.4%) were added, compared to the control with 38.0% efflorescences. SHMP significantly affected the occurrence (8weeks) of magnesium on the surface: +85.5%, +23.7%, +3.5%, and -28.2% for 0.0, 1.0, 3.0, and 5.0g/kg, respectively. The addition of 4.785g/kg was calculated to fully inhibit the formation of efflorescences by complexing magnesium ions. Copyright © 2018 Elsevier Ltd. All rights reserved.

The effect of butterfly-scale inspired patterning on leading-edge vortex growth

NASA Astrophysics Data System (ADS)

Wilroy, Jacob; Lang, Amy; Wahidi, Redha

2014-11-01

Leading edge vortices (LEVs) are important for generating thrust and lift in flapping flight, and the surface patterning (scales) on butterfly wings is hypothesized to play a role in the vortex formation of the LEV. To simplify this complex flow problem, we designed an experiment to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically we are interested in the secondary vorticity generated by the LEV interacting at the patterned surface and how this can affect the growth rate of the circulation in the LEV. For this experiment we used rapid-prototyped longitudinal and transverse square grooves attached to a flat plate and compared the vortex formation as the plate moved vertically. The plate is impulsively started in quiescent water and flow fields at Re = 1500, 3000, and 6000 are examined using Digital Particle Image Velocimetry (DPIV). The vortex formation time is 0.6 and is based on the flat plate travel length and chord length. Support for this research came from NSF REU Grant 1358991 and CBET 1335848.

The effect of butterfly-scale inspired patterning on leading-edge vortex growth

NASA Astrophysics Data System (ADS)

Wilroy, Jacob; Lang, Amy

2015-11-01

Leading edge vortices (LEVs) are important for generating thrust and lift in flapping flight, and the surface patterning (scales) on butterfly wings is hypothesized to play a role in the vortex formation of the LEV. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied and the subsequent affect on the growth rate of the circulation in the LEV. For this experiment we used butterfly inspired grooves attached to a flat plate and compared the vortex formation to a smooth plate case as the plate moved vertically. The plate is impulsively started in quiescent water and flow fields at Re = 1500, 3000, and 6000 are examined using Digital Particle Image Velocimetry (DPIV). The vortex formation time is 3.0 and is based on the flat plate travel length and chord length. We would like to thank the National Science Foundation REU Site Award 1358991 for funding this research.

The Formation and Binding of Gold Nanoparticles onto Wool Fibres

NASA Astrophysics Data System (ADS)

Johnston, James H.; Burridge, Kerstin A.; Kelly, Fern M.

2009-07-01

This paper presents the novel use of nanosize gold with different plasmon resonance colours, as stable colourfast colourants on wool fibres for use in high quality fabrics and textiles. The gold nanoparticles are synthesised by the controlled reduction of Au3+ in the AuCl4- complex to Au0 onto the surface of the wool where they attach to the S in the cystine amino acids in wool keratin proteins. Scanning electronmicroscopy shows the nanoparticles are present on the cuticles of the fibre surface and are concentrated at the edges of these cuticles. EDS analysis shows a strong correlation of Au with S and X-ray photoelectron spectroscopy suggests Au-S bond formation. Hence the nanogold colourants are chemically bound to the wool fibre surface and do not fade as traditional organic dyes do. A range of coloured fibres have been produced.

The Formation and Binding of Gold Nanoparticles onto Wool Fibres

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

Johnston, James H.; Burridge, Kerstin A.; Kelly, Fern M.

2009-07-23

This paper presents the novel use of nanosize gold with different plasmon resonance colours, as stable colourfast colourants on wool fibres for use in high quality fabrics and textiles. The gold nanoparticles are synthesised by the controlled reduction of Au{sup 3+} in the AuCl{sub 4}{sup -} complex to Au{sup 0} onto the surface of the wool where they attach to the S in the cystine amino acids in wool keratin proteins. Scanning electronmicroscopy shows the nanoparticles are present on the cuticles of the fibre surface and are concentrated at the edges of these cuticles. EDS analysis shows a strong correlationmore » of Au with S and X-ray photoelectron spectroscopy suggests Au-S bond formation. Hence the nanogold colourants are chemically bound to the wool fibre surface and do not fade as traditional organic dyes do. A range of coloured fibres have been produced.« less

The Formation of Glycine in Hot Cores: New Gas-grain Chemical Simulations of Star-forming Regions

NASA Astrophysics Data System (ADS)

Garrod, Robin

2012-07-01

Organic molecules of increasing complexity have been detected in the warm envelopes of star-forming cores, commonly referred to as "hot cores". Spectroscopic searches at mm/sub-mm wavelengths have uncovered both amines and carboxylic acids in these regions, as well as a range of other compounds including alcohols, ethers, esters, and nitriles. However, the simplest amino acid, glycine (NH2CH2COOH), has not yet been reliably detected in the ISM. There has been much interest in this molecule, due to its importance to the formation of proteins, and to life, while the positive identification of interstellar molecules of similar or greater complexity suggests that its existence in star-forming regions is plausible. I will present the results of recent models of hot-core chemistry that simulate the formation of both simple and complex molecules on the surfaces or within the ice mantles of dust grains. I will also present results from the first gas-grain astrochemical model to approach the question of amino-acid formation in hot cores. The formation of glycine in moderate abundance is found to be as efficient as that for similarly complex species, while its sublimation from the grains occurs at somewhat higher temperatures. However, simulated emission spectra based on the model results show that the degree of compactness of high-abundance regions, and the density and temperature profiles of the cores may be the key variables affecting the future detection of glycine, as well as other amino acids, and may explain its non-detection to date.

FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

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

Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

2016-04-10

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The modelmore » calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.« less

GRAIL gravity observations of the transition from complex crater to peak-ring basin on the Moon: Implications for crustal structure and impact basin formation

NASA Astrophysics Data System (ADS)

Baker, David M. H.; Head, James W.; Phillips, Roger J.; Neumann, Gregory A.; Bierson, Carver J.; Smith, David E.; Zuber, Maria T.

2017-08-01

High-resolution gravity data from the Gravity Recovery and Interior Laboratory (GRAIL) mission provide the opportunity to analyze the detailed gravity and crustal structure of impact features in the morphological transition from complex craters to peak-ring basins on the Moon. We calculate average radial profiles of free-air anomalies and Bouguer anomalies for peak-ring basins, protobasins, and the largest complex craters. Complex craters and protobasins have free-air anomalies that are positively correlated with surface topography, unlike the prominent lunar mascons (positive free-air anomalies in areas of low elevation) associated with large basins. The Bouguer gravity anomaly profiles of complex craters are highly irregular, with central positive anomalies that are generally absent or not clearly tied to interior morphology. In contrast, gravity profiles for peak-ring basins (∼200 km to 580 km) are much more regular and are highly correlated with surface morphology. A central positive Bouguer anomaly is confined within the peak ring and a negative Bouguer anomaly annulus extends from the edge of the positive anomaly outward to about the rim crest. A number of degraded basins lacking interior peak rings have diameters and gravity patterns similar to those of well-preserved peak-ring basins. If these structures represent degraded peak-ring basins, the number of peak-ring basins on the Moon would increase by more than a factor of two to 34. The gravity anomalies within basins are interpreted to be due to uplift of the mantle confined within the peak ring and an annulus of thickened crust between the peak ring and rim crest. We hypothesize that mantle uplift is influenced by interaction between the transient cavity and the mantle. Further, mascon formation is generally disconnected from the number of basin rings formed and occurs over a wide range of basin sizes. These observations have important implications for models of basin and mascon formation on the Moon and other planetary bodies.

Human Lipopolysaccharide-binding Protein (LBP) and CD14 Independently Deliver Triacylated Lipoproteins to Toll-like Receptor 1 (TLR1) and TLR2 and Enhance Formation of the Ternary Signaling Complex*

PubMed Central

Ranoa, Diana Rose E.; Kelley, Stacy L.; Tapping, Richard I.

2013-01-01

Bacterial lipoproteins are the most potent microbial agonists for the Toll-like receptor 2 (TLR2) subfamily, and this pattern recognition event induces cellular activation, leading to host immune responses. Triacylated bacterial lipoproteins coordinately bind TLR1 and TLR2, resulting in a stable ternary complex that drives intracellular signaling. The sensitivity of TLR-expressing cells to lipoproteins is greatly enhanced by two lipid-binding serum proteins known as lipopolysaccharide-binding protein (LBP) and soluble CD14 (sCD14); however, the physical mechanism that underlies this increased sensitivity is not known. To address this, we measured the ability of LBP and sCD14 to drive ternary complex formation between soluble extracellular domains of TLR1 and TLR2 and a synthetic triacylated lipopeptide agonist. Importantly, addition of substoichiometric amounts of either LBP or sCD14 significantly enhanced formation of a TLR1·TLR2 lipopeptide ternary complex as measured by size exclusion chromatography. However, neither LBP nor sCD14 was physically associated with the final ternary complex. Similar results were obtained using outer surface protein A (OspA), a naturally occurring triacylated lipoprotein agonist from Borrelia burgdorferi. Activation studies revealed that either LBP or sCD14 sensitized TLR-expressing cells to nanogram levels of either the synthetic lipopeptide or OspA lipoprotein agonist. Together, our results show that either LBP or sCD14 can drive ternary complex formation and TLR activation by acting as mobile carriers of triacylated lipopeptides or lipoproteins. PMID:23430250

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols.

PubMed

Finlayson-Pitts, Barbara J

2009-09-28

While particles have significant deleterious impacts on human health, visibility and climate, quantitative understanding of their formation, composition and fates remains problematic. Indeed, in many cases, even qualitative understanding is lacking. One area of particular uncertainty is the nature of particle surfaces and how this determines interactions with gases in the atmosphere, including water, which is important for cloud formation and properties. The focus in this Perspective article is on some chemistry relevant to airborne particles and especially to reactions occurring on their surfaces. The intent is not to provide a comprehensive review, but rather to highlight a few selected examples of interface chemistry involving inorganic and organic species that may be important in the lower atmosphere. This includes sea salt chemistry, nitrate and nitrite ion photochemistry, organics on surfaces and heterogeneous reactions of oxides of nitrogen on proxies for airborne mineral dust and boundary layer surfaces. Emphasis is on the molecular level understanding that can only be gained by fully integrating experiment and theory to elucidate these complex systems.

Formation of silver nanoparticle at phospholipid template using Langmuir-Blodgett technique and its Surface-enhanced Raman Spectroscopy application

NASA Astrophysics Data System (ADS)

Mahato, M.; Sarkar, R.; Pal, P.; Talapatra, G. B.

2015-10-01

The biosynthesis of metal nanoparticle and their suitable assembly has recently gained tremendous interest for its application in biomedical arena such as substrates for surface-enhanced Raman scattering and others. In this article, an easy, low-cost, fast, bio-friendly and toxic-reducing agent free protocol has been described for the preparation of silver nanoparticle film using biocompatible 1,2-dipalmitoyl-sn-glycero-3-phosphocholine phospholipid Langmuir monolayer template. Interactions, docking and attachment of silver ions to the above-mentioned phospholipid monolayer have been studied by surface pressure-area isotherm and compressibility analysis at the air-water interface. We have deposited the Langmuir-Blodgett monolayer/multilayer containing silver nanoparticle onto glass/SiO2/quartz substrates. The formation of phospholipid-silver nanoparticle complex in Langmuir-Blodgett film has been characterized by field emission-scanning electron microscopy and high-resolution tunneling electron microscopy images. We have applied this deposited film as a substrate for surface-enhanced Raman scattering application using rhodamine 123 to understand the existence of the surface plasmon activity of silver nanoparticle.

Basic Research of Intrinsic Tamper Indication Markings Defined by Pulsed Laser Irradiation (Quad Chart).

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

Moody, Neville R.

Objective: We will research how short (ns) and ultrashort (fs) laser pulses interact with the surfaces of various materials to create complex color layers and morphological patterns. Method: We are investigating the site-specific, formation of microcolor features. Also, research includes a fundamental study of the physics underlying periodic ripple formation during femtosecond laser irradiation. Status of effort: Laser induced color markings were demonstrated on an increased number of materials (including metal thin films) and investigated for optical properties and microstructure. Technology that allows for marking curved surfaces (and large areas) has been implemented. We have used electro-magnetic solvers to modelmore » light-solid interactions leading to periodic surface ripple patterns. This includes identifying the roles of surface plasmon polaritons. Goals/Milestones: Research corrosion resistance of oxide color markings (salt spray, fog, polarization tests); Through modeling, investigate effects of multi-source scattering and interference on ripple patterns; Investigate microspectrophotometry for mapping color; and Investigate new methods for laser color marking curved surfaces and large areas.« less

[DNA complexes, formed on aqueous phase surfaces: new planar polymeric and composite nanostructures].

PubMed

Antipina, M N; Gaĭnutdinov, R V; Rakhnianskaia, A A; Sergeev-Cherenkov, A N; Tolstikhina, A L; Iurova, T V; Kislov, V V; Khomutov, G B

2003-01-01

The formation of DNA complexes with Langmuir monolayers of the cationic lipid octadecylamine (ODA) and the new amphiphilic polycation poly-4-vinylpyridine with 16% of cetylpyridinium groups (PVP-16) on the surface of an aqueous solution of native DNA of low ionic strength was studied. Topographic images of Langmuir-Blodgett films of DNA/ODA and DNA/PVP-16 complexes applied to micaceous substrates were investigated by the method of atomic force microscopy. It was found that films of the amphiphilic polycation have an ordered planar polycrystalline structure. The morphology of planar DNA complexes with the amphiphilic cation substantially depended on the incubation time and the phase state of the monolayer on the surface of the aqueous DNA solution. Complex structures and individual DNA molecules were observed on the surface of the amphiphilic monolayer. Along with quasi-linear individual bound DNA molecules, characteristic extended net-like structures and quasi-circular toroidal condensed conformations of planar DNA complexes were detected. Mono- and multilayer films of DNA/PVP-16 complexes were used as templates and nanoreactors for the synthesis of inorganic nanostructures via the binding of metal cations from the solution and subsequent generation of the inorganic phase. As a result, ultrathin polymeric composite films with integrated DNA building blocks and quasi-linear arrays of inorganic semiconductor (CdS) and iron oxide nanoparticles and nanowires were obtained. The nanostructures obtained were characterized by scanning probe microscopy and transmission electron microscopy techniques. The methods developed are promising for investigating the mechanisms of structural organization and transformation in DNA and polyelectrolyte complexes at the gas-liquid interface and for the design of new extremely thin highly ordered planar polymeric and composite materials, films, and coatings with controlled ultrastructure for applications in nanoelectronics and nanobiotechnology.

Biomimetic design of platelet adhesion inhibitors to block integrin α2β1-collagen interactions: I. Construction of an affinity binding model.

PubMed

Zhang, Lin; Sun, Yan

2014-04-29

Platelet adhesion on a collagen surface through integrin α2β1 has been proven to be significant for the formation of arterial thrombus. However, the molecular determinants mediating the integrin-collagen complex remain unclear. In the present study, the dynamics of integrin-collagen binding and molecular interactions were investigated using molecular dynamics (MD) simulations and molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) analysis. Hydrophobic interaction is identified as the major driving force for the formation of the integrin-collagen complex. On the basis of the MD simulation and MM-PBSA results, an affinity binding model (ABM) of integrin for collagen is constructed; it is composed of five residues, including Y157, N154, S155, R288, and L220. The ABM has been proven to capture the major binding motif contributing 84.8% of the total binding free energy. On the basis of the ABM, we expect to establish a biomimetic design strategy of platelet adhesion inhibitors, which would be beneficial for the development of potent peptide-based drugs for thrombotic diseases.

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes.

PubMed

Zhu, Fei-Die; Choo, Kwang-Ho; Chang, Hyun-Shik; Lee, Byunghwan

2012-05-01

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels. Copyright © 2012 Elsevier Ltd. All rights reserved.

Dynamics of Defects and Dopants in Complex Systems: Si and Oxide Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

Kirichenko, Taras; Yu, Decai; Banarjee, Sanjay; Hwang, Gyeong

2004-10-01

Fabrication of forthcoming nanometer scale electronic devices faces many difficulties including formation of extremely shallow and highly doped junctions. At present, ultra-low-energy ion implantation followed by high-temperature thermal annealing is most widely used to fabricate such ultra-shallow junctions. In the process, a great challenge lies in achieving precise control of redistribution and electrical activation of dopant impurities. Native defects (such as vacancies and interstitials) generated during implantation are known to be mainly responsible for the TED and also influence significantly the electrical activation/deactivation. Defect-dopant dynamics is rather well understood in crystalline Si and SiO2. However, little is known about their diffusion and annihilation (or precipitation) at the surfaces and interfaces, despite its growing importance in determining junction profiles as device dimensions get smaller. In this talk, we will present our density functional theory calculation results on the atomic and electronic structure and dynamical behavior of native defects and dopant-defect complexes in disordered/strained Si and oxide systems, such as i) clean and absorbent-modified Si(100) surface and subsurface layers, ii) amorphous-crystalline Si interfaces and iii) amorphous SiO2/Si interfaces. The fundamental understanding and data is essential in developing a comprehensive kinetic model for junction formation, which would contribute greatly in improving current process technologies.

Fine tuning cellular recognition: The function of the leucine rich repeat (LRR) trans-membrane protein, LRT, in muscle targeting to tendon cells.

PubMed

Gilsohn, Eli; Volk, Talila

2010-01-01

The formation of complex tissues during embryonic development is often accompanied by directed cellular migration towards a target tissue. Specific mutual recognition between the migrating cell and its target tissue leads to the arrest of the cell migratory behavior and subsequent contact formation between the two interacting cell types. Recent studies implicated a novel family of surface proteins containing a trans-membrane domain and single leucine-rich repeat (LRR) domain in inter-cellular recognition and the arrest of cell migration. Here, we describe the involvement of a novel LRR surface protein, LRT, in targeting migrating muscles towards their corresponding tendon cells in the Drosophila embryo. LRT is specifically expressed by the target tendon cells and is essential for arresting the migratory behavior of the muscle cells. Additional studies in Drosophila S2 cultured cells suggest that LRT forms a protein complex with the Roundabout (Robo) receptor, essential for guiding muscles towards their tendon partners. Genetic analysis supports a model in which LRT performs its activity non-autonomously through its interaction with the Robo receptors expressed on the muscle surfaces. These results suggest a novel mechanism of intercellular recognition through interactions between LRR family members and Robo receptors.

PRince: a web server for structural and physicochemical analysis of protein-RNA interface.

PubMed

Barik, Amita; Mishra, Abhishek; Bahadur, Ranjit Prasad

2012-07-01

We have developed a web server, PRince, which analyzes the structural features and physicochemical properties of the protein-RNA interface. Users need to submit a PDB file containing the atomic coordinates of both the protein and the RNA molecules in complex form (in '.pdb' format). They should also mention the chain identifiers of interacting protein and RNA molecules. The size of the protein-RNA interface is estimated by measuring the solvent accessible surface area buried in contact. For a given protein-RNA complex, PRince calculates structural, physicochemical and hydration properties of the interacting surfaces. All these parameters generated by the server are presented in a tabular format. The interacting surfaces can also be visualized with software plug-in like Jmol. In addition, the output files containing the list of the atomic coordinates of the interacting protein, RNA and interface water molecules can be downloaded. The parameters generated by PRince are novel, and users can correlate them with the experimentally determined biophysical and biochemical parameters for better understanding the specificity of the protein-RNA recognition process. This server will be continuously upgraded to include more parameters. PRince is publicly accessible and free for use. Available at http://www.facweb.iitkgp.ernet.in/~rbahadur/prince/home.html.

Structural requirements of endopolygalacturonase for the interaction with PGIP (polygalacturonase-inhibiting protein)

PubMed Central

Federici, L.; Caprari, C.; Mattei, B.; Savino, C.; Di Matteo, A.; De Lorenzo, G.; Cervone, F.; Tsernoglou, D.

2001-01-01

To invade a plant tissue, phytopathogenic fungi produce several cell wall-degrading enzymes; among them, endopolygalacturonase (PG) catalyzes the fragmentation and solubilization of homogalacturonan. Polygalacturonase-inhibiting proteins (PGIPs), found in the cell wall of many plants, counteract fungal PGs by forming specific complexes with them. We report the crystal structure at 1.73 Å resolution of PG from the phytopathogenic fungus Fusarium moniliforme (FmPG). The structure of FmPG was useful to study the mode of interaction of the enzyme with PGIP-2 from Phaseolus vulgaris. Several amino acids of FmPG were mutated, and their contribution to the formation of the complex with PGIP-2 was investigated by surface plasmon resonance. The residues Lys-269 and Arg-267, located inside the active site cleft, and His-188, at the edge of the active site cleft, are critical for the formation of the complex, which is consistent with the observed competitive inhibition of the enzyme played by PGIP-2. The replacement of His-188 with a proline or the insertion of a tryptophan after position 270, variations that both occur in plant PGs, interferes with the formation of the complex. We suggest that these variations are important structural requirements of plant PGs to prevent PGIP binding. PMID:11687632

Effects of the incorporation of ε-aminocaproic acid/chitosan particles to fibrin on cementoblast differentiation and cementum regeneration.

PubMed

Park, Chan Ho; Oh, Joung-Hwan; Jung, Hong-Moon; Choi, Yoonnyoung; Rahman, Saeed Ur; Kim, Sungtae; Kim, Tae-Il; Shin, Hong-In; Lee, Yun-Sil; Yu, Frank H; Baek, Jeong-Hwa; Ryoo, Hyun-Mo; Woo, Kyung Mi

2017-10-01

Cementum formation on the exposed tooth-root surface is a critical process in periodontal regeneration. Although various therapeutic approaches have been developed, regeneration of integrated and functional periodontal complexes is still wanting. Here, we found that the OCCM30 cementoblasts cultured on fibrin matrix express substantial levels of matrix proteinases, leading to the degradation of fibrin and the apoptosis of OCCM30 cells, which was reversed upon treatment with a proteinase inhibitor, ε-aminocaproic acid (ACA). Based on these findings, ACA-releasing chitosan particles (ACP) were fabricated and ACP-incorporated fibrin (fibrin-ACP) promoted the differentiation of cementoblasts in vitro, as confirmed by bio-mineralization and expressions of molecules associated with mineralization. In a periodontal defect model of beagle dogs, fibrin-ACP resulted in substantial cementum formation on the exposed root dentin in vivo, compared to fibrin-only and enamel matrix derivative (EMD) which is used clinically for periodontal regeneration. Remarkably, the fibrin-ACP developed structural integrations of the cementum-periodontal ligament-bone complex by the Sharpey's fiber insertion. In addition, fibrin-ACP promoted alveolar bone regeneration through increased bone volume of tooth roof-of-furcation defects and root coverage. Therefore, fibrin-ACP can promote cementogenesis and osteogenesis by controlling biodegradability of fibrin, implicating the feasibility of its therapeutic use to improve periodontal regeneration. Cementum, the mineralized layer on root dentin surfaces, functions to anchor fibrous connective tissues on tooth-root surfaces with the collagenous Sharpey's fibers integration, of which are essential for periodontal functioning restoration in the complex. Through the cementum-responsible fiber insertions on tooth-root surfaces, PDLs transmit various mechanical responses to periodontal complexes against masticatory/occlusal stimulations to support teeth. In this study, periodontal tissue regeneration was enhanced by use of modified fibrin biomaterial which significantly promoted cementogenesis within the periodontal complex with structural integration by collagenous Sharpey's fiber insertions in vivo by controlling fibrin degradation and consequent cementoblast apoptosis. Furthermore, the modified fibrin could improve repair and regeneration of tooth roof-of-furcation defects, which has spatial curvatures and geometrical difficulties and hardly regenerates periodontal tissues. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Bifunctional redox tagging of carbon nanoparticles

NASA Astrophysics Data System (ADS)

Poon, Jeffrey; Batchelor-McAuley, Christopher; Tschulik, Kristina; Palgrave, Robert G.; Compton, Richard G.

2015-01-01

Despite extensive work on the controlled surface modification of carbon with redox moieties, to date almost all available methodologies involve complex chemistry and are prone to the formation of polymerized multi-layer surface structures. Herein, the facile bifunctional redox tagging of carbon nanoparticles (diameter 27 nm) and its characterization is undertaken using the industrial dye Reactive Blue 2. The modification route is demonstrated to be via exceptionally strong physisorption. The modified carbon is found to exhibit both well-defined oxidative and reductive voltammetric redox features which are quantitatively interpreted. The method provides a generic approach to monolayer modifications of carbon and carbon nanoparticle surfaces.

Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char

USGS Publications Warehouse

Lizzio, A.A.; DeBarr, J.A.

1996-01-01

The objective of this study was to determine whether activated char produced from Illinois coal could be used effectively to remove sulfur dioxide from coal combustion flue gas. Chars were prepared from a high-volatile Illinois bituminous coal under a wide range of pyrolysis and activation conditions. A novel char preparation technique was developed to prepare chars with SO2 adsorption capacities significantly greater than that of a commercial activated carbon. In general, there was no correlation between SO2 adsorption capacity and surface area. Temperature-programmed desorption (TPD) was used to determine the nature and extent of carbon-oxygen (C-O) complexes formed on the char surface. TPD data revealed that SO2 adsorption was inversely proportional to the amount of C-O complex. The formation of a stable C-O complex during char preparation may have served only to occupy carbon sites that were otherwise reactive towards SO2 adsorption. A fleeting C(O) complex formed during SO2 adsorption is postulated to be the reaction intermediate necessary for conversion of SO2 to H2SO4. Copyright ?? 1996 Elsevier Science Ltd.

High fluorescence emission of carboxylic acid functionalized polystyrene/BaTiO{sub 3} nanocomposites and rare earth metal complexes: Preparation and characterization

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

Cao, X. T.; Showkat, A. M.; Wang, Z.

2015-03-30

Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb{sup 3+}) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S’-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb{sup 3+} ions afforded fluorescent Tb{sup 3+} tagged aryl carboxylic acid functionalized polystyrenemore » grafted barium titanate (BTO-g-PSt-Tb{sup 3+}) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb{sup 3+}nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb{sup 3+} complexes were investigated by fluorescence spectroscopy.« less

Complexes of silver(I) ions and silver phosphate nanoparticles with hyaluronic acid and/or chitosan as promising antimicrobial agents for vascular grafts.

PubMed

Chudobova, Dagmar; Nejdl, Lukas; Gumulec, Jaromir; Krystofova, Olga; Rodrigo, Miguel Angel Merlos; Kynicky, Jindrich; Ruttkay-Nedecky, Branislav; Kopel, Pavel; Babula, Petr; Adam, Vojtech; Kizek, Rene

2013-06-28

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes.

Complexes of Silver(I) Ions and Silver Phosphate Nanoparticles with Hyaluronic Acid and/or Chitosan as Promising Antimicrobial Agents for Vascular Grafts

PubMed Central

Chudobova, Dagmar; Nejdl, Lukas; Gumulec, Jaromir; Krystofova, Olga; Rodrigo, Miguel Angel Merlos; Kynicky, Jindrich; Ruttkay-Nedecky, Branislav; Kopel, Pavel; Babula, Petr; Adam, Vojtech; Kizek, Rene

2013-01-01

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes. PMID:23812079

Interaction of ribonucleotides with oxide and silicate minerals under varying environmental conditions

NASA Astrophysics Data System (ADS)

Feuillie, C.; Sverjensky, D. A.; Hazen, R. M.

2013-12-01

Large quantities of nucleic acids are found in natural environments, released after the death of an organism and subsequent cell lysis [1]. Nucleic acids are known to adsorb on mineral surfaces [2, 3, 4], which protect them from degradation, whether enzymatic [5, 6] or UV-mediated [7]. It may then contribute to the extracellular genetic pool available in soils to microorganisms for horizontal gene transfers [8]. In order to better understand the behaviour of extracellular nucleic acids in soils, we have investigated the interactions between nucleotides, 5'-GMP, 5'-CMP, 5'-AMP and 5'-UMP, and α-alumina as a model compound for Al in six-fold coordination in soil minerals. We carried out batch adsorption experiments over a wide range of pH, ionic strength and surface loading. Alumina adsorbs high amounts of nucleotides > 2 μmol/m2. In similar environmental conditions, swelling clays such as nontronite and montmorillonite adsorb less than 0.1 μmol/m2 if the total surface area is taken under consideration. However, if only the edges of clay particles are considered, the amount of nucleotides adsorbed reaches values between 1.2 and 2 μmol/m2 [9], similar to the alumina and consistent with ';oxide-like' surface sites on the edges of the clay particles. Surface complexation modeling enabled us to predict the speciation of the surface species on the alumina, as well as the stoichiometry and thermodynamic equilibrium constants for the adsorption of nucleotides. We used the extended triple-layer model (ETLM), that takes into account the electrical work linked to the desorption of chemisorbed water molecules during the formation of inner-sphere complexes. Two surface species are thought to form on the surface of corundum: a monodentate inner-sphere complex, dominant at pH < 7.5, and a bidentate outer-sphere complex, dominant at higher pH. Both complexes involve interactions between the negatively charged phosphate group and the positively charged surface of alumina. Our results provide a better understanding of how nucleic acids attach to mineral surfaces under varying environmental conditions in soil environments. Moreover, the predicted configuration of nucleotide surface species, bound via the phosphate group, could have implications for the abiotic formation and concentration of nucleic acids in the context of the origin of life. References : [1] Lorenz and Wackernagel (1987), Applied and environmental microbial., 2948-2952 [2] Ferris (2005), Reviews in mineralogy & geochemistry 59, 187-210 [3] Cleaves H.J. et al. (2011), Chemosphere 83, 1560-1567 [4] Arora & Kamaluddin (2009), Astrobiology 9, 165-171 [5] Cai et al. (2006), Environ. Sci. Technol. 40 (9), 2971-2976 [6] Franchi and Gallori (2005),Gene 346, 205-214 [7] Scappini et al. (2004), International Journal of Astrobiology 3(1), 17-19 [8] Levy-Booth et al. (2007), Soil Biol. Biochem. 39, 2977-2991. [9] Feuillie et al. (2013), Geochimica et Cosmochimica Acta (in press)

Facile NOx interconversion over preoxidized Ag(111)

NASA Astrophysics Data System (ADS)

Klacar, S.; Martin, N. M.; Gustafson, J.; Blomberg, S.; Liu, Z.; Axnanda, S.; Chang, R.; Lundgren, E.; Grönbeck, H.

2013-11-01

X-ray photoelectron spectroscopy and density functional theory calculations are used to investigate NO adsorption at low (100 K) and room temperature (RT) over preoxidized Ag(111). At 100 K, the data indicates presence of NO and N2O2, with little or no nitrite/nitrate formation. This is consistent with the calculated surface core level shifts and the pronounced barrier for nitrite formation. At RT, the recorded spectra indicate a complex interconversion between adsorbed species with an initial formation of a p(4 × 4) nitrate overlayer. With increasing NO pressure, the experimental results are best rationalized by partial nitrate decomposition into nitrites and subsequent NO physisorption, which leads to the formation of N2O3-like species.

Titan's Complex Chemistry: Insights from the Lab

NASA Astrophysics Data System (ADS)

Horst, Sarah

2018-06-01

The Cassini-Huygens mission revealed Titan to be a complex world with physical processes reminiscent of other terrestrial planets, but chemistry that is unlike anywhere else in the Solar System. Titan's complex atmospheric chemistry converts N2 and CH4 into numerous, abundant organic molecules ranging from relatively simple hydrocarbons to ions with mass to charge ratios up to 10,000 amu/q. The molecules eventually settle to the surface where they can participate in and be modified by geological processes such as aeolian and fluvial erosion or undergo subsequent chemistry in Titan's lakes and seas or impact craters and potential cryovolcanic flows. From the processes leading to massive ion formation in the atmosphere to the behavior of saltating organic sands on the surface, laboratory experiments are playing a pivotal role in understanding Titan and expanding our understanding of planetary processes into new, exciting phase space.

An installed nacelle design code using a multiblock Euler solver. Volume 2: User guide

NASA Technical Reports Server (NTRS)

Chen, H. C.

1992-01-01

This is a user manual for the general multiblock Euler design (GMBEDS) code. The code is for the design of a nacelle installed on a geometrically complex configuration such as a complete airplane with wing/body/nacelle/pylon. It consists of two major building blocks: a design module developed by LaRC using directive iterative surface curvature (DISC); and a general multiblock Euler (GMBE) flow solver. The flow field surrounding a complex configuration is divided into a number of topologically simple blocks to facilitate surface-fitted grid generation and improve flow solution efficiency. This user guide provides input data formats along with examples of input files and a Unix script for program execution in the UNICOS environment.

Formation and Regional to Global Impacts of Severe Haze in China

NASA Astrophysics Data System (ADS)

Zhang, R.

2017-12-01

As the world's second largest economy, China has experienced severe haze pollution, with fine particulate matter (PM) recently reaching unprecedentedly high levels across many cities. An understanding of the PM formation mechanism is critical in the development of efficient mediation policies to minimize its regional to global impacts. The formation mechanisms leading to severe haze episodes with exceedingly high PM2.5 levels in China remain uncertain, and the abundance and chemical constituents of PM2.5 vary considerably, depending on complex interplay between meteorology, pollution sources, and atmospheric chemical processes. In addition, aerosols interact directly and indirectly with the Earth's radiation budget and climate. For the direct effect, aerosols scatter and absorb solar radiation. Light scattering by aerosols changes the radiative fluxes at the top-of-atmosphere (TOA), at the surface, and within the atmospheric column, while aerosol absorption modifies the atmospheric temperature structure, decreases the solar radiation at the surface, and lowers surface sensible and latent fluxes, suppressing convection and reducing cloud fraction. Furthermore, aerosols by serving as cloud condensation nuclei indirectly impact climate by altering cloud development, lifetime, precipitation, and albedo. This talk will discuss the latest progress in understanding of severe haze formation in China and the regional to global impacts of Asian pollution.

Hydration Differences Explain the Large Variations in the Complexation Thermodynamics of Modified γ-Cyclodextrins with Bile Salts.

PubMed

Køhler, Jonatan; Schönbeck, Christian; Westh, Peter; Holm, René

2016-01-28

The structure and thermodynamics of inclusion complexes of seven different γ-cyclodextrins (γCDs) and three biologically relevant bile salts (BS) were investigated in the present study. Natural γCD and six modified γCDs [two methyl-γCDs, one sulfobutyl ether-γCD (SBEγCD), and three 2-hydroxypropyl-γCDs (HPγCD)] and their complexes with BS were investigated by isothermal titration calorimetry, NMR, and molecular dynamics simulations. With the exception of the fully methylated γCD, which did not bind the BSs investigated, all of the γCDs formed 1:1 complexes with the BS, and the structures were similar to those with natural γCD; i.e., the modifications of the γCD had limited structural impact on the formation of complexes. Isothermal titration calorimetry was carried out over in the temperature interval 5-55 °C to enable the calculation of the stability constant (K) and the thermodynamic parameters enthalpy (ΔH°), entropy (ΔS°), and heat capacity (ΔCp°). The stability constants decreased with an increased degree of substitution (DS), with methyl substituents having a lower effect on the stability constant than the sulfobutyl ether and hydroxypropyl substituents on the stability constants. Enthalpy-entropy compensation was observed, since both enthalpy and entropy increased with the degree of substitution, which may reflect dehydration of the hydrophobic surface on both CD and BS. Calculations based on ΔCp° data suggested that each of the substituents dehydrated 10-20 (hydroxypropyl), 22-33 (sulfobutyl ether), and 10-15 Å(2) (methyl) of the BS surface area, in reasonable agreement with estimates from the molecular dynamics simulations. Combined with earlier investigations on modified βCDs, these results indicate general trends of the substituents on the thermodynamics of complex formation.

Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

PubMed

Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P

2013-11-12

In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

Design of a sensor for the blood AB0 group antibodies detection

NASA Astrophysics Data System (ADS)

Kolesov, D. V.; Kiselev, G. A.; Moiseev, M. A.; Kudrinskiy, A. A.; Yaminskiy, I. V.

2012-02-01

Control the content of the blood group antibodies in the plasma of the recipient is an important task in modern transplantation. In this paper we proposed to use micromechanical cantilever sensors for detection of the low concentrations of AB0 blood group antibodies in serum. The technique of chemical modification of cantilever surface to create the receptor layer was developed. The apparatus, which provides data acquisition from multiple microconsoles simultaneously was created. We carried out experiments by the detection in a solution the β antibodies with a concentration of 300 times less than the native content of antibodies in the blood. Change in surface stress due to formation of antigen-antibody complexes on the cantilever surface was 0.075 N/m. The resulting lateral strain, apparently, induced by repulsion between the complexes during the sorption of antibodies in layer of antigens, immobilized on the surface. The possibility of regeneration of sensory layer for repeated measurements was shown.

Structures of Cu surfaces developing in benzotriazole solutions: Effect of pH

NASA Astrophysics Data System (ADS)

Kondoh, Eiichi; Kawakami, Tatsuya; Watanabe, Mitsuhiro; Jin, Linhua; Hamada, Satomi; Shima, Shohei; Hiyama, Hirokuni

2017-07-01

The effect of pH on layer formation onto clean Cu surfaces in benzotriazole (BTA) aqueous solutions was studied by in situ spectroscopic ellipsometry. The effect of H2O2 addition was also investigated. Time changes in the ellipsometric parameters Ψ and Δ, which correspond to the structural changes of the layers on Cu, were discussed. In acidic solutions, a BTA or a Cu-BTA complex layer grows directly on Cu. The out-diffusion of Cu is suppressed at the Cu layer interface. When H2O2 was mixed, the Cu surface is eroded in acidic solutions. In alkaline solutions, the BTA layer grows on the oxidized Cu layer, or no growth occurs, depending on the composition of the solutions. In neutral solutions, the Cu-BTA complex layer forms on Cu, and the uncovered part is oxidized in the presence of H2O2.

Supported metallocene catalysts by surface organometallic chemistry. Synthesis, characterization, and reactivity in ethylene polymerization of oxide-supported mono- and biscyclopentadienyl zirconium alkyl complexes: establishment of structure/reactivity relationships.

PubMed

Jezequel, M; Dufaud, V; Ruiz-Garcia, M J; Carrillo-Hermosilla, F; Neugebauer, U; Niccolai, G P; Lefebvre, F; Bayard, F; Corker, J; Fiddy, S; Evans, J; Broyer, J P; Malinge, J; Basset, J M

2001-04-18

The reactions of CpZr(CH(3))(3), 1, and Cp(2)Zr(CH(3))(2), 2, with partially dehydroxylated silica, silica-alumina, and alumina surfaces have been carried out with careful identification of the resulting surface organometallic complexes in order to probe the relationship between catalyst structure and polymerization activity. The characterization of the supported complexes has been achieved in most cases by in situ infrared spectroscopy, surface microanalysis, qualitative and quantitative analysis of evolved gases during surface reactions with labeled surface, solid state (1)H and (13)C NMR using (13)C-enriched compounds, and EXAFS. 1 and 2 react with silica(500) and silica-alumina(500) by simple protonolysis of one Zr-Me bond by surface silanols with formation of a single well-defined neutral compound. In the case of silica-alumina, a fraction of the supported complexes exhibits some interactions with electronically unsaturated surface aluminum sites. 1 and 2 also react with the hydroxyl groups of gamma-alumina(500), leading to several surface structures. Correlation between EXAFS and (13)C NMR data suggests, in short, two main surface structures having different environments for the methyl group: [Al](3)-OZrCp(CH(3))(2) and [Al](2)-OZrCp(CH(3))(mu-CH(3))-[Al] for the monoCp series and [Al](2)-OZrCp(2)(CH(3)) and [Al]-OZrCp(2)(mu-CH(3))-[Al] for the bisCp series. Ethylene polymerization has been carried out with all the supported complexes under various reaction conditions. Silica-supported catalysts in the absence of any cocatalyst exhibited no activity whatsoever for ethylene polymerization. When the oxide contained Lewis acidic sites, the resulting surface species were active. The activity, although improved by the presence of additional cocatalysts, remained very low by comparison with that of the homogeneous metallocene systems. This trend has been interpreted on the basis of various possible parameters, including the (p-pi)-(d-pi) back-donation of surface oxygen atoms to the zirconium center.

Atomic and polyatomic molecules at metal surfaces studied by synchrotron far-IR RAIRS

NASA Astrophysics Data System (ADS)

Raval, Rasmita; Roberts, Adam J.; Williams, Jamie; Nunney, Timothy S.; Surman, Mark

1997-10-01

Far-IR Reflection Absorption Infrared Spectroscopy (RAIRS) has been used to probe submonolayers of adsorbates created under clean controlled conditions on small area single crystal surfaces, using the newly commissioned Daresbury 13.3 Far-IR synchrotron beamline. Adsorbed formate species on Cu(110) were studied as an example of an adsorbate for which a large structural data-base already exists in the literature from other surface science techniques. Our high resolution Far-IR data has allowed two distinct vCu-O vibrations to be monitored for 0.25 monolayer of formate adsorbed on Cu(110) at 300 K. We rule out a lower symmetry formate complex giving rise to these vibrations and, instead, attribute the two bands to at least two chemically distinct species at the surface, a possibility that has hitherto not been included in the analyses of this system using other techniques. In addition, we also report the first RAIRS spectrum of the vCu-O stretching vibration for adsorbed atomic O on the Cu(110) surface at 300 K. The dissociative adsorption of oxygen, at room temperature, on this surface is known to induce a massive reconstruction of the surface in which `added' rows of Cu-O-Cu strings form on the surface in the [001] direction to give rise to the (1 X 2) missing row structure. The vCu-O vibration frequency is found to be invariant as a function of coverage, suggesting that the chemical nature of the Cu-O-Cu entity remains essentially unaltered during the growth of the reconstructed phase.

Cell-fusion method to visualize interphase nuclear pore formation.

PubMed

Maeshima, Kazuhiro; Funakoshi, Tomoko; Imamoto, Naoko

2014-01-01

In eukaryotic cells, the nucleus is a complex and sophisticated organelle that organizes genomic DNA to support essential cellular functions. The nuclear surface contains many nuclear pore complexes (NPCs), channels for macromolecular transport between the cytoplasm and nucleus. It is well known that the number of NPCs almost doubles during interphase in cycling cells. However, the mechanism of NPC formation is poorly understood, presumably because a practical system for analysis does not exist. The most difficult obstacle in the visualization of interphase NPC formation is that NPCs already exist after nuclear envelope formation, and these existing NPCs interfere with the observation of nascent NPCs. To overcome this obstacle, we developed a novel system using the cell-fusion technique (heterokaryon method), previously also used to analyze the shuttling of macromolecules between the cytoplasm and the nucleus, to visualize the newly synthesized interphase NPCs. In addition, we used a photobleaching approach that validated the cell-fusion method. We recently used these methods to demonstrate the role of cyclin-dependent protein kinases and of Pom121 in interphase NPC formation in cycling human cells. Here, we describe the details of the cell-fusion approach and compare the system with other NPC formation visualization methods. Copyright © 2014 Elsevier Inc. All rights reserved.

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

PubMed Central

2017-01-01

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms. PMID:28885841

The Impact of Alkaliphilic Biofilm Formation on the Release and Retention of Carbon Isotopes from Nuclear Reactor Graphite.

PubMed

Rout, S P; Payne, L; Walker, S; Scott, T; Heard, P; Eccles, H; Bond, G; Shah, P; Bills, P; Jackson, B R; Boxall, S A; Laws, A P; Charles, C; Williams, S J; Humphreys, P N

2018-03-13

14 C is an important consideration within safety assessments for proposed geological disposal facilities for radioactive wastes, since it is capable of re-entering the biosphere through the generation of 14 C bearing gases. The irradiation of graphite moderators in the UK gas-cooled nuclear power stations has led to the generation of a significant volume of 14 C-containing intermediate level wastes. Some of this 14 C is present as a carbonaceous deposit on channel wall surfaces. Within this study, the potential of biofilm growth upon irradiated and 13 C doped graphite at alkaline pH was investigated. Complex biofilms were established on both active and simulant samples. High throughput sequencing showed the biofilms to be dominated by Alcaligenes sp at pH 9.5 and Dietzia sp at pH 11.0. Surface characterisation revealed that the biofilms were limited to growth upon the graphite surface with no penetration of the deeper porosity. Biofilm formation resulted in the generation of a low porosity surface layer without the removal or modification of the surface deposits or the release of the associated 14 C/ 13 C. Our results indicated that biofilm formation upon irradiated graphite is likely to occur at the pH values studied, without any additional release of the associated 14 C.

Modeling the surface tension of complex, reactive organic-inorganic mixtures

NASA Astrophysics Data System (ADS)

Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. Faye

2013-11-01

Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as heterogeneous reactivity, ice nucleation, and cloud droplet formation. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two semi-empirical surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling of aerosol systems because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling results and goodness-of-fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

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.

Bone bonding at natural and biomaterial surfaces.

PubMed

Davies, John E

2007-12-01

Bone bonding is occurring in each of us and all other terrestrial vertebrates throughout life at bony remodeling sites. The surface created by the bone-resorbing osteoclast provides a three-dimensionally complex surface with which the cement line, the first matrix elaborated during de novo bone formation, interdigitates and is interlocked. The structure and composition of this interfacial bony matrix has been conserved during evolution across species; and we have known for over a decade that this interfacial matrix can be recapitulated at a biomaterial surface implanted in bone, given appropriate healing conditions. No evidence has emerged to suggest that bone bonding to artificial materials is any different from this natural biological process. Given this understanding it is now possible to explain why bone-bonding biomaterials are not restricted to the calcium-phosphate-based bioactive materials as was once thought. Indeed, in the absence of surface porosity, calcium phosphate biomaterials are not bone bonding. On the contrary, non-bonding materials can be rendered bone bonding by modifying their surface topography. This paper argues that the driving force for bone bonding is bone formation by contact osteogenesis, but that this has to occur on a sufficiently stable recipient surface which has micron-scale surface topography with undercuts in the sub-micron scale-range.

Surface energetics and protein-protein interactions: analysis and mechanistic implications

PubMed Central

Peri, Claudio; Morra, Giulia; Colombo, Giorgio

2016-01-01

Understanding protein-protein interactions (PPI) at the molecular level is a fundamental task in the design of new drugs, the prediction of protein function and the clarification of the mechanisms of (dis)regulation of biochemical pathways. In this study, we use a novel computational approach to investigate the energetics of aminoacid networks located on the surface of proteins, isolated and in complex with their respective partners. Interestingly, the analysis of individual proteins identifies patches of surface residues that, when mapped on the structure of their respective complexes, reveal regions of residue-pair couplings that extend across the binding interfaces, forming continuous motifs. An enhanced effect is visible across the proteins of the dataset forming larger quaternary assemblies. The method indicates the presence of energetic signatures in the isolated proteins that are retained in the bound form, which we hypothesize to determine binding orientation upon complex formation. We propose our method, BLUEPRINT, as a complement to different approaches ranging from the ab-initio characterization of PPIs, to protein-protein docking algorithms, for the physico-chemical and functional investigation of protein-protein interactions. PMID:27050828

Cryo-electron microscopy study of bacteriophage T4 displaying anthrax toxin proteins

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

Fokine, Andrei; Bowman, Valorie D.; Battisti, Anthony J.

2007-10-25

The bacteriophage T4 capsid contains two accessory surface proteins, the small outer capsid protein (Soc, 870 copies) and the highly antigenic outer capsid protein (Hoc, 155 copies). As these are dispensable for capsid formation, they can be used for displaying proteins and macromolecular complexes on the T4 capsid surface. Anthrax toxin components were attached to the T4 capsid as a fusion protein of the N-terminal domain of the anthrax lethal factor (LFn) with Soc. The LFn-Soc fusion protein was complexed in vitro with Hoc{sup -}Soc{sup -}T4 phage. Subsequently, cleaved anthrax protective antigen heptamers (PA63){sub 7} were attached to the exposedmore » LFn domains. A cryo-electron microscopy study of the decorated T4 particles shows the complex of PA63 heptamers with LFn-Soc on the phage surface. Although the cryo-electron microscopy reconstruction is unable to differentiate on its own between different proposed models of the anthrax toxin, the density is consistent with a model that had predicted the orientation and position of three LFn molecules bound to one PA63 heptamer.« less

Multifrequency acoustics as a probe of mesoscopic blood coagulation dynamics

NASA Astrophysics Data System (ADS)

Ganesan, Adarsh; Rajendran, Gokulnath; Ercole, Ari; Seshia, Ashwin

2016-08-01

Coagulation is a complex enzymatic polymerisation cascade. Disordered coagulation is common in medicine and may be life-threatening yet clinical assays are typically bulky and/or provide an incomplete picture of clot mechanical evolution. We present the adaptation of an in-plane acoustic wave device: quartz crystal microbalance with dissipation at multiple harmonics to determine the time-evolution of mesoscale mechanical properties of clot formation in vitro. This approach is sensitive to changes in surface and bulk clot structure in various models of induced coagulopathy. Furthermore, we are able to show that clot formation at surfaces has different kinetics and mechanical strength to that in the bulk, which may have implications for the design of bioprosthetic materials. The "Multifrequency acoustics" approach thus enables unique capability to portray biological processes concerning blood coagulation.

Precision lens molding of asphero diffractive surfaces in chalcogenide materials

NASA Astrophysics Data System (ADS)

Nelson, J.; Scordato, M.; Schwertz, K.; Bagwell, J.

2015-10-01

Finished lens molding, and the similar process of precision lens molding, have long been practiced for high volume, accurate replication of optical surfaces on oxide glass. The physics surrounding these processes are well understood, and the processes are capable of producing high quality optics with great fidelity. However, several limitations exist due to properties inherent with oxide glasses. Tooling materials that can withstand the severe environmental conditions of oxide glass molding cannot easily be machined to produce complex geometries such as diffractive surfaces, lens arrays, and off axis features. Current machining technologies coupled with a limited selection of tool materials greatly limits the type of structures that can be molded into the finished optic. Tooling for chalcogenide glasses are not bound by these restrictions since the molding temperatures required are much lower than for oxide glasses. Innovations in tooling materials and manufacturing techniques have enabled the production of complex geometries to optical quality specifications and have demonstrated the viability of creating tools for molding diffractive surfaces, off axis features, datums, and arrays. Applications for optics having these features are found in automotive, defense, security, medical, and industrial domains. This paper will discuss results achieved in the study of various molding techniques for the formation of positive diffractive features on a concave spherical surface molded from As2Se3 chalcogenide glass. Examples and results of molding with tools having CTE match with the glass and non CTE match will be reviewed. The formation of stress within the glass during molding will be discussed, and methods of stress management will also be demonstrated and discussed. Results of process development methods and production of good diffractive surfaces will be shown.

Non-water-ice constituents in the surface material of the icy Galilean satellites from the Galileo near-infrared mapping spectrometer investigation

USGS Publications Warehouse

McCord, T.B.; Hansen, G.B.; Clark, R.N.; Martin, P.D.; Hibbitts, C.A.; Fanale, F.P.; Granahan, J.C.; Segura, M.; Matson, D.L.; Johnson, T.V.; Carlson, R.W.; Smythe, W.D.; Danielson, G.E.

1998-01-01

We present evidence for several non-ice constituents in the surface material of the icy Galilean satellites, using the reflectance spectra returned by the Galileo near infrared mapping spectrometer (NIMS) experiment. Five new absorption features are described at 3.4, 3.88, 4.05, 4.25, and 4.57 ??m for Callisto and Ganymede, and some seem to exist for Europa as well. The four absorption bands strong enough to be mapped on Callisto and Ganymede are each spatially distributed in different ways, indicating different materials are responsible for each absorption. The spatial distributions are correlated at the local level in complex ways with surface features and in some cases show global patterns. Suggested candidate spectrally active groups, perhaps within larger molecules, producing the five absorptions include C-H, S-H, SO2, CO2, and C???N. Organic material like tholins are candidates for the 4.57- and 3.4-??m features. We suggest, based on spectroscopic evidence, that CO2 is present as a form which does not allow rotational modes and that SO2 is present neither as a frost nor a free gas. The CO2, SO2, and perhaps cyanogen (4.57 ??m) may be present as very small collections of molecules within the crystal structure, perhaps following models for radiation damage and/or for comet and interstellar grain formation at low temperatures. Some of the dark material on these surfaces may be created by radiation damage of the CO2 and other carbon-bearing species and the formation of graphite. These spectra suggest a complex chemistry within the surface materials and an important role for non-ice materials in the evolution of the satellite surfaces. Copyright 1998 by the American Geophysical Union.

Sastrugi Geometrical Properties and Morphometry Over Two Winter Seasons at col du Lac Blanc (french Alps, 2700 m a.s.l)

NASA Astrophysics Data System (ADS)

Naaim, Florence; Picard, Ghislain; Bellot, Hervé; Arnaud, Laurent; Vionnet, Vincent

2017-04-01

Some elements of snow surface roughness, such as ripple or sastrugi, are a direct manifestation of wind erosion and in turn modify the near-surface wind field and consequently the horizontal snow mass fluxes. This leads to a negative feedback between wind strength and surface roughness that must be taken into account in numerical models. Formation of sastrugi, which are elongated metric-scale ridges of wind-packed snow whose longitudinal axis is parallel to the prevailing wind at the time of their formation, is still not well-understood. The first step to provide new information about the formation and evolution of such features is to integrate meteorological data and accurate description of geometrical properties. But the complex and dynamic surface of sastrugi cannot be easily captured by manual measurements (Bellot et al., 2014), which furthermore must be frequent as the formation of new landforms can happen very quickly. That's why the potential of a low-cost time-lapse terrestrial laserscan RLS (Picard et al., 2016) has been investigated during the winter seasons 2015-2016 and 2016-2017 at Col du Lac Blanc in the French Alps. This experimental test site, dedicated to drifting snow studies, and subject to the formation of sastrugi is well-suited for such study : accurate meteorological data, including drifting snow fluxes, are available each 10 minutes. RLS covered a surface area of around 200 m2 for a spatial horizontal resolution of nearly 2 cm and monitored successfully surface roughness once a day during the whole winter seasons. Sastrugi geometrical parameters, such as the frontal area and average height of roughness elements has been extracted from the RLS data and the sastrugi morphometry has be examined over two winter seasons in link with snow fall, drifting snow occurence and intensity and wind speed.

BIOPHYSICAL PROPERTIES OF NUCLEIC ACIDS AT SURFACES RELEVANT TO MICROARRAY PERFORMANCE.

PubMed

Rao, Archana N; Grainger, David W

2014-04-01

Both clinical and analytical metrics produced by microarray-based assay technology have recognized problems in reproducibility, reliability and analytical sensitivity. These issues are often attributed to poor understanding and control of nucleic acid behaviors and properties at solid-liquid interfaces. Nucleic acid hybridization, central to DNA and RNA microarray formats, depends on the properties and behaviors of single strand (ss) nucleic acids (e.g., probe oligomeric DNA) bound to surfaces. ssDNA's persistence length, radius of gyration, electrostatics, conformations on different surfaces and under various assay conditions, its chain flexibility and curvature, charging effects in ionic solutions, and fluorescent labeling all influence its physical chemistry and hybridization under assay conditions. Nucleic acid (e.g., both RNA and DNA) target interactions with immobilized ssDNA strands are highly impacted by these biophysical states. Furthermore, the kinetics, thermodynamics, and enthalpic and entropic contributions to DNA hybridization reflect global probe/target structures and interaction dynamics. Here we review several biophysical issues relevant to oligomeric nucleic acid molecular behaviors at surfaces and their influences on duplex formation that influence microarray assay performance. Correlation of biophysical aspects of single and double-stranded nucleic acids with their complexes in bulk solution is common. Such analysis at surfaces is not commonly reported, despite its importance to microarray assays. We seek to provide further insight into nucleic acid-surface challenges facing microarray diagnostic formats that have hindered their clinical adoption and compromise their research quality and value as genomics tools.

BIOPHYSICAL PROPERTIES OF NUCLEIC ACIDS AT SURFACES RELEVANT TO MICROARRAY PERFORMANCE

PubMed Central

Rao, Archana N.; Grainger, David W.

2014-01-01

Both clinical and analytical metrics produced by microarray-based assay technology have recognized problems in reproducibility, reliability and analytical sensitivity. These issues are often attributed to poor understanding and control of nucleic acid behaviors and properties at solid-liquid interfaces. Nucleic acid hybridization, central to DNA and RNA microarray formats, depends on the properties and behaviors of single strand (ss) nucleic acids (e.g., probe oligomeric DNA) bound to surfaces. ssDNA’s persistence length, radius of gyration, electrostatics, conformations on different surfaces and under various assay conditions, its chain flexibility and curvature, charging effects in ionic solutions, and fluorescent labeling all influence its physical chemistry and hybridization under assay conditions. Nucleic acid (e.g., both RNA and DNA) target interactions with immobilized ssDNA strands are highly impacted by these biophysical states. Furthermore, the kinetics, thermodynamics, and enthalpic and entropic contributions to DNA hybridization reflect global probe/target structures and interaction dynamics. Here we review several biophysical issues relevant to oligomeric nucleic acid molecular behaviors at surfaces and their influences on duplex formation that influence microarray assay performance. Correlation of biophysical aspects of single and double-stranded nucleic acids with their complexes in bulk solution is common. Such analysis at surfaces is not commonly reported, despite its importance to microarray assays. We seek to provide further insight into nucleic acid-surface challenges facing microarray diagnostic formats that have hindered their clinical adoption and compromise their research quality and value as genomics tools. PMID:24765522

Myosin 7 and its adaptors link cadherins to actin

PubMed Central

Yu, I-Mei; Planelles-Herrero, Vicente J.; Sourigues, Yannick; Moussaoui, Dihia; Sirkia, Helena; Kikuti, Carlos; Stroebel, David; Titus, Margaret A.; Houdusse, Anne

2017-01-01

Cadherin linkages between adjacent stereocilia and microvilli are essential for mechanotransduction and maintaining their organization. They are anchored to actin through interaction of their cytoplasmic domains with related tripartite complexes consisting of a class VII myosin and adaptor proteins: Myo7a/SANS/Harmonin in stereocilia and Myo7b/ANKS4B/Harmonin in microvilli. Here, we determine high-resolution structures of Myo7a and Myo7b C-terminal MyTH4-FERM domain (MF2) and unveil how they recognize harmonin using a novel binding mode. Systematic definition of interactions between domains of the tripartite complex elucidates how the complex assembles and prevents possible self-association of harmonin-a. Several Myo7a deafness mutants that map to the surface of MF2 disrupt harmonin binding, revealing the molecular basis for how they impact the formation of the tripartite complex and disrupt mechanotransduction. Our results also suggest how switching between different harmonin isoforms can regulate the formation of networks with Myo7a motors and coordinate force sensing in stereocilia. PMID:28660889

Effect of humic acid preloading on phosphate adsorption onto zirconium-modified zeolite.

PubMed

Lin, Jianwei; Zhang, Zhe; Zhan, Yanhui

2017-05-01

A zirconium-modified zeolite (ZrMZ) was prepared, and then, humic acid (HA) was immobilized on the ZrMZ surface to prepare HA-loaded ZrMZ (HA-ZrMZ). The obtained ZrMZ and HA-ZrMZ were characterized by energy dispersive X-ray spectroscopy, elemental analyzer, N 2 adsorption/desorption isotherms, pH at the point of zero charge, and X-ray photoelectron spectroscopy. The adsorption characteristics of phosphate on ZrMZ and HA-ZrMZ were comparatively investigated in batch mode. The adsorption mechanism of phosphate on ZrMZ and HA-ZrMZ was investigated by ionic strength effect and 31 P nuclear magnetic resonance. The mechanism for phosphate adsorption onto ZrMZ was the formation of inner-sphere phosphate complexes at the solid/solution interface. The preloading of HA on ZrMZ reduced the phosphate adsorption capacity, and the more the HA loading amount, the lower the phosphate adsorption capacity. However, the preloading of HA on ZrMZ did not change the phosphate adsorption mechanism; i.e., the formation of inner-sphere phosphate surface complexes was still responsible for the adsorption of phosphate on HA-ZrMZ. The decreased phosphate adsorption capacity for ZrMZ after HA coating could be attributed to the fact that the coating of HA on ZrMZ reduced the amount of binding active sites available for phosphate adsorption, changed the adsorbent surface charges, and reduced the specific surface areas and pore volumes of ZrMZ.

Poly(amido)amine (PAMAM) dendrimer-cisplatin complexes for chemotherapy of cisplatin-resistant ovarian cancer cells

NASA Astrophysics Data System (ADS)

Yellepeddi, Venkata Kashyap; Vangara, Kiran Kumar; Palakurthi, Srinath

2013-09-01

Dendrimer-cisplatin complexes were prepared using PAMAM dendrimers with terminal -NH2 and -COOH groups as well as biotin-conjugated dendrimers. Preformulation parameters of dendrimer-cisplatin complexes were studied using differential scanning calorimetry (DSC) and inductively coupled plasma-mass spectrometry (ICP-MS). Cytotoxicity and mechanism of cytotoxicity of dendrimer-cisplatin complexes was investigated in OVCAR-3, SKOV, A2780 and cisplatin-resistant CP70 human ovarian cancer cell lines. The loading of cisplatin in dendrimers was 11 % (w/w). PAMAM G4 dendrimers with amine surface groups (biotinylated and native) have shown 2.5- to 3.0-fold reduction in IC50 values in ovarian cancer cells when compared with carboxylate surface dendrimers ( p < 0.05). A correlation was observed among cytotoxicity of the complexes, cellular uptake, and platinum-DNA adduct formation. Treatment with dendrimer-cisplatin complexes resulted in a 7.0-fold increase ( p < 0.05) in expression of apoptotic genes ( Bcl2, Bax, p53) and 13.2- to 27.1-fold increase ( p < 0.05) in the activity of caspases 3, 8, and 9 in vitro. Results suggest that PAMAM dendrimers can be used as potential carrier for cisplatin chemotherapy of ovarian cancer.

Nanostructured PdO Thin Film from Langmuir-Blodgett Precursor for Room-Temperature H2 Gas Sensing.

PubMed

Choudhury, Sipra; Betty, C A; Bhattacharyya, Kaustava; Saxena, Vibha; Bhattacharya, Debarati

2016-07-06

Nanoparticulate thin films of PdO were prepared using the Langmuir-Blodgett (LB) technique by thermal decomposition of a multilayer film of octadecylamine (ODA)-chloropalladate complex. The stable complex formation of ODA with chloropalladate ions (present in subphase) at the air-water interface was confirmed by the surface pressure-area isotherm and Brewster angle microscopy. The formation of nanocrystalline PdO thin film after thermal decomposition of as-deposited LB film was confirmed by X-ray diffraction and Raman spectroscopy. Nanocrystalline PdO thin films were further characterized by using UV-vis and X-ray photoelectron spectroscopic (XPS) measurements. The XPS study revealed the presence of prominent Pd(2+) with a small quantity (18%) of reduced PdO (Pd(0)) in nanocrystalline PdO thin film. From the absorption spectroscopic measurement, the band gap energy of PdO was estimated to be 2 eV, which was very close to that obtained from specular reflectance measurements. Surface morphology studies of these films using atomic force microscopy and field-emission scanning electron microscopy indicated formation of nanoparticles of size 20-30 nm. These PdO film when employed as a chemiresistive sensor showed H2 sensitivity in the range of 30-4000 ppm at room temperature. In addition, PdO films showed photosensitivity with increase in current upon shining of visible light.

The low salinity effect at high temperatures

DOE PAGES

Xie, Quan; Brady, Patrick V.; Pooryousefy, Ehsan; ...

2017-04-05

The mechanism(s) of low salinity water flooding (LSWF) must be better understood at high temperatures and pressures if the method is to be applied in high T/P kaolinite-bearing sandstone reservoirs. We measured contact angles between a sandstone and an oil (acid number, AN = 3.98 mg KOH/g, base number, BN = 1.3 mg KOH/g) from a reservoir in the Tarim Field in western China in the presence of various water chemistries. We examined the effect of aqueous ionic solutions (formation brine, 100X diluted formation brine, and softened water), temperature (60, 100 and 140 °C) and pressure (20, 30, 40, andmore » 50 MPa) on the contact angle. We also measured the zeta potential of the oil/water and water/rock interfaces to calculate oil/brine/rock disjoining pressures. A surface complexation model was developed to interpret contact angle measurements and compared with DLVO theory predictions. Contact angles were greatest in formation water, followed by the softened water, and low salinity water at the same pressure and temperature. Contact angles increased slightly with temperature, whereas pressure had little effect. DLVO and surface complexation modelling predicted similar wettability trends and allow reasonably accurate interpretation of core-flood results. Water chemistry has a much larger impact on LSWF than reservoir temperature and pressure. As a result, low salinity water flooding should work in high temperature and high pressure kaolinite-bearing sandstone reservoirs.« less

The low salinity effect at high temperatures

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

Xie, Quan; Brady, Patrick V.; Pooryousefy, Ehsan

The mechanism(s) of low salinity water flooding (LSWF) must be better understood at high temperatures and pressures if the method is to be applied in high T/P kaolinite-bearing sandstone reservoirs. We measured contact angles between a sandstone and an oil (acid number, AN = 3.98 mg KOH/g, base number, BN = 1.3 mg KOH/g) from a reservoir in the Tarim Field in western China in the presence of various water chemistries. We examined the effect of aqueous ionic solutions (formation brine, 100X diluted formation brine, and softened water), temperature (60, 100 and 140 °C) and pressure (20, 30, 40, andmore » 50 MPa) on the contact angle. We also measured the zeta potential of the oil/water and water/rock interfaces to calculate oil/brine/rock disjoining pressures. A surface complexation model was developed to interpret contact angle measurements and compared with DLVO theory predictions. Contact angles were greatest in formation water, followed by the softened water, and low salinity water at the same pressure and temperature. Contact angles increased slightly with temperature, whereas pressure had little effect. DLVO and surface complexation modelling predicted similar wettability trends and allow reasonably accurate interpretation of core-flood results. Water chemistry has a much larger impact on LSWF than reservoir temperature and pressure. As a result, low salinity water flooding should work in high temperature and high pressure kaolinite-bearing sandstone reservoirs.« less

ROUND TRIP FROM SPACE

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

Calvin, Melvin

1958-10-29

Whence came life on the surface of the earth? Whether or not a complete answer to this question may be found within the context, and content, of modern science, may be a moot question. It is our purpose to see how far we can devise an answer, and how satisfactory it may be, within that context. We trace a path from the primitive molecules of the primeval earth's atmosphere condensed from space through the random formation of more or less complex organic molecules, using the available energy sources of ultraviolet light, ionizing radiation or atmospheric electrical discharge, through the selectivemore » formation of complex organic molecules via autocatalysis, finally, to the informatiion-transmitting molecule which is capable of self-reproduction and variation. In addition, somewhere, either during the course of this Chemical Evolution, or perhaps succeeding it, a system has been evolved in which the concentration of the reaction materials was retained in a relatively small volume of space, leading to the formation of cellular structures. Man is about to send back into space some bits of the dust from whence it originally came, It is thus not only timely but more significant than ever before to ask again the question: What are the probabilities that cellular life as we know it may exist at other sites in the universe than the surface of the earth?« less

Estimation of equilibrium surface precipitation constants for trivalent metal sorption onto hydrous ferric oxide and calcite

NASA Astrophysics Data System (ADS)

Ragavan, Anpalaki J.; Adams, Dean V.

2009-06-01

Equilibrium constants for modeling surface precipitation of trivalent metal cations ( M) onto hydrous ferric oxide and calcite were estimated from linear correlations of standard state Gibbs free energies of formation, ( ΔGf,MvX(ss)0) of the surface precipitates. The surface precipitation reactions were derived from Farley et. al. [K.J. Farley, D.A. Dzombak, F.M.M. Morel, J. Colloid Interface Sci. 106 (1985) 226] surface precipitation model, which are based on surface complexation model coupled with solid solution representation for surface precipitation on the solid surface. The ΔGf,MvX(ss)0 values were correlated through the following linear free energy relations ΔGf,M(OH)3(ss)0-791.70r=0.1587ΔGn,M0-1273.07 and ΔGf,M2(CO3)3(ss)0-197.241r=0.278ΔGn,M0-1431.27 where 'ss' stands for the end-member solid component of surface precipitate, ΔGf,MvX(ss)0 is in kJ/mol, r is the Shannon-Prewitt radius of M in a given coordination state (nm), and ΔGn,M0 is the non-solvation contribution to the Gibbs free energy of formation of the aqueous M ion. Results indicate that the above surface precipitation correlations are useful tools where experimental data are not available.

Risk evaluation of uranium mining: A geochemical inverse modelling approach

NASA Astrophysics Data System (ADS)

Rillard, J.; Zuddas, P.; Scislewski, A.

2011-12-01

It is well known that uranium extraction operations can increase risks linked to radiation exposure. The toxicity of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. In areas where U mining is planned, a careful assessment of toxic and radioactive element concentrations is recommended before the start of mining activities. A background evaluation of harmful elements is important in order to prevent and/or quantify future water contamination resulting from possible migration of toxic metals coming from ore and waste water interaction. Controlled leaching experiments were carried out to investigate processes of ore and waste (leached ore) degradation, using samples from the uranium exploitation site located in Caetité-Bahia, Brazil. In experiments in which the reaction of waste with water was tested, we found that the water had low pH and high levels of sulphates and aluminium. On the other hand, in experiments in which ore was tested, the water had a chemical composition comparable to natural water found in the region of Caetité. On the basis of our experiments, we suggest that waste resulting from sulphuric acid treatment can induce acidification and salinization of surface and ground water. For this reason proper storage of waste is imperative. As a tool to evaluate the risks, a geochemical inverse modelling approach was developed to estimate the water-mineral interaction involving the presence of toxic elements. We used a method earlier described by Scislewski and Zuddas 2010 (Geochim. Cosmochim. Acta 74, 6996-7007) in which the reactive surface area of mineral dissolution can be estimated. We found that the reactive surface area of rock parent minerals is not constant during time but varies according to several orders of magnitude in only two months of interaction. We propose that parent mineral heterogeneity and particularly, neogenic phase formation may explain the observed variation of the reactive mineral surface area. The formation of coatings on dissolving mineral surfaces significantly reduces the amount of surface available to react with fluids. Our results show that negatively charged ion complexes, responsible for U transport, decreases when alkalinity and rock buffer capacity is similarly lower. Carbonate ion pairs however, may increase U mobility when radionuclide concentration is high and rock buffer capacity is low. The present work helps to orient future monitoring of this site in Brazil as well as of other sites where uranium is linked to igneous rock formations, without the presence of sulphides. Monitoring SO4 migration (in acidic leaching uranium sites) seems to be an efficient and simple way to track different hazards, especially in tropical conditions, where the succession of dry and wet periods increases the weathering action of the residual H2SO4. Nevertheless, models of risk evaluation should take into account reactive surface areas and neogenic minerals since they determine the U ion complex formation, which in turn, controls uranium mobility in natural systems. Keywords: uranium mining, reactive mineral surface area, uranium complexes, inverse modelling approach, risk evaluation

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species.

PubMed

Brites, Vincent; Cimas, Alvaro; Spezia, Riccardo; Sieffert, Nicolas; Lisy, James M; Gaigeot, Marie-Pierre

2015-03-10

Combined theoretical DFT-MD and RRKM methodologies and experimental spectroscopic infrared predissociation (IRPD) strategies to map potential energy surfaces (PES) of complex ionic clusters are presented, providing lowest and high energy conformers, thresholds to isomerization, and cluster formation pathways. We believe this association not only represents a significant advance in the field of mapping minima and transition states on the PES but also directly measures dynamical pathways for the formation of structural conformers and isomers. Pathways are unraveled over picosecond (DFT-MD) and microsecond (RRKM) time scales while changing the amount of internal energy is experimentally achieved by changing the loss channel for the IRPD measurements, thus directly probing different kinetic and isomerization pathways. Demonstration is provided for Li(+)(H2O)3,4 ionic clusters. Nonstatistical formation of these ionic clusters by both direct and cascade processes, involving isomerization processes that can lead to trapping of high energy conformers along the paths due to evaporative cooling, has been unraveled.

Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

PubMed

Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

2014-05-01

Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Complex formation between the protein components of methane monooxygenase from Methylosinus trichosporium OB3b. Identification of sites of component interaction.

PubMed

Fox, B G; Liu, Y; Dege, J E; Lipscomb, J D

1991-01-05

Kinetic, spectroscopic, and chemical evidence for the formation of specific catalytically essential complexes between the three protein components of the soluble form of methane monooxygenase from Methylosinus trichosporium OB3b is reported. The effects of the concentrations of the reductase and component B on the hydroxylation activity of the reconstituted enzyme system has been numerically simulated based on a kinetic model which assumes formation of multiple high affinity complexes with the hydroxylase component during catalysis. The formation of several of these complexes has been directly demonstrated. By using EPR spectroscopy, the binding of approximately 2 mol of component B/mol of hydroxylase (subunit structure (alpha beta gamma)2) is shown to significantly change the electronic environment of the mu-(H/R)-oxo-bridged binuclear iron cluster of the hydroxylase in both the mixed valent (Fe(II).Fe(III)) and fully reduced (Fe(II).Fe(II)) states. Protein-protein complexes between the reductase and component B as well as between the reductase and hydroxylase have been shown to form by monitoring quenching of the tryptophan fluorescence spectrum of either the component B (KD approximately 0.4 microM) or hydroxylase (two binding sites, KDa approximately 10 nM, KDb approximately 8 microM). The observed KD values are in agreement with the best fit values from the kinetic simulation. Through the use of the covalent zero length cross-linking reagent 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC), the binding sites of the component B and reductase were shown to be on the hydroxylase alpha and beta subunits, respectively. The alpha and beta subunits of the hydroxylase are cross-linked by EDC suggesting that they are juxtaposed. EDC also caused the rapid loss of the ability of the monomeric component B to stimulate the hydroxylation reaction suggesting that cross-linking of reactive groups on the protein surface had occurred. This effect was inhibited by the presence of hydroxylase and was accompanied by a loss of the ability of the component B to bind to the hydroxylase. Thus, formation of a component B-hydroxylase complex is apparently required for effective catalysis linked to NADH oxidation. When present in concentrations greater than required to saturate the initial hydroxylase complex, component B inhibited both the rate of the enzymic reaction and the cross-linking of the reductase to the hydroxylase. This suggests that a second complex involving component B can form that negatively regulates catalysis by preventing formation of the reductase-hydroxylase complex.

Computational study of pristine and titanium-doped sodium alanates for hydrogen storage applications

NASA Astrophysics Data System (ADS)

Dathar, Gopi Krishna Phani

The emphasis of this research is to study and elucidate the underlying mechanisms of reversible hydrogen storage in pristine and Ti-doped sodium aluminum hydrides using molecular modeling techniques. An early breakthrough in using complex metal hydrides as hydrogen storage materials is from the research on sodium alanates by Bogdanovic et al., in 1997 reporting reversible hydrogen storage is possible at moderate temperatures and pressures in transition metal doped sodium alanates. Anton reported titanium salts as the best catalysts compared to all other transition metal salts from his further research on transition metal doped sodium alanates. However, a few questions remained unanswered regarding the role of Ti in reversible hydrogen storage of sodium alanates with improved thermodynamics and kinetics of hydrogen desorption. The first question is about the position of transition metal dopants in the sodium aluminum hydride lattice. The position is investigated by identifying the possible sites for titanium dopants in NaAlH4 lattice and studying the structure and dynamics of possible compounds resulting from titanium doping in sodium alanates. The second question is the role of titanium dopants in improved thermodynamics of hydrogen desorption in Ti-doped NaAlH4. Though it is accepted in the literature that formation of TiAl alloys (Ti-Al and TiAl3) is favorable, reaction pathways are not clearly established. Furthermore, the source of aluminum for Ti-Al alloy formation is not clearly understood. The third question in this area is the role of titanium dopants in improved kinetics of hydrogen absorption and desorption in Ti-doped sodium alanates. This study is directed towards addressing the three longstanding questions in this area. Thermodynamic and kinetic pathways for hydrogen desorption in pristine NaAlH4 and formation of Ti-Al alloys in Ti-doped NaAlH 4, are elucidated to understand the underlying mechanisms of hydrogen desorption. Density functional theory formalism as implemented in CASTEP (Cambridge Serial Total Energy Package) is used to study the structure and energetics of pristine and Ti-doped sodium alanates. From investigations of various models of sodium alanates with Ti dopants, it is shown that the difference between the energy required for Ti→SNa (Ti-substituted Na at the lattice site on the surface) and Ti→TI (Ti placed on top of the surface interstitial SI site) is 0.003 eV atom-1, and is minimal compared to other models. Since less energy is required for Ti→S Na and Ti→TI, these two sites (SNa and T I) would be preferred by the Ti dopants. In Ti→SNa model, Ti is coordinated to two aluminum and seven hydrogen atoms resulting in the possible formation of a TiAl2H7 complex. At elevated temperatures (423 and 448 K), the number of aluminum atoms coordinating with titanium in the complex increase from two (at distances in the 2.6-2.7 A range) to five (at distances in the 2.6-2.7 A range). Besides the formation of a Ti-Al-H complex, Al-Al association (with a 2.97 A bond length) is also seen from the DFT-MD results. In the case of Ti→TI, Ti is coordinated to two aluminum and two hydrogen atoms resulting in the possible formation of a TiAl2H2 complex. TiAl2 H2 complex becomes TiAl3H6 and TiAl 3H7 at elevated temperatures of 423 and 448 K, respectively. The investigation of thermodynamics pathways in Ti-doped sodium alanates illustrates a three step reaction pathway to the formation of TiAl3 (Ti and AlH3 after the first reaction, TiAl after the second and finally TiAl3). This investigation also suggests aluminum in its +3 oxidation state present in aluminum hydride species is responsible in the formation of Ti-Al alloys. From kinetics studies, the proposed mechanism is related to transition from AlH4- to AlH6 3-. The rate limiting step is determined to be associated with hydrogen evolution from association of AlH3 species nucleating aluminum phase. This step is 15 kJ/mol higher than the nearest highest barrier in the reaction path related to transition from AlH52- to AlH63-. From the DFT-MD simulations, it is observed that the titanium dopants are present on the surface during the entire simulation time and exhibit the role in catalytic splitting of hydrogen from surrounding AlH4 groups. Besides the catalytic role, Ti dopants also form bonds with Al, and we also see that the AlH4 groups on the surface and that are present in the sub-surface layers are drawn towards the Ti dopants. This association of Al around titanium indicates the initiation of Al nucleation site facilitated by Ti dopants residing on the surface.

Biofilm formation in geometries with different surface curvature and oxygen availability

NASA Astrophysics Data System (ADS)

Chang, Ya-Wen; Fragkopoulos, Alexandros A.; Marquez, Samantha M.; Kim, Harold D.; Angelini, Thomas E.; Fernández-Nieves, Alberto

2015-03-01

Bacteria in the natural environment exist as interface-associated colonies known as biofilms . Complex mechanisms are often involved in biofilm formation and development. Despite the understanding of the molecular mechanisms involved in biofilm formation, it remains unclear how physical effects in standing cultures influence biofilm development. The topology of the solid interface has been suggested as one of the physical cues influencing bacteria-surface interactions and biofilm development. Using the model organism Bacillus subtilis, we study the transformation of swimming bacteria in liquid culture into robust biofilms in a range of confinement geometries (planar, spherical and toroidal) and interfaces (air/water, silicone/water, and silicone elastomer/water). We find that B. subtilis form submerged biofilms at both solid and liquid interfaces in addition to air-water pellicles. When confined, bacteria grow on curved surfaces of both positive and negative Gaussian curvature. However, the confinement geometry does affect the resulting biofilm roughness and relative coverage. We also find that the biofilm location is governed by oxygen availability as well as by gravitational effects; these compete with each other in some situations. Overall, our results demonstrate that confinement geometry is an effective way to control oxygen availability and subsequently biofilm growth.

NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

DOEpatents

Balmer-Millar, Mari Lou [Chillicothe, IL; Park, Paul W [Peoria, IL; Panov, Alexander G [Peoria, IL

2007-06-26

The activity and durability of a zeolite lean-burn NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

DOEpatents

Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

2006-08-22

The activity and durability of a zeolite lean-bum NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

Mechanism for chelated sulfate formation from SO2 and bis (triphenylphosphine) platinum

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

Structure and energy surface calculations using the atom superposition and electron delocalization molecular orbital theory show that the first step in the reaction between SO2 and the dioxygen complex (PPh3)2PtO2 is the coordination of SO2 with one oxygen atom of the complex, followed by metal-oxygen bond breaking and reorientation, leading to a five-membered cyclic structure. This then rearranges to form the bidentate coordinated sulfate. Alternative pathways are considered and are found to be less favorable.

The crystal structure of DR6 in complex with the amyloid precursor protein provides insight into death receptor activation

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

Xu, Kai; Olsen, Olav; Tzvetkova-Robev, Dorothea

The amyloid precursor protein (APP) has garnered considerable attention due to its genetic links to Alzheimer's disease. Death receptor 6 (DR6) was recently shown to bind APP via the protein extracellular regions, stimulate axonal pruning, and inhibit synapse formation. Here, we report the crystal structure of the DR6 ectodomain in complex with the E2 domain of APP and show that it supports a model for APP-induced dimerization and activation of cell surface DR6.

The crystal structure of DR6 in complex with the amyloid precursor protein provides insight into death receptor activation

DOE PAGES

Xu, Kai; Olsen, Olav; Tzvetkova-Robev, Dorothea; ...

2015-04-02

The amyloid precursor protein (APP) has garnered considerable attention due to its genetic links to Alzheimer's disease. Death receptor 6 (DR6) was recently shown to bind APP via the protein extracellular regions, stimulate axonal pruning, and inhibit synapse formation. Here, we report the crystal structure of the DR6 ectodomain in complex with the E2 domain of APP and show that it supports a model for APP-induced dimerization and activation of cell surface DR6.

Management of laser welding based on analysis informative signals

NASA Astrophysics Data System (ADS)

Zvezdin, V. V.; Rakhimov, R. R.; Saubanov, Ruz R.; Israfilov, I. H.; Akhtiamov, R. F.

2017-09-01

Features of formation precision weld of metal were presented. It has been shown that the quality of the welding process depends not only on the energy characteristics of the laser processing facility, the temperature of the surface layer, but also on the accuracy of positioning laser focus relative to seam and the workpiece surface. So the laser focus positioning accuracy is an estimate of the quality of the welding process. This approach allows to build a system automated control of the laser technological complex with the stabilization of the setpoint accuracy of of positioning of the laser beam relative to the workpiece surface.

Mechanical intermixing of components in (CoMoNi)-based systems and the formation of (CoMoNi)/WC nanocomposite layers on Ti sheets under ball collisions

NASA Astrophysics Data System (ADS)

Romankov, S.; Park, Y. C.; Shchetinin, I. V.

2017-11-01

Cobalt (Co), molybdenum (Mo), and nickel (Ni) components were simultaneously introduced onto titanium (Ti) surfaces from a composed target using ball collisions. Tungsten carbide (WC) balls were selected for processing as the source of a cemented carbide reinforcement phase. During processing, ball collisions continuously introduced components from the target and the grinding media onto the Ti surface and induced mechanical intermixing of the elements, resulting in formation of a complex nanocomposite structure onto the Ti surface. The as-fabricated microstructure consisted of uniformly dispersed WC particles embedded within an integrated metallic matrix composed of an amorphous phase with nanocrystalline grains. The phase composition of the alloyed layers, atomic reactions, and the matrix grain sizes depended on the combination of components introduced onto the Ti surface during milling. The as-fabricated layer exhibited a very high hardness compared to industrial metallic alloys and tool steel materials. This approach could be used for the manufacture of both cemented carbides and amorphous matrix composite layers.

Growth and structural evolution of Sn on Ag(001): Epitaxial monolayer to thick alloy film

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

Chakraborty, Suvankar; Menon, Krishnakumar S. R., E-mail: krishna.menon@saha.ac.in

The growth and structure of Sn on Ag(001), from submonolayer to thick film coverages at room temperature, are studied using low energy electron diffraction, x-ray photoemission spectroscopy and angle-resolved photoemission spectroscopy (ARPES) techniques. The authors observe different growth modes for submonolayer Sn coverages and for higher Sn coverages. Systematic surface structural evolution, consistent with the substitution of surface Ag atoms by Sn atoms, is observed for submonolayer Sn coverages while an ordered Ag-Sn bulk alloy film is formed for higher Sn coverages with an Ag overlayer. For monolayer coverage of Sn, a pseudomorphic growth of a Sn layer without alloyingmore » is determined. ARPES results also confirm the presence of an ordered Ag overlayer on the bulk Ag-Sn alloy film, suggesting the formation of an Ag/Ag{sub 3}Sn/Ag(001) sandwich structure at the surface for higher Sn coverages. The present results illustrate the complex interplay of atomic mobilities, surface free-energies, and alloy formation energies in determining the growth and structural properties of the system.« less

Evaluation of Cu(i) binding to the E2 domain of the amyloid precursor protein - a lesson in quantification of metal binding to proteins via ligand competition.

PubMed

Young, Tessa R; Wedd, Anthony G; Xiao, Zhiguang

2018-01-24

The extracellular domain E2 of the amyloid precursor protein (APP) features a His-rich metal-binding site (denoted as the M1 site). In conjunction with surrounding basic residues, the site participates in interactions with components of the extracellular matrix including heparins, a class of negatively charged polysaccharide molecules of varying length. This work studied the chemistry of Cu(i) binding to APP E2 with the probe ligands Bcs, Bca, Fz and Fs. APP E2 forms a stable Cu(i)-mediated ternary complex with each of these anionic ligands. The complex with Bca was selected for isolation and characterization and was demonstrated, by native ESI-MS analysis, to have the stoichiometry E2 : Cu(i) : Bca = 1 : 1 : 1. Formation of these ternary complexes is specific for the APP E2 domain and requires Cu(i) coordination to the M1 site. Mutation of the M1 site was consistent with the His ligands being part of the E2 ligand set. It is likely that interactions between the negatively charged probe ligands and a positively charged patch on the surface of APP E2 are one aspect of the generation of the stable ternary complexes. Their formation prevented meaningful quantification of the affinity of Cu(i) binding to the M1 site with these probe ligands. However, the ternary complexes are disrupted by heparin, allowing reliable determination of a picomolar Cu(i) affinity for the E2/heparin complex with the Fz or Bca probe ligands. This is the first documented example of the formation of stable ternary complexes between a Cu(i) binding protein and a probe ligand. The ready disruption of the complexes by heparin identified clear 'tell-tale' signs for diagnosis of ternary complex formation and allowed a systematic review of conditions and criteria for reliable determination of affinities for metal binding via ligand competition. This study also provides new insights into a potential correlation of APP functions regulated by copper binding and heparin interaction.

Supra-molecular inclusion complexation of ionic liquid 1-butyl-3-methylimidazolium octylsulphate with α- and β-cyclodextrins

NASA Astrophysics Data System (ADS)

Banjare, Manoj Kumar; Behera, Kamalakanta; Satnami, Manmohan L.; Pandey, Siddharth; Ghosh, Kallol K.

2017-12-01

Host-guest complexation between ionic liquid (IL) 1-butyl-3-methylimidazolium octylsulphate [Bmim][OS] and cyclodextrins (α- and β- CDs) have been studied. Surface tension, conductivity measurements revealed the formation of 1:1 (M) stoichiometry for inclusion complexes (ICs) and further confirmed by UV-Visible and FT-IR results. The nature of the complexes has been established using interfacial and thermodynamic parameters. The aggregation number, Stern-Volmer constants, association constants were obtained from fluorescence quenching and Benesi-Hildebrand methods. The critical micelle concentration (cmc) and association constants of [Bmim][OS] are higher for β-CD as compared to α-CD. FT-IR spectra indicated that CDs and [Bmim][OS] could from ICs with stoichiometry 1:1 (M).

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

2018-02-01

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum.

Saponin Interactions with Model Membrane Systems - Langmuir Monolayer Studies, Hemolysis and Formation of ISCOMs.

PubMed

de Groot, Carolin; Müller-Goymann, Christel C

2016-12-01

Saponins are used in medicine due to their pharmacological and immunological effects. To better understand interactions of saponins with model membranes and natural membranes of, for example, erythrocytes, Langmuir film balance experiments are well established. For most saponins, a strong interaction with cholesterol was demonstrated in dependence of both the aglycone part and the sugar moieties and is suggested to be correlated with a strong hemolytic activity, high toxicity, and high surface activity, as was demonstrated for the steroid saponin digitonin. In general, changes in the sugar chain or in substituents of the aglycone result in a modification of the saponin properties. A promising saponin with regard to fairly low hemolytic activity and high adjuvant effect is α -tomatine, which still shows a high affinity for cholesterol. An interaction with cholesterol and lipids has also been proven for the Quillaja saponin from the bark of Quillaja saponaria Molina. This triterpene saponin was approved in marketed vaccines as an adjuvant due to the formation of immunostimulating complexes. Immunostimulating complexes consist of a Quillaja saponin, cholesterol, phospholipids, and a corresponding antigen. Recently, another saponin from Quillaja brasiliensis was successfully tested in immunostimulating complexes, too. Based on the results of interaction studies, the formation of drug delivery systems such as immunostimulating complexes or similar self-assembled colloids is postulated for a variety of saponins. Georg Thieme Verlag KG Stuttgart · New York.

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

Red mud carbonation using carbon dioxide: Effects of carbonate and calcium ions on goethite surface properties and settling.

PubMed

Liang, Gaojie; Chen, Wenmi; Nguyen, Anh V; Nguyen, Tuan A H

2018-05-01

Carbonation using CO 2 appears as an attractive solution for disposing of red mud suspensions, an aluminum industry hazardous waste since it also offers an option for CO 2 sequestration. Here we report the novel findings that CO 3 2- together with Ca 2+ can significantly affect the surface properties and settling of goethite, a major component of red mud. Specifically, their effects on the goethite surface chemistry, colloidal interaction forces and settling in alkaline solutions are investigated. The surface potential becomes more negative by the formation of carbonate inner-sphere complexes on goethite surface. It is consistent with the strong repulsion, decreased particle size and settling velocity with increased carbonate concentrations as measured by atomic force microscopy, particle size analysis, and particle settling. Adding Ca 2+ that forms outer-sphere complexes with pre-adsorbed carbonate changes goethite surface charge negligibly. Changing repulsion to the attraction between goethite surfaces by increasing calcium dosage indicates the surface bridging, in accordance with the increased settling velocity. The adverse effect of carbonate on goethite flocculation is probably due to its specific chemisorption and competition with flocculants. By forming outer-sphere complexes together with the flocculant-calcium bridging effect, calcium ions can eliminate the negative influence of carbonate and improve the flocculation of goethite particles. These findings contribute to a better understanding of goethite particle interaction with salt ions and flocculants in controlling the particle behavior in the handling processes, including the red mud carbonation. Copyright © 2018 Elsevier Inc. All rights reserved.

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

Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empiricallymore » determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs.« less

Crystal structure of human proteasome assembly chaperone PAC4 involved in proteasome formation.

PubMed

Kurimoto, Eiji; Satoh, Tadashi; Ito, Yuri; Ishihara, Eri; Okamoto, Kenta; Yagi-Utsumi, Maho; Tanaka, Keiji; Kato, Koichi

2017-05-01

The 26S proteasome is a large protein complex, responsible for degradation of ubiquinated proteins in eukaryotic cells. Eukaryotic proteasome formation is a highly ordered process that is assisted by several assembly chaperones. The assembly of its catalytic 20S core particle depends on at least five proteasome-specific chaperones, i.e., proteasome-assembling chaperons 1-4 (PAC1-4) and proteasome maturation protein (POMP). The orthologues of yeast assembly chaperones have been structurally characterized, whereas most mammalian assembly chaperones are not. In the present study, we determined a crystal structure of human PAC4 at 1.90-Å resolution. Our crystallographic data identify a hydrophobic surface that is surrounded by charged residues. The hydrophobic surface is complementary to that of its binding partner, PAC3. The surface also exhibits charge complementarity with the proteasomal α4-5 subunits. This will provide insights into human proteasome-assembling chaperones as potential anticancer drug targets. © 2017 The Protein Society.

An ice-rich flow origin for the banded terrain in the Hellas basin, Mars

NASA Astrophysics Data System (ADS)

Diot, X.; El-Maarry, M. R.; Guallini, L.; Schlunegger, F.; Norton, K. P.; Thomas, N.; Sutton, S.; Grindrod, P. M.

2015-12-01

The interior of Hellas Basin displays a complex landscape and a variety of geomorphological domains. One of these domains, the enigmatic banded terrain covers much of the northwestern part of the basin. We use high-resolution (Context Camera and High-Resolution Imaging Science Experiment) Digital Terrain Models to show that most of the complex viscous flowing behavior exhibited by the banded terrain is controlled by topography and flow-like interactions between neighboring banded terrain. Furthermore, the interior of the basin hosts several landforms suggestive of the presence of near-surface ice, which include polygonal patterns with elongated pits, scalloped depressions, isolated mounds, and collapse structures. We suggest that thermal contraction cracking and sublimation of near-surface ice are responsible for the formation and the development of most of the ice-related landforms documented in Hellas. The relatively pristine form, lack of superposed craters, and strong association with the banded terrain, suggest an Amazonian (<3 Ga) age of formation for these landforms. Finally, relatively high surface pressures (above the triple point of water) expected in Hellas and summertime temperatures often exceeding the melting point of water ice suggest that the basin may have recorded relatively "temperate" climatic conditions compared to other places on Mars. Therefore, the potentially ice-rich banded terrain may have deformed with lower viscosity and stresses compared to other locations on Mars, which may account for its unique morphology.

The dynamics of complex formation between amylose brushes on gold and fatty acids by QCM-D.

PubMed

Cao, Zheng; Tsoufis, Theodoros; Svaldo-Lanero, Tiziana; Duwez, Anne-Sophie; Rudolf, Petra; Loos, Katja

2013-10-14

Amylose brushes were synthesized by enzymatic polymerization with glucose-1-phosphate as monomer and rabbit muscle phosphorylase b as catalyst on gold-covered surfaces of a quartz crystal microbalance. Fourier transform infrared (FT-IR) spectra confirmed the presence of the characteristic absorption peaks of amylose between 3100 cm(-1) and 3500 cm(-1). The thickness of the amylose brushes-measured by Spectroscopic Ellipsometry--can be tailored from 4 to 20 nm, depending on the reaction time. The contour length of the stretched amylose chains on gold surfaces has been evaluated by single molecule force spectroscopy, and a total chain length of about 20 nm for 16.2 nm thick amylose brushes was estimated. X-ray photoelectron spectroscopy (XPS) was employed to characterize the amylose brushes before and after the adsorption of fatty acids. The dynamics of inclusion complex formation between amylose brushes and two fatty acids (octanoic acid and myristic acid) with different chain length was investigated as a function of time using a quartz crystal microbalance with dissipation monitoring (QCM-D) immersed in the liquid phase. QCM-D signals including the frequency and dissipation shifts elucidated the effects of the fatty acid concentration, the solvent types, the chain length of the fatty acids and the thickness of the amylose brushes on the dynamics of fatty acid molecule adsorption on the amylose brush-modified sensor surfaces.

Sinuous flow in metals

PubMed Central

Yeung, Ho; Viswanathan, Koushik; Compton, Walter Dale; Chandrasekar, Srinivasan

2015-01-01

Annealed metals are surprisingly difficult to cut, involving high forces and an unusually thick “chip.” This anomaly has long been explained, based on ex situ observations, using a model of smooth plastic flow with uniform shear to describe material removal by chip formation. Here we show that this phenomenon is actually the result of a fundamentally different collective deformation mode—sinuous flow. Using in situ imaging, we find that chip formation occurs via large-amplitude folding, triggered by surface undulations of a characteristic size. The resulting fold patterns resemble those observed in geophysics and complex fluids. Our observations establish sinuous flow as another mesoscopic deformation mode, alongside mechanisms such as kinking and shear banding. Additionally, by suppressing the triggering surface undulations, sinuous flow can be eliminated, resulting in a drastic reduction of cutting forces. We demonstrate this suppression quite simply by the application of common marking ink on the free surface of the workpiece material before the cutting. Alternatively, prehardening a thin surface layer of the workpiece material shows similar results. Besides obvious implications to industrial machining and surface generation processes, our results also help unify a number of disparate observations in the cutting of metals, including the so-called Rehbinder effect. PMID:26216980

Sinuous flow in metals.

PubMed

Yeung, Ho; Viswanathan, Koushik; Compton, Walter Dale; Chandrasekar, Srinivasan

2015-08-11

Annealed metals are surprisingly difficult to cut, involving high forces and an unusually thick "chip." This anomaly has long been explained, based on ex situ observations, using a model of smooth plastic flow with uniform shear to describe material removal by chip formation. Here we show that this phenomenon is actually the result of a fundamentally different collective deformation mode--sinuous flow. Using in situ imaging, we find that chip formation occurs via large-amplitude folding, triggered by surface undulations of a characteristic size. The resulting fold patterns resemble those observed in geophysics and complex fluids. Our observations establish sinuous flow as another mesoscopic deformation mode, alongside mechanisms such as kinking and shear banding. Additionally, by suppressing the triggering surface undulations, sinuous flow can be eliminated, resulting in a drastic reduction of cutting forces. We demonstrate this suppression quite simply by the application of common marking ink on the free surface of the workpiece material before the cutting. Alternatively, prehardening a thin surface layer of the workpiece material shows similar results. Besides obvious implications to industrial machining and surface generation processes, our results also help unify a number of disparate observations in the cutting of metals, including the so-called Rehbinder effect.

Surface microtopography modulates sealing zone development in osteoclasts cultured on bone

PubMed Central

Addadi, Lia; Geiger, Benjamin

2017-01-01

Bone homeostasis is continuously regulated by the coordinated action of bone-resorbing osteoclasts and bone-forming osteoblasts. Imbalance between these two cell populations leads to pathological bone diseases such as osteoporosis and osteopetrosis. Osteoclast functionality relies on the formation of sealing zone (SZ) rings that define the resorption lacuna. It is commonly assumed that the structure and dynamic properties of the SZ depend on the physical and chemical properties of the substrate. Considering the unique complex structure of native bone, elucidation of the relevant parameters affecting SZ formation and stability is challenging. In this study, we examined in detail the dynamic response of the SZ to the microtopography of devitalized bone surfaces, taken from the same area in cattle femur. We show that there is a significant enrichment in large and stable SZs (diameter larger than 14 µm; lifespan of hours) in cells cultured on rough bone surfaces, compared with small and fast turning over SZ rings (diameter below 7 µm; lifespan approx. 7 min) formed on smooth bone surfaces. Based on these results, we propose that the surface roughness of the physiologically relevant substrate of osteoclasts, namely bone, affects primarily the local stability of growing SZs. PMID:28202594

Diallyl disulphide as natural organosulphur friction modifier via the in-situ tribo-chemical formation of tungsten disulphide

NASA Astrophysics Data System (ADS)

Rodríguez Ripoll, Manel; Totolin, Vladimir; Gabler, Christoph; Bernardi, Johannes; Minami, Ichiro

2018-01-01

The present work shows a novel method for generating in-situ low friction tribofilms containing tungsten disulphide in lubricated contacts using diallyl disulphide as sulphur precursor. The approach relies on the tribo-chemical interaction between the diallyl disulphide and a surface containing embedded sub-micrometer tungsten carbide particles. The results show that upon sliding contact between diallyl disulphide and the tungsten-containing surface, the coefficient of friction drops to values below 0.05 after an induction period. The reason for the reduction in friction is due to tribo-chemical reactions that leads to the in-situ formation of a complex tribofilm that contains iron and tungsten components. X-ray photoelectron spectroscopy analyses indicate the presence of tungsten disulphide at the contact interface, thus justifying the low coefficient of friction achieved during the sliding experiments. It was proven that the low friction tribofilms can only be formed by the coexistence of tungsten and sulphur species, thus highlighting the synergy between diallyl disulphide and the tungsten-containing surface. The concept of functionalizing surfaces to react with specific additives opens up a wide range of possibilities, which allows tuning on-site surfaces to target additive interactions.

Myelin Proteolipid Protein Complexes with αv Integrin and AMPA Receptors In Vivo and Regulates AMPA-Dependent Oligodendrocyte Progenitor Cell Migration through the Modulation of Cell-Surface GluR2 Expression

PubMed Central

Harlow, Danielle E.; Saul, Katherine E.; Komuro, Hitoshi

2015-01-01

In previous studies, stimulation of ionotropic AMPA/kainate glutamate receptors on cultured oligodendrocyte cells induced the formation of a signaling complex that includes the AMPA receptor, integrins, calcium-binding proteins, and, surprisingly, the myelin proteolipid protein (PLP). AMPA stimulation of cultured oligodendrocyte progenitor cells (OPCs) also caused an increase in OPC migration. The current studies focused primarily on the formation of the PLP–αv integrin–AMPA receptor complex in vivo and whether complex formation impacts OPC migration in the brain. We found that in wild-type cerebellum, PLP associates with αv integrin and the calcium-impermeable GluR2 subunit of the AMPA receptor, but in mice lacking PLP, αv integrin did not associate with GluR2. Live imaging studies of OPC migration in ex vivo cerebellar slices demonstrated altered OPC migratory responses to neurotransmitter stimulation in the absence of PLP and GluR2 or when αv integrin levels were reduced. Chemotaxis assays of purified OPCs revealed that AMPA stimulation was neither attractive nor repulsive but clearly increased the migration rate of wild-type but not PLP null OPCs. AMPA receptor stimulation of wild-type OPCs caused decreased cell-surface expression of the GluR2 AMPA receptor subunit and increased intracellular Ca2+ signaling, whereas PLP null OPCs did not reduce GluR2 at the cell surface or increase Ca2+ signaling in response to AMPA treatment. Together, these studies demonstrate that PLP is critical for OPC responses to glutamate signaling and has important implications for OPC responses when levels of glutamate are high in the extracellular space, such as following demyelination. SIGNIFICANCE STATEMENT After demyelination, such as occurs in multiple sclerosis, remyelination of axons is often incomplete, leading to loss of neuronal function and clinical disability. Remyelination may fail because oligodendrocyte precursor cells (OPCs) do not completely migrate into demyelinated areas or OPCs in lesions may not mature into myelinating oligodendrocytes. We have found that the myelin proteolipid protein is critical to regulating OPC migratory responses to the neurotransmitter glutamate through modulation of cell-surface expression of the calcium-impermeable GluR2 subunit of the AMPA glutamate receptor and increased intercellular Ca2+ signaling. Altered glutamate homeostasis has been reported in demyelinated lesions. Therefore, understanding how OPCs respond to glutamate has important implications for treatment after white matter injury and disease. PMID:26311781

Principles of biofouling protection in marine sponges: a model for the design of novel biomimetic and bio-inspired coatings in the marine environment?

PubMed

Müller, Werner E G; Wang, Xiaohong; Proksch, Peter; Perry, Carole C; Osinga, Ronald; Gardères, Johan; Schröder, Heinz C

2013-08-01

The process of biofouling of marine structures and substrates, such as platforms or ship hulls, proceeds in multiple steps. Soon after the formation of an initial conditioning film, formed via the adsorption of organic particles to natural or man-made substrates, a population of different bacterial taxa associates under the formation of a biofilm. These microorganisms communicate through a complex quorum sensing network. Macro-foulers, e.g., barnacles, then settle and form a fouling layer on the marine surfaces, a process that globally has severe impacts both on the economy and on the environment. Since the ban of tributyltin, an efficient replacement of this antifouling compound by next-generation antifouling coatings that are environmentally more acceptable and also showing longer half-lives has not yet been developed. The sponges, as sessile filter-feeder animals, have evolved antifouling strategies to protect themselves against micro- and subsequent macro-biofouling processes. Experimental data are summarized and suggest that coating of the sponge surface with bio-silica contributes to the inhibition of the formation of a conditioning film. A direct adsorption of the surfaces by microorganisms can be impaired through poisoning the organisms with direct-acting secondary metabolites or toxic peptides. In addition, first, compounds from sponges have been identified that interfere with the anti-quorum sensing network. Sponge secondary metabolites acting selectively on diatom colonization have not yet been identified. Finally, it is outlined that direct-acting secondary metabolites inhibiting the growth of macro-fouling animals and those that poison the multidrug resistance pump are available. It is concluded that rational screening programs for inhibitors of the complex and dynamic problem of biofilm production, based on multidisciplinary studies and using sponges as a model, are required in the future.

Surface-active ionic liquids for palladium-catalysed cross coupling in water: effect of ionic liquid concentration on the catalytically active species† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ra07757b

PubMed Central

Taskin, Meltem; Cognigni, Alice; Zirbs, Ronald; Reimhult, Erik

2017-01-01

We report the design and synthesis of surface-active ionic liquids for application in palladium-catalyzed cross coupling reactions. A series of dodecylimidazolium-based ionic liquids were applied as additives in the Heck reaction of ethyl acrylate and iodobenzene, and high yields of >90% could be obtained in water without the addition of further ligands. Our results indicate that the ionic liquid concentration in water is the key factor affecting the formation of the catalytically active species and hence the yield. Moreover, imidazolium-based ionic liquids that are able to form a carbene species differ significantly from conventional cationic surfactants, as a concentration dependent formation of the N-heterocyclic carbene complex was observed. PMID:29308189

Analysis of impact craters on Mercury's surface.

NASA Astrophysics Data System (ADS)

Martellato, E.; Cremonese, G.; Marzari, F.; Massironi, M.; Capria, M. T.

The formation of a crater is a complex process, which can be analyzed with numerical simulations and/or observational methods. This work reports a preliminary analysis of some craters on Mercury, based on the Mariner 10 images. The physical and dynamical properties of the projectile may not derive from the knowledge of the crater alone, since the size of an impact crater depends on many parameters. We have calculated the diameter of the projectile using the scaling law of Schmidt and Housen (\\citep{SandM87}). It is performed for different projectile compositions and impact velocities, assuming an anorthositic composition of the surface. The melt volume production at the initial phases of the crater formation is also calculated by the experimental law proposed by O'Keefe and Ahrens (\\citep{OA82}), giving the ratio between melt and projectile mass.

Nanoparticle-Protein Interaction: The Significance and Role of Protein Corona.

PubMed

Ahsan, Saad Mohammad; Rao, Chintalagiri Mohan; Ahmad, Md Faiz

2018-01-01

The physico-chemical properties of nanoparticles, as characterized under idealized laboratory conditions, have been suggested to differ significantly when studied under complex physiological environments. A major reason for this variation has been the adsorption of biomolecules (mainly proteins) on the nanoparticle surface, constituting the so-called "biomolecular corona". The formation of biomolecular corona on the nanoparticle surface has been reported to influence various nanoparticle properties viz. cellular targeting, cellular interaction, in vivo clearance, toxicity, etc. Understanding the interaction of nanoparticles with proteins upon administration in vivo thus becomes important for the development of effective nanotechnology-based platforms for biomedical applications. In this chapter, we describe the formation of protein corona on nanoparticles and the differences arising in its composition due to variations in nanoparticle properties. Also discussed is the influence of protein corona on various nanoparticle activities.

Formation and dissolution of bacterial colonies.

PubMed

Weber, Christoph A; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

2015-09-01

Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation.

KENNEDY SPACE CENTER, FLA. - NASA T-38 jets fly over the Space Mirror Memorial at the Kennedy Space Center Visitor Complex in the Missing Man Formation. During this dedication ceremony, the names of the STS-107 astronauts who lost their lives during the Columbia accident -- Rick Husband, Willie McCool, Laurel Clark, Michael Anderson, David Brown, Kalpana Chawla, and Ilan Ramon -- join the names of 17 other space heroes who gave their lives for the U.S. space program. The "Space Mirror," 42 1/2 feet high by 50 feet wide, illuminates the names of the fallen astronauts cut through the monument's black granite surface.

NASA Image and Video Library

2003-10-28

KENNEDY SPACE CENTER, FLA. - NASA T-38 jets fly over the Space Mirror Memorial at the Kennedy Space Center Visitor Complex in the Missing Man Formation. During this dedication ceremony, the names of the STS-107 astronauts who lost their lives during the Columbia accident -- Rick Husband, Willie McCool, Laurel Clark, Michael Anderson, David Brown, Kalpana Chawla, and Ilan Ramon -- join the names of 17 other space heroes who gave their lives for the U.S. space program. The "Space Mirror," 42 1/2 feet high by 50 feet wide, illuminates the names of the fallen astronauts cut through the monument's black granite surface.

The evolution of organic matter in space.

PubMed

Ehrenfreund, Pascale; Spaans, Marco; Holm, Nils G

2011-02-13

Carbon, and molecules made from it, have already been observed in the early Universe. During cosmic time, many galaxies undergo intense periods of star formation, during which heavy elements like carbon, oxygen, nitrogen, silicon and iron are produced. Also, many complex molecules, from carbon monoxide to polycyclic aromatic hydrocarbons, are detected in these systems, like they are for our own Galaxy. Interstellar molecular clouds and circumstellar envelopes are factories of complex molecular synthesis. A surprisingly high number of molecules that are used in contemporary biochemistry on the Earth are found in the interstellar medium, planetary atmospheres and surfaces, comets, asteroids and meteorites and interplanetary dust particles. Large quantities of extra-terrestrial material were delivered via comets and asteroids to young planetary surfaces during the heavy bombardment phase. Monitoring the formation and evolution of organic matter in space is crucial in order to determine the prebiotic reservoirs available to the early Earth. It is equally important to reveal abiotic routes to prebiotic molecules in the Earth environments. Materials from both carbon sources (extra-terrestrial and endogenous) may have contributed to biochemical pathways on the Earth leading to life's origin. The research avenues discussed also guide us to extend our knowledge to other habitable worlds.

Exopolysaccharide microchannels direct bacterial motility and organize multicellular behavior

DOE PAGES

Berleman, James E.; Zemla, Marcin; Remis, Jonathan P.; ...

2016-05-06

The myxobacteria are a family of soil bacteria that form biofilms of complex architecture, aligned multilayered swarms or fruiting body structures that are simple or branched aggregates containing myxospores. Here, we examined the structural role of matrix exopolysaccharide (EPS) in the organization of these surface-dwelling bacterial cells. Using time-lapse light and fluorescence microscopy, as well as transmission electron microscopy and focused ion beam/scanning electron microscopy (FIB/SEM) electron microscopy, we found that Myxococcus xanthus cell organization in biofilms is dependent on the formation of EPS microchannels. Cells are highly organized within the three-dimensional structure of EPS microchannels that are required formore » cell alignment and advancement on surfaces. Mutants lacking EPS showed a lack of cell orientation and poor colony migration. Purified, cell-free EPS retains a channel-like structure, and can complement EPS - mutant motility defects. In addition, EPS provides the cooperative structure for fruiting body formation in both the simple mounds of M. xanthus and the complex, tree-like structures of Chondromyces crocatus. We furthermore investigated the possibility that EPS impacts community structure as a shared resource facilitating cooperative migration among closely related isolates of M. xanthus.« less

Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen

2017-07-01

Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of prebiotic interest. Our results suggest that imine acetaldehyde could be a feasible candidate molecule to be searched for in space.

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments.

PubMed

Brechbühl, Yves; Christl, Iso; Elzinga, Evert J; Kretzschmar, Ruben

2012-07-01

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures. Copyright © 2012 Elsevier Inc. All rights reserved.

Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

USGS Publications Warehouse

Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

2001-01-01

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

Hybridization behavior of mixed DNA/alkylthiol monolayers on gold: characterization by surface plasmon resonance and 32P radiometric assay.

PubMed

Gong, Ping; Lee, Chi-Ying; Gamble, Lara J; Castner, David G; Grainger, David W

2006-05-15

Nucleic acid assay from a complex biological milieu is attractive but currently difficult and far from routine. In this study, DNA hybridization from serum dilutions into mixed DNA/mercaptoundecanol (MCU) adlayers on gold was monitored by surface plasmon resonance (SPR). Immobilized DNA probe and hybridized target densities on these surfaces were quantified using 32P-radiometric assays as a function of MCU diluent exposure. SPR surface capture results correlated with radiometric analysis for hybridization performance, demonstrating a maximum DNA hybridization on DNA/MCU mixed adlayers. The maximum target surface capture produced by MCU addition to the DNA probe layer correlates with structural and conformational data on identical mixed DNA/MCU adlayers on gold derived from XPS, NEXAFS, and fluorescence intensity measurements reported in a related study (Lee, C.-Y.; Gong, P.; Harbers, G. M.; Grainger, D. W.; Castner, D. G.; Gamble, L. J. Anal. Chem. 2006, 78, 3316-3325.). MCU addition into the DNA adlayer on gold also improved surface resistance to both nonspecific DNA and serum protein adsorption. Target DNA hybridization from serum dilutions was monitored with SPR on the optimally mixed DNA/MCU adlayers. Both hybridization kinetics and efficiency were strongly affected by nonspecific protein adsorption from a complex milieu even at a minimal serum concentration (e.g., 1%). No target hybridization was detected in SPR assays from serum concentrations above 30%, indicating nonspecific protein adsorption interference of DNA capture and hybridization from complex milieu. Removal of nonsignal proteins from nucleic acid targets prior to assay represents a significant issue for direct sample-to-assay nucleic acid diagnostics from food, blood, tissue, PCR mixtures, and many other biologically complex sample formats.

Complex surface rupturing and related formation mechanisms in the Xiaoyudong area for the 2008 Mw 7.9 Wenchuan Earthquake, China

NASA Astrophysics Data System (ADS)

Tan, Xi-bin; Yuan, Ren-mao; Xu, Xi-wei; Chen, Gui-hua; Klinger, Yann; Chang, Chung-Pai; Ren, Jun-jie; Xu, Chong; Li, Kang

2012-09-01

The large oblique reverse slip shock of the 2008 Mw = 7.9 Wenchuan earthquake, China, produced one of the longest and most complicated surface ruptures ever known. The complexity is particularly evident in the Xiaoyudong area, where three special phenomena occurred: the 7 km long Xiaoyudong rupture perpendicular to the Beichuan-Yingxiu fault; the occurrence of two parallel faults rupturing simultaneously, and apparent discontinuity of the Beichuan-Yingxiu rupture. This paper systematically documents these co-seismic rupture phenomena for the Xiaoyudong area. The discussion and results are based on field investigations and analyses of faulting mechanisms and prevalent stress conditions. The results show that the Beichuan-Yingxiu fault formed a 3.5 km wide restraining stepover at the Xiaoyudong area. The Xiaoyudong fault is not a tear fault suggested by previous researches, but a frontal reverse fault induced by the oblique compression at this stepover; it well accommodates the 'deformation gap' of the Beichuan-Yingxiu fault in the Xiaoyudong area. Further, stress along the Peng-Guan fault plane doubles due to a change in dip angle of the Beichuan-Yingxiu fault across the Xiaoyudong restraining stepover. This resulted in two faults rupturing the ground's surface simultaneously, to the north of the Xiaoyudong area. These results are helpful in deepening our understanding of the dynamic processes that produced surface ruptures during the Wenchuan earthquake. Furthermore, the results suggest more attention be focused on the influence of dextral slip component, the change of the control fault's attitude, and property differences in rocks on either side of faults when discussing the formation mechanism of surface ruptures.

Presynaptic dystroglycan-pikachurin complex regulates the proper synaptic connection between retinal photoreceptor and bipolar cells.

PubMed

Omori, Yoshihiro; Araki, Fumiyuki; Chaya, Taro; Kajimura, Naoko; Irie, Shoichi; Terada, Koji; Muranishi, Yuki; Tsujii, Toshinori; Ueno, Shinji; Koyasu, Toshiyuki; Tamaki, Yasuhiro; Kondo, Mineo; Amano, Shiro; Furukawa, Takahisa

2012-05-02

Dystroglycan (DG) is a key component of the dystrophin-glycoprotein complex (DGC) at the neuromuscular junction postsynapse. In the mouse retina, the DGC is localized at the presynapse of photoreceptor cells, however, the function of presynaptic DGC is poorly understood. Here, we developed and analyzed retinal photoreceptor-specific DG conditional knock-out (DG CKO) mice. We found that the DG CKO retina showed a reduced amplitude and a prolonged implicit time of the ERG b-wave. Electron microscopic analysis revealed that bipolar dendrite invagination into the photoreceptor terminus is perturbed in the DG CKO retina. In the DG CKO retina, pikachurin, a DG ligand in the retina, is markedly decreased at photoreceptor synapses. Interestingly, in the Pikachurin(-/-) retina, the DG signal at the ribbon synaptic terminus was severely reduced, suggesting that pikachurin is required for the presynaptic accumulation of DG at the photoreceptor synaptic terminus, and conversely DG is required for pikachurin accumulation. Furthermore, we found that overexpression of pikachurin induces formation and clustering of a DG-pikachurin complex on the cell surface. The Laminin G repeats of pikachurin, which are critical for its oligomerization and interaction with DG, were essential for the clustering of the DG-pikachurin complex as well. These results suggest that oligomerization of pikachurin and its interaction with DG causes DG assembly on the synapse surface of the photoreceptor synaptic terminals. Our results reveal that the presynaptic interaction of pikachurin with DG at photoreceptor terminals is essential for both the formation of proper photoreceptor ribbon synaptic structures and normal retinal electrophysiology.

Electrostatic Rate Enhancement and Transient Complex of Protein-Protein Association

PubMed Central

Alsallaq, Ramzi; Zhou, Huan-Xiang

2012-01-01

The association of two proteins is bounded by the rate at which they, via diffusion, find each other while in appropriate relative orientations. Orientational constraints restrict this rate to ~105 – 106 M−1s−1. Proteins with higher association rates generally have complementary electrostatic surfaces; proteins with lower association rates generally are slowed down by conformational changes upon complex formation. Previous studies (Zhou, Biophys. J. 1997;73:2441–2445) have shown that electrostatic enhancement of the diffusion-limited association rate can be accurately modeled by kD = kD0 exp(−*/ kBT), where kD and kD0 are the rates in the presence and absence of electrostatic interactions, respectively, * is the average electrostatic interaction energy in a “transient-complex” ensemble, and kBT is thermal energy. The transient-complex ensemble separates the bound state from the unbound state. Predictions of the transient-complex theory on four protein complexes were found to agree well with experiment when the electrostatic interaction energy was calculated with the linearized Poisson-Boltzmann (PB) equation (Alsallaq and Zhou, Structure 2007, 15:215–224). Here we show that the agreement is further improved when the nonlinear PB equation is used. These predictions are obtained with the dielectric boundary defined as the protein van der Waals surface. When the dielectric boundary is instead specified as the molecular surface, electrostatic interactions in the transient complex become repulsive and are thus predicted to retard association. Together these results demonstrate that the transient-complex theory is predictive of electrostatic rate enhancement and can help parameterize PB calculations. PMID:17932929

A positive-strand RNA virus uses alternative protein-protein interactions within a viral protease/cofactor complex to switch between RNA replication and virion morphogenesis.

PubMed

Dubrau, Danilo; Tortorici, M Alejandra; Rey, Félix A; Tautz, Norbert

2017-02-01

The viruses of the family Flaviviridae possess a positive-strand RNA genome and express a single polyprotein which is processed into functional proteins. Initially, the nonstructural (NS) proteins, which are not part of the virions, form complexes capable of genome replication. Later on, the NS proteins also play a critical role in virion formation. The molecular basis to understand how the same proteins form different complexes required in both processes is so far unknown. For pestiviruses, uncleaved NS2-3 is essential for virion morphogenesis while NS3 is required for RNA replication but is not functional in viral assembly. Recently, we identified two gain of function mutations, located in the C-terminal region of NS2 and in the serine protease domain of NS3 (NS3 residue 132), which allow NS2 and NS3 to substitute for uncleaved NS2-3 in particle assembly. We report here the crystal structure of pestivirus NS3-4A showing that the NS3 residue 132 maps to a surface patch interacting with the C-terminal region of NS4A (NS4A-kink region) suggesting a critical role of this contact in virion morphogenesis. We show that destabilization of this interaction, either by alanine exchanges at this NS3/4A-kink interface, led to a gain of function of the NS3/4A complex in particle formation. In contrast, RNA replication and thus replicase assembly requires a stable association between NS3 and the NS4A-kink region. Thus, we propose that two variants of NS3/4A complexes exist in pestivirus infected cells each representing a basic building block required for either RNA replication or virion morphogenesis. This could be further corroborated by trans-complementation studies with a replication-defective NS3/4A double mutant that was still functional in viral assembly. Our observations illustrate the presence of alternative overlapping surfaces providing different contacts between the same proteins, allowing the switch from RNA replication to virion formation.

GRAIL Gravity Observations of the Transition from Complex Crater to Peak-Ring Basin on the Moon: Implications for Crustal Structure and Impact Basin Formation

NASA Technical Reports Server (NTRS)

Baker, David M. H.; Head, James W.; Phillips, Roger J.; Neumann, Gregory A.; Bierson, Carver J.; Smith, David E.; Zuber, Maria T.

2017-01-01

High-resolution gravity data from the Gravity Recovery and Interior Laboratory (GRAIL) mission provide the opportunity to analyze the detailed gravity and crustal structure of impact features in the morphological transition from complex craters to peak-ring basins on the Moon. We calculate average radial profiles for free-air anomalies and Bouguer anomalies for peak-ring basins, proto-basins, and the largest complex craters. Complex craters and proto-basins have free-air anomalies that are positively correlated with surface topography, unlike the prominent lunar mascons (positive free-air anomalies in areas of low elevation) associated with large basins. The Bouguer gravity anomaly profiles of complex craters are highly irregular, with central positive anomalies that are generally absent or not clearly tied to interior morphology. In contrast, gravity profiles for peak-ring basins (approx. 200 km to 580 km) are much more regular and are highly correlated with surface morphology. A central positive Bouguer anomaly is confined within the peak ring and a negative Bouguer anomaly annulus extends from the edge of the positive anomaly outward to about the rim crest. A number of degraded basins lacking interior peak rings have diameters and gravity patterns similar to those of well-preserved peak-ring basins. If these structures represent degraded peak-ring basins, the number of peak-ring basins on the Moon would increase by more than a factor of two to 34. The gravity anomalies within basins are interpreted to be due to uplift of the mantle confined within the peak ring and an annulus of thickened crust between the peak ring and rim crest. We hypothesize that mantle uplift is influenced by interaction between the transient cavity and the mantle. Further, mascon formation is generally disconnected from the number of basin rings formed and occurs over a wide range of basin sizes. These observations have important implications for models of basin and mascon formation on the Moon and other planetary bodies.

Climatic Impact of a Change in North Atlantic Deep Water Formation

NASA Technical Reports Server (NTRS)

Rind, D.

1984-01-01

The response of the ocean to climate changes is one of the most uncertain questions regarding the impact of increasing CO2 on climate and society. North Atlantic deep water (NADW) formation apparently depends on a complex confluence of different water masses originating in different areas, all of which will presumably be affected by changes in wind, evaporation, etc., as the atmosphere warms. To analyze from first principles what the effect will be on NADW formation is a task which requires an ocean modeling capability not yet available. As a substitute, past climates can be investigated to see if there is any evidence for alterations in NADW formation. In addition, the possible impact of such changes on climate can be explored. An estimate of NADW sensitivity (at least in the past) and of the climate consequences can be studied. The North Atlantic surface water temperatures can be reconstructed to indicate a substantial cooling between 11,000 and 10,000 years B.P. Were NADW formation to have ceased, it would have resulted in cooler surface waters; whether the reconstructed temperatures were due to this or some other effect cannot be determined at this time. Nevertheless, it was decided that it would be useful to see what the effect these colder temperatures would have had on the climate.

The effect of simulated low earth orbit radiation on polyimides (UV degradation study)

NASA Technical Reports Server (NTRS)

Forsythe, John S.; George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1995-01-01

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-cenetered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was two fold higher than for vacuum irradiation, and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C-O binding energy peak relative to the C-C peak was believed to be associated with an aromatic ring opening reaction.

The mechanism of a nuclear pore assembly: a molecular biophysics view.

PubMed

Kuvichkin, Vasily V

2011-06-01

The basic problem of nuclear pore assembly is the big perinuclear space that must be overcome for nuclear membrane fusion and pore creation. Our investigations of ternary complexes: DNA-PC liposomes-Mg²⁺, and modern conceptions of nuclear pore structure allowed us to introduce a new mechanism of nuclear pore assembly. DNA-induced fusion of liposomes (membrane vesicles) with a single-lipid bilayer or two closely located nuclear membranes is considered. After such fusion on the lipid bilayer surface, traces of a complex of ssDNA with lipids were revealed. At fusion of two identical small liposomes (membrane vesicles) < 100 nm in diameter, a "big" liposome (vesicle) with ssDNA on the vesicle equator is formed. ssDNA occurrence on liposome surface gives a biphasic character to the fusion kinetics. The "big" membrane vesicle surrounded by ssDNA is the base of nuclear pore assembly. Its contact with the nuclear envelope leads to fast fusion of half of the vesicles with one nuclear membrane; then ensues a fusion delay when ssDNA reaches the membrane. The next step is to turn inside out the second vesicle half and its fusion to other nuclear membrane. A hole is formed between the two membranes, and nucleoporins begin pore complex assembly around the ssDNA. The surface tension of vesicles and nuclear membranes along with the kinetic energy of a liquid inside a vesicle play the main roles in this process. Special cases of nuclear pore formation are considered: pore formation on both nuclear envelope sides, the difference of pores formed in various cell-cycle phases and linear nuclear pore clusters.

Fusion Stage of HIV-1 Entry Depends on Virus-Induced Cell Surface Exposure of Phosphatidylserine.

PubMed

Zaitseva, Elena; Zaitsev, Eugene; Melikov, Kamran; Arakelyan, Anush; Marin, Mariana; Villasmil, Rafael; Margolis, Leonid B; Melikyan, Gregory B; Chernomordik, Leonid V

2017-07-12

HIV-1 entry into host cells starts with interactions between the viral envelope glycoprotein (Env) and cellular CD4 receptors and coreceptors. Previous work has suggested that efficient HIV entry also depends on intracellular signaling, but this remains controversial. Here we report that formation of the pre-fusion Env-CD4-coreceptor complexes triggers non-apoptotic cell surface exposure of the membrane lipid phosphatidylserine (PS). HIV-1-induced PS redistribution depends on Ca 2+ signaling triggered by Env-coreceptor interactions and involves the lipid scramblase TMEM16F. Externalized PS strongly promotes Env-mediated membrane fusion and HIV-1 infection. Blocking externalized PS or suppressing TMEM16F inhibited Env-mediated fusion. Exogenously added PS promoted fusion, with fusion dependence on PS being especially strong for cells with low surface density of coreceptors. These findings suggest that cell-surface PS acts as an important cofactor that promotes the fusogenic restructuring of pre-fusion complexes and likely focuses the infection on cells conducive to PS signaling. Published by Elsevier Inc.

Gradient complex protective coatings for single-crystal turbine blades of high-heat gas turbine engines

NASA Astrophysics Data System (ADS)

Kuznetsov, V. P.; Lesnikov, V. P.; Muboyadzhyan, S. A.; Repina, O. V.

2007-05-01

Complex diffusion-condensation protective coatings characterized by gradient distribution of alloying elements over the thickness due to formation of a diffusion barrier layer on the surface of blades followed by deposition of condensation alloyed layers based on the Ni-Co-Cr-Al-Y system and an external layer based on a NiAl alloyed β-phase and a ZrO2: Y2O3 ceramics are presented. A complex gradient coating possessing unique protective properties at t = 1100-1200°C for single-crystal blades from alloy ZhS36VI for advanced gas turbine engines with gas temperature of 1550°C at the inlet to the turbine is described.

Spectroscopic studies of nanoparticle-sensitised photorefractive polymers

NASA Astrophysics Data System (ADS)

Aslam, Farzana; Binks, David J.; Daniels, Steve; Pickett, Nigel; O'Brien, Paul

2005-09-01

We report on the absorbance and photoluminescence spectra of photorefractive polymer composites sensitized by three different types of nanoparticles. Each nanoparticle is passivated by 1-hexadecylamine (HDA) and the composites also consist of the charge transporting matrix poly( N-vinylcarbazole) and the dye 1-(2'-ethylhexyloxy)-2,5-dimethyl-4-(4-nitrophenylazo) benzene. A strong spectral feature is observed that is attributed to a complex formed between the dye and HDA; elemental analysis indicates that the formation of this complex is determined by the metal content of the nanoparticle surface. The photoluminescence quantum yield for the complex is greatly reduced when the HDA is attached to the nanoparticle, indicating that a charge transfer occurs.

Multifunctional nanoparticulate polyelectrolyte complexes.

PubMed

Hartig, Sean M; Greene, Rachel R; DasGupta, Jayasri; Carlesso, Gianluca; Dikov, Mikhail M; Prokop, Ales; Davidson, Jeffrey M

2007-12-01

Water-soluble, biodegradable, polymeric, polyelectrolyte complex dispersions (PECs) have evolved because of the limitations, in terms of toxicity, of the currently available systems. These aqueous nanoparticulate architectures offer a significant advantage for products that may be used as drug delivery systems in humans. PECs are created by mixing oppositely charged polyions. Their hydrodynamic diameter, surface charge, and polydispersity are highly dependent on concentration, ionic strength, pH, and molecular parameters of the polymers that are used. In particular, the complexation between polyelectrolytes with significantly different molecular weights leads to the formation of water-insoluble aggregates. Several PEC characteristics are favorable for cellular uptake and colloidal stability, including hydrodynamic diameter less than 200 nm, surface charge of >30 mV or <-30 mV, spherical morphology, and polydispersity index (PDI) indicative of a homogeneous distribution. Maintenance of these properties is critical for a successful delivery vehicle. This review focuses on the development and potential applications of PECs as multi-functional, site-specific nanoparticulate drug/gene delivery and imaging devices.

Equilibration of a polycation - anionic surfactant mixture at the water/vapor interface.

PubMed

Akanno, Andrew; Guzmán, Eduardo; Fernández-Peña, Laura; Llamas, Sara; Ortega, Francisco; Rubio, Ramon Gonzalez

2018-06-01

The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC) - sodium lauryl ether sulfate (SLES) mixtures at the water / vapor interface has been studied by different surface tension techniques and dilational visco-elasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte - surfactant complexes in the bulk affects to the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC - SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work helps on the understanding of the most fundamental bases of the physico-chemical behavior of concentrated polyelectrolyte - surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

Preliminary results report: Conasauga near-surface heater experiment

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

Krumhansl, J.L.

From November 1977 to August 1978, two near-surface heater experiments were operated in two somewhat different stratigraphic sequences within the Conasauga formation which consist predominantly of shale. Specific phenomena investigated were the thermal and mechanical responses of the formation to an applied heat load, as well as the mineralogical changes induced by heating. Objective was to provide a minimal integrated field and laboratory study that would supply a data base which could be used in planning more expensive and complex vault-type experiments in other localities. The experiments were operated with heater power levels of between 6 and 8 kW formore » heater mid-plane temperatures of 385/sup 0/C. The temperature fields within the shale were measured and analysis is in progress. Steady state conditions were achieved within 90 days. Conduction appears to be the principal mechanism of heat transport through the formation. Limited mechanical response measurements consisting of vertical displacement and stress data indicate general agreement with predictions. Posttest data, collection of which await experiment shutdown and cooling of the formation, include the mineralogy of posttest cores, posttest transmissivity measurements and corrosion data on metallurgical samples.« less

Integrated approaches to terminal Proterozoic stratigraphy: an example from the Olenek Uplift, northeastern Siberia

NASA Technical Reports Server (NTRS)

Knoll, A. H.; Grotzinger, J. P.; Kaufman, A. J.; Kolosov, P.

1995-01-01

In the Olenek Uplift of northeastern Siberia, the Khorbusuonka Group and overlying Kessyusa and Erkeket formations preserve a significant record of terminal Proterozoic and basal Cambrian Earth history. A composite section more than 350 m thick is reconstructed from numerous exposures along the Khorbusuonka River. The Khorbusuonka Group comprises three principal sedimentary sequences: peritidal dolomites of the Mastakh Formation, which are bounded above and below by red beds; the Khatyspyt and most of the overlying Turkut formations, which shallow upward from relatively deep-water carbonaceous micrites to cross-bedded dolomitic grainstones and stromatolites; and a thin upper Turkut sequence bounded by karst surfaces. The overlying Kessyusa Formation is bounded above and below by erosional surfaces and contains additional parasequence boundaries internally. Ediacaran metazoans, simple trace fossils, and vendotaenids occur in the Khatyspyt Formation; small shelly fossils, more complex trace fossils, and acritarchs all appear near the base of the Kessyusa Formation and diversify upward. The carbon-isotopic composition of carbonates varies stratigraphically in a pattern comparable to that determined for other terminal Proterozoic and basal Cambrian successions. In concert, litho-, bio-, and chemostratigraphic data indicate the importance of the Khorbusuonka Group in the global correlation of terminal Proterozoic sedimentary rocks. Stratigraphic data and a recently determined radiometric date on basal Kessyusa volcanic breccias further underscore the significance of the Olenek region in investigations of the Proterozoic-cambrian boundary.

Integrated approaches to terminal Proterozoic stratigraphy: an example from the Olenek Uplift, northeastern Siberia.

PubMed

Knoll, A H; Grotzinger, J P; Kaufman, A J; Kolosov, P

1995-01-01

In the Olenek Uplift of northeastern Siberia, the Khorbusuonka Group and overlying Kessyusa and Erkeket formations preserve a significant record of terminal Proterozoic and basal Cambrian Earth history. A composite section more than 350 m thick is reconstructed from numerous exposures along the Khorbusuonka River. The Khorbusuonka Group comprises three principal sedimentary sequences: peritidal dolomites of the Mastakh Formation, which are bounded above and below by red beds; the Khatyspyt and most of the overlying Turkut formations, which shallow upward from relatively deep-water carbonaceous micrites to cross-bedded dolomitic grainstones and stromatolites; and a thin upper Turkut sequence bounded by karst surfaces. The overlying Kessyusa Formation is bounded above and below by erosional surfaces and contains additional parasequence boundaries internally. Ediacaran metazoans, simple trace fossils, and vendotaenids occur in the Khatyspyt Formation; small shelly fossils, more complex trace fossils, and acritarchs all appear near the base of the Kessyusa Formation and diversify upward. The carbon-isotopic composition of carbonates varies stratigraphically in a pattern comparable to that determined for other terminal Proterozoic and basal Cambrian successions. In concert, litho-, bio-, and chemostratigraphic data indicate the importance of the Khorbusuonka Group in the global correlation of terminal Proterozoic sedimentary rocks. Stratigraphic data and a recently determined radiometric date on basal Kessyusa volcanic breccias further underscore the significance of the Olenek region in investigations of the Proterozoic-cambrian boundary.

Interaction of NaOH solutions with silica surfaces

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

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Interaction of NaOH solutions with silica surfaces

DOE PAGES

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

2018-01-16

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Geochemistry of Rock Samples Collected from the Iron Hill Carbonatite Complex, Gunnison County, Colorado

USGS Publications Warehouse

Van Gosen, Bradley S.

2008-01-01

A study conducted in 2006 by the U.S. Geological Survey collected 57 surface rock samples from nine types of intrusive rock in the Iron Hill carbonatite complex. This intrusive complex, located in Gunnison County of southwestern Colorado, is known for its classic carbonatite-alkaline igneous geology and petrology. The Iron Hill complex is also noteworthy for its diverse mineral resources, including enrichments in titanium, rare earth elements, thorium, niobium (columbium), and vanadium. This study was performed to reexamine the chemistry and metallic content of the major rock units of the Iron Hill complex by using modern analytical techniques, while providing a broader suite of elements than the earlier published studies. The report contains the geochemical analyses of the samples in tabular and digital spreadsheet format, providing the analytical results for 55 major and trace elements.

Vibrational Stark effect spectroscopy at the interface of Ras and Rap1A bound to the Ras binding domain of RalGDS reveals an electrostatic mechanism for protein-protein interaction.

PubMed

Stafford, Amy J; Ensign, Daniel L; Webb, Lauren J

2010-11-25

Electrostatic fields at the interface of the Ras binding domain of the protein Ral guanine nucleotide dissociation stimulator (RalGDS) with the structurally analogous GTPases Ras and Rap1A were measured with vibrational Stark effect (VSE) spectroscopy. Eleven residues on the surface of RalGDS that participate in this protein-protein interaction were systematically mutated to cysteine and subsequently converted to cyanocysteine in order to introduce a nitrile VSE probe in the form of the thiocyanate (SCN) functional group. The measured SCN absorption energy on the monomeric protein was compared with solvent-accessible surface area (SASA) calculations and solutions to the Poisson-Boltzmann equation using Boltzmann-weighted structural snapshots from molecular dynamics simulations. We found a weak negative correlation between SASA and measured absorption energy, indicating that water exposure of protein surface amino acids can be estimated from experimental measurement of the magnitude of the thiocyanate absorption energy. We found no correlation between calculated field and measured absorption energy. These results highlight the complex structural and electrostatic nature of the protein-water interface. The SCN-labeled RalGDS was incubated with either wild-type Ras or wild-type Rap1A, and the formation of the docked complex was confirmed by measurement of the dissociation constant of the interaction. The change in absorption energy of the thiocyanate functional group due to complex formation was related to the change in electrostatic field experienced by the nitrile functional group when the protein-protein interface forms. At some locations, the nitrile experiences the same shift in field when bound to Ras and Rap1A, but at others, the change in field is dramatically different. These differences identify residues on the surface of RalGDS that direct the specificity of RalGDS binding to its in vivo binding partner, Rap1A, through an electrostatic mechanism.

Formation of a physiological complex between TRPV2 and RGA protein promotes cell surface expression of TRPV2.

PubMed

Stokes, Alexander J; Wakano, Clay; Del Carmen, Kimberly A; Koblan-Huberson, Murielle; Turner, Helen

2005-03-01

The transient receptor potential, sub-family Vanilloid (TRPV)(2) cation channel is activated in response to extreme temperature elevations in sensory neurons. However, TRPV2 is widely expressed in tissues with no sensory function, including cells of the immune system. Regulation of GRC, the murine homolog of TRPV2 has been studied in insulinoma cells and myocytes. GRC is activated in response to certain growth factors and neuropeptides, via a mechanism that involves regulated access of the channel to the plasma membrane. This is likely to be an important primary control mechanism for TRPV2 outside the CNS. Here, we report that a regulated trafficking step controls the access of TRPV2 to the cell surface in mast cells. In mast cells, elevations in cytosolic cAMP are sufficient to drive plasma membrane localization of TRPV2. We have previously proposed that the recombinase gene activator protein (RGA), a four-transmembrane domain, intracellular protein, associates with TRPV2 during the biosynthesis and early trafficking of the channel. We use a polyclonal antibody to RGA to confirm the formation of a physiological complex between RGA and TRPV2. Finally, we show that over-expression of the RGA protein potentiates the basal surface localization of TRPV2. We propose that trafficking and activation mechanisms intersect for TRPV2, and that cAMP mobilizing stimuli may regulate TRPV2 localization in non-sensory cells. RGA participates in the control of TRPV2 surface levels, and co-expression of RGA may be a key component of experimental systems that seek to study TRPV2 physiology.

Self-organized pattern formation at organic-inorganic interfaces during deposition: Experiment versus modeling

NASA Astrophysics Data System (ADS)

Szillat, F.; Mayr, S. G.

2011-09-01

Self-organized pattern formation during physical vapor deposition of organic materials onto rough inorganic substrates is characterized by a complex morphological evolution as a function of film thickness. We employ a combined experimental-theoretical study using atomic force microscopy and numerically solved continuum rate equations to address morphological evolution in the model system: poly(bisphenol A carbonate) on polycrystalline Cu. As the key ingredients for pattern formation, (i) curvature and interface potential driven surface diffusion, (ii) deposition noise, and (iii) interface boundary effects are identified. Good agreement of experiments and theory, fitting only the Hamaker constant and diffusivity within narrow physical parameter windows, corroborates the underlying physics and paves the way for computer-assisted interface engineering.

The laser radiation action on the crystal formation processes in the biological fluids

NASA Astrophysics Data System (ADS)

Malov, Alexander N.; Vaichas, Andrey A.; Novikova, Evgeniya A.

2016-11-01

The results of an experimental study of the laser radiation effect on the crystal`s formation in the volume of biological fluids that are complex multi-component solutions have been discussing. Are investigated white and natural bile in vitro. The qualitative changes were observed. Thus, at the bottom of the cell in which bile is not exposed to the laser radiation, the crystals are formed. In the irradiated bile gallstone has a thin layer of a homogeneous viscous colloidal liquid with very small, visible in polarized light crystalline formations was got. Irradiated laser bile's gallstone was covered evenly white deposit without surface defect unlike gallstone in bile without radiation exposure. A possible mechanism to explain the laser radiation action on the mineral formation in biological fluids and also practical application of this effect have been suggesting too.

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

PubMed

Rodrigues, Maria A A; Mendes, Débora C; Ramamurthy, Vaidhyanathan; Da Silva, José P

2017-11-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br - , Cl - , F - ) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

Formation of HDL-like complexes from apolipoprotein A-I(M) and DMPC.

PubMed

Suurkuusk, M; Singh, S K

2000-01-20

Conditions for the preparation of reconstituted high density lipoproteins (HDLs) by incubation of the synthetic lipid dimyristoylphosphatidylcholine (DMPC) and recombinant apolipoprotein A-I(M) have been investigated as a function of ratio of incubation lipid to protein, incubation temperature and the lipid form (multilamellar (MLV) or small unilamellar (SUV) vesicles). The size distributions of the resultant lipid-protein complex particles from various incubations have been evaluated by native gel electrophoresis. Structural changes of the protein after incorporation into these complex particles have been estimated by CD. Thermal characteristics of the particles has been examined by DSC and correlated with CD results. Titration calorimetry has been used to obtain interaction parameters based on a simplified binding model. It is hypothesized that the major enthalpic step in the production of rHDLs is the primary association step between protein and lipid vesicles. It has been shown that by raising the temperature and incubation ratio, the formation of rHDL particles can be directed towards smaller size and a narrower size distribution. The results have been described on the basis of a model where formation of discoidal particles requires prior saturation of vesicle surface area by adsorbed protein, thus explaining differences between particles formed from MLVs and SUVs.

Complex Pattern Formation from Current-Driven Dynamics of Single-Layer Epitaxial Islands on Crystalline Conducting Substrates

NASA Astrophysics Data System (ADS)

Kumar, Ashish; Dasgupta, Dwaipayan; Maroudas, Dimitrios

We report a systematic study of complex pattern formation resulting from the driven dynamics of single-layer homoepitaxial islands on face-centered cubic (FCC) crystalline conducting substrate surfaces under the action of an externally applied electric field. The analysis is based on an experimentally validated nonlinear model of mass transport via island edge atomic diffusion, which also accounts for edge diffusional anisotropy. We analyze the morphological stability and simulate the field-driven evolution of rounded islands for an electric field oriented along the fast diffusion direction. For larger than critical island sizes on {110} and {100} FCC substrates, we show that multiple necking instabilities generate complex island patterns, including void-containing islands, mediated by sequences of breakup and coalescence events and distributed symmetrically with respect to the electric field direction. We analyze the dependence of the formed patterns on the original island size and on the duration of application of the external field. Starting from a single large rounded island, we characterize the evolution of the number of daughter islands and their average size and uniformity. The analysis reveals that the pattern formation kinetics follows a universal scaling relation. Division of Materials Sciences & Engineering, Office of Basic Energy Sciences, U.S. Department of Energy (Award No.: DE-FG02-07ER46407).

The radiation environment on the surface of Mars - Summary of model calculations and comparison to RAD data

NASA Astrophysics Data System (ADS)

Matthiä, Daniel; Hassler, Donald M.; de Wet, Wouter; Ehresmann, Bent; Firan, Ana; Flores-McLaughlin, John; Guo, Jingnan; Heilbronn, Lawrence H.; Lee, Kerry; Ratliff, Hunter; Rios, Ryan R.; Slaba, Tony C.; Smith, Michael; Stoffle, Nicholas N.; Townsend, Lawrence W.; Berger, Thomas; Reitz, Günther; Wimmer-Schweingruber, Robert F.; Zeitlin, Cary

2017-08-01

The radiation environment at the Martian surface is, apart from occasional solar energetic particle events, dominated by galactic cosmic radiation, secondary particles produced in their interaction with the Martian atmosphere and albedo particles from the Martian regolith. The highly energetic primary cosmic radiation consists mainly of fully ionized nuclei creating a complex radiation field at the Martian surface. This complex field, its formation and its potential health risk posed to astronauts on future manned missions to Mars can only be fully understood using a combination of measurements and model calculations. In this work the outcome of a workshop held in June 2016 in Boulder, CO, USA is presented: experimental results from the Radiation Assessment Detector of the Mars Science Laboratory are compared to model results from GEANT4, HETC-HEDS, HZETRN, MCNP6, and PHITS. Charged and neutral particle spectra and dose rates measured between 15 November 2015 and 15 January 2016 and model results calculated for this time period are investigated.

Self-organizing layers from complex molecular anions

DOE PAGES

Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L.; ...

2018-05-14

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation ofmore » neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.« less

Cellular Binding of Anionic Nanoparticles is Inhibited by Serum Proteins Independent of Nanoparticle Composition.

PubMed

Fleischer, Candace C; Kumar, Umesh; Payne, Christine K

2013-09-01

Nanoparticles used in biological applications encounter a complex mixture of extracellular proteins. Adsorption of these proteins on the nanoparticle surface results in the formation of a "protein corona," which can dominate the interaction of the nanoparticle with the cellular environment. The goal of this research was to determine how nanoparticle composition and surface modification affect the cellular binding of protein-nanoparticle complexes. We examined the cellular binding of a collection of commonly used anionic nanoparticles: quantum dots, colloidal gold nanoparticles, and low-density lipoprotein particles, in the presence and absence of extracellular proteins. These experiments have the advantage of comparing different nanoparticles under identical conditions. Using a combination of fluorescence and dark field microscopy, flow cytometry, and spectroscopy, we find that cellular binding of these anionic nanoparticles is inhibited by serum proteins independent of nanoparticle composition or surface modification. We expect these results will aid in the design of nanoparticles for in vivo applications.

Self-organizing layers from complex molecular anions

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

Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L.

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation ofmore » neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.« less

Structure of a Water Monolayer on the Anatase TiO2(101) Surface

NASA Astrophysics Data System (ADS)

Patrick, Christopher E.; Giustino, Feliciano

2014-07-01

Titanium dioxide (TiO2) plays a central role in the study of artificial photosynthesis, owing to its ability to perform photocatalytic water splitting. Despite over four decades of intense research efforts in this area, there is still some debate over the nature of the first water monolayer on the technologically relevant anatase TiO2(101) surface. In this work, we use first-principles calculations to reverse engineer the experimental high-resolution x-ray photoelectron spectra measured for this surface by Walle et al. [J. Phys. Chem. C 115, 9545 (2011)] and find evidence supporting the existence of a mix of dissociated and molecular water in the first monolayer. Using both semilocal and hybrid functional calculations, we revise the current understanding of the adsorption energetics by showing that the energetic cost of water dissociation is reduced via the formation of a hydrogen-bonded hydroxyl-water complex. We also show that such a complex can provide an explanation of an unusual superstructure observed in high-resolution scanning tunneling microscopy experiments.

Synthesis of platinum nanowire networks using a soft template.

PubMed

Song, Yujiang; Garcia, Robert M; Dorin, Rachel M; Wang, Haorong; Qiu, Yan; Coker, Eric N; Steen, William A; Miller, James E; Shelnutt, John A

2007-12-01

Platinum nanowire networks have been synthesized by chemical reduction of a platinum complex using sodium borohydride in the presence of a soft template formed by cetyltrimethylammonium bromide in a two-phase water-chloroform system. The interconnected polycrystalline nanowires possess the highest surface area (53 +/- 1 m2/g) and electroactive surface area (32.4 +/- 3.6 m2/g) reported for unsupported platinum nanomaterials; the high surface area results from the small average diameter of the nanowires (2.2 nm) and the 2-10 nm pores determined by nitrogen adsorption measurements. Synthetic control over the network was achieved simply by varying the stirring rate and reagent concentrations, in some cases leading to other types of nanostructures including wormlike platinum nanoparticles. Similarly, substitution of a palladium complex for platinum gives palladium nanowire networks. A mechanism of formation of the metal nanowire networks is proposed based on confined metal growth within a soft template consisting of a network of swollen inverse wormlike micelles.

Structure of a Glomulin-RBX1-CUL1 complex: inhibition of a RING E3 ligase through masking of its E2-binding surface

PubMed Central

Duda, David M.; Olszewski, Jennifer L.; Tron, Adriana E.; Hammel, Michal; Lambert, Lester J.; Waddell, M. Brett; Mittag, Tanja; DeCaprio, James A.; Schulman, Brenda A.

2012-01-01

Summary The ~300 human Cullin-RING ligases (CRLs) are multisubunit E3s in which a RING protein, either RBX1 or RBX2, recruits an E2 to catalyze ubiquitination. RBX1-containing CRLs also can bind Glomulin (GLMN), which binds RBX1’s RING domain, regulates the RBX1-CUL1-containing SCFFBW7 complex, and is disrupted in the disease Glomuvenous Malformation. Here we report the crystal structure of a complex between GLMN, RBX1, and a fragment of CUL1. Structural and biochemical analyses reveal that GLMN adopts a HEAT-like repeat fold that tightly binds the E2-interacting surface of RBX1, inhibiting CRL-mediated chain formation by the E2 CDC34. The structure explains the basis for GLMN’s selectivity toward RBX1 over RBX2, and how disease-associated mutations disrupt GLMN-RBX1 interactions. Our study reveals a mechanism for RING E3 ligase regulation whereby an inhibitor blocks E2 access, and raises the possibility that other E3s are likewise controlled by cellular proteins that mask E2-binding surfaces to mediate inhibition. PMID:22748924

Chirality of weakly bound complexes: The potential energy surfaces for the hydrogen-peroxide−noble-gas interactions

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

Roncaratti, L. F., E-mail: lz@fis.unb.br; Leal, L. A.; Silva, G. M. de

2014-10-07

We consider the analytical representation of the potential energy surfaces of relevance for the intermolecular dynamics of weakly bound complexes of chiral molecules. In this paper we study the H{sub 2}O{sub 2}−Ng (Ng=He, Ne, Ar, Kr, and Xe) systems providing the radial and the angular dependence of the potential energy surface on the relative position of the Ng atom. We accomplish this by introducing an analytical representation which is able to fit the ab initio energies of these complexes in a wide range of geometries. Our analysis sheds light on the role that the enantiomeric forms and the symmetry ofmore » the H{sub 2}O{sub 2} molecule play on the resulting barriers and equilibrium geometries. The proposed theoretical framework is useful to study the dynamics of the H{sub 2}O{sub 2} molecule, or other systems involving O–O and S–S bonds, interacting by non-covalent forces with atoms or molecules and to understand how the relative orientation of the O–H bonds changes along collisional events that may lead to a hydrogen bond formation or even to selectivity in chemical reactions.« less

A SERS characterization of the stability of polythionates at the gold-electrolyte interface

NASA Astrophysics Data System (ADS)

Mirza, Jeff; Smith, Scott R.; Baron, Janet Y.; Choi, Yeonuk; Lipkowski, Jacek

2015-01-01

A gold nanorod (AuNR) array electrode was employed to record SERS spectra as a function of immersion time in electrolyte solutions of tetrathionate, trithionate, the [Au(S2O3)2]3- complex, sulfide and thiosulfate. The generalized two-dimensional correlation spectroscopy was employed to deconvolute broad bands in the SERS spectra. The results show that the polythionates, tetrathionate and trithionate, sulfide, and the [Au(S2O3)2]3- complex decompose to form cyclo-S8, polymeric and monoatomic sulfur at the gold surface. The relative amount of these different forms of sulfur in the film formed at the surface depends on the nature of the electrolyte species. The decomposition of tetrathionate leads predominantly to the formation of cyclo-S8. Comparable amounts of all three forms of sulfur are formed in the solution of the [Au(S2O3)2]3- complex. Monoatomic sulfur is formed predominantly at the gold surface in solutions of trithionate and thiosulfate. In contrast to the previous suggestions, the results of this study demonstrate that polythionates are not present in the passive layer during gold leaching from thiosulfate solutions at a prolonged leaching times.

Synthesis of nitrosobenzene via photocatalytic oxidation of aniline over MgO/TiO2 under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Jinsong; Xiong, Jinhua; Song, Yujie; Yu, Yan; Wu, Ling

2018-05-01

MgO/TiO2 (Degussa P25 TiO2) composites were prepared and were used as visible-light-driven photocatalysts for the oxidation of aniline to nitrosobenzene under oxygen atmosphere. The typical sample with 5 wt% MgO loaded P25 (MP5) shows comparable photocatalytic activity with 2 wt% Pt/P25. The analyzed results of XPS indicate that the lattice oxygen in the MP5 possess higher electron density than those in P25. The electron-rich lattice oxygen, formed as a result of MgO loaded, would facilitate the deprontonation of aniline. A new peak at 3310 cm-1 was observed in in-situ FTIR spectrum for aniline adsorbed on the sample MP5, suggesting that anilino species were formed. These species may be produced via the deprontonation of aniline and result in the formation of the surface complexes. Further XPS studies for aniline adsorbed on the catalysts also indicate the existence of the surface complexes. Under visible light irradiation, the electrons may excite from the surface complexes and initiate the oxidation processes. Finally, speculated photocatalytic processes for the oxidation of aniline to nitrosobenzene were proposed at molecular level.

Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite

PubMed Central

Lund, Tracy J; Koretsky, Carla M; Landry, Christopher J; Schaller, Melinda S; Das, Soumya

2008-01-01

Background The application of surface complexation models (SCMs) to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO), pure kaolinite (from two sources) and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs) describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples. PMID:18783619

Tensiometry and dilational rheology of mixed β-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

PubMed

Dan, Abhijit; Gochev, Georgi; Miller, Reinhard

2015-07-01

Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of β-lactoglobulin (BLG, 1 μM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface. Copyright © 2015 Elsevier Inc. All rights reserved.

Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

NASA Astrophysics Data System (ADS)

Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

2016-09-01

In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the photothermal vaporization and Coulomb explosion processes of the Pd and Pt nanoparticles are invoked as possible mechanisms for the lumpy nanoparticles formation.

Implant materials generate different peri-implant inflammatory factors: poly-ether-ether-ketone promotes fibrosis and microtextured titanium promotes osteogenic factors.

PubMed

Olivares-Navarrete, Rene; Hyzy, Sharon L; Slosar, Paul J; Schneider, Jennifer M; Schwartz, Zvi; Boyan, Barbara D

2015-03-15

An in vitro study examining factors produced by human mesenchymal stem cells on spine implant materials. The aim of this study was to examine whether the inflammatory microenvironment generated by cells on titanium-aluminum-vanadium (Ti-alloy, TiAlV) surfaces is affected by surface microtexture and whether it differs from that generated on poly-ether-ether-ketone (PEEK). Histologically, implants fabricated from PEEK have a fibrous connective tissue surface interface whereas Ti-alloy implants demonstrate close approximation with surrounding bone. Ti-alloy surfaces with complex micron/submicron scale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation whereas PEEK favors fibrous tissue formation. Human mesenchymal stem cells were cultured on tissue culture polystyrene, PEEK, smooth TiAlV, or macro-/micro-/nano-textured rough TiAlV (mmnTiAlV) disks. Osteoblastic differentiation and secreted inflammatory interleukins were assessed after 7 days. Fold changes in mRNAs for inflammation, necrosis, DNA damage, or apoptosis with respect to tissue culture polystyrene were measured by low-density polymerase chain reaction array. Data were analyzed by analysis of variance, followed by Bonferroni's correction of Student's t-test. Cells on PEEK upregulated mRNAs for chemokine ligand-2, interleukin (IL) 1β, IL6, IL8, and tumor necrosis factor. Cells grown on the mmnTiAlV had an 8-fold reduction in mRNAs for toll-like receptor-4. Cells grown on mmnTiAlV had reduced levels of proinflammatory interleukins. Cells on PEEK had higher mRNAs for factors strongly associated with cell death/apoptosis, whereas cells on mmnTiAlV exhibited reduced cytokine factor levels. All results were significant (P < 0.05). These results suggest that fibrous tissue around PEEK implants may be due to several factors: reduced osteoblastic differentiation of progenitor cells and production of an inflammatory environment that favors cell death via apoptosis and necrosis. Ti alloy surfaces with complex macro/micro/nanoscale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation. N/A.

Electrostatic rate enhancement and transient complex of protein-protein association.

PubMed

Alsallaq, Ramzi; Zhou, Huan-Xiang

2008-04-01

The association of two proteins is bounded by the rate at which they, via diffusion, find each other while in appropriate relative orientations. Orientational constraints restrict this rate to approximately 10(5)-10(6) M(-1) s(-1). Proteins with higher association rates generally have complementary electrostatic surfaces; proteins with lower association rates generally are slowed down by conformational changes upon complex formation. Previous studies (Zhou, Biophys J 1997;73:2441-2445) have shown that electrostatic enhancement of the diffusion-limited association rate can be accurately modeled by $k_{\\bf D}$ = $k_{D}0\\ {exp} ( - \\langle U_{el} \\rangle;{\\star}/k_{B} T),$ where k(D) and k(D0) are the rates in the presence and absence of electrostatic interactions, respectively, U(el) is the average electrostatic interaction energy in a "transient-complex" ensemble, and k(B)T is the thermal energy. The transient-complex ensemble separates the bound state from the unbound state. Predictions of the transient-complex theory on four protein complexes were found to agree well with the experiment when the electrostatic interaction energy was calculated with the linearized Poisson-Boltzmann (PB) equation (Alsallaq and Zhou, Structure 2007;15:215-224). Here we show that the agreement is further improved when the nonlinear PB equation is used. These predictions are obtained with the dielectric boundary defined as the protein van der Waals surface. When the dielectric boundary is instead specified as the molecular surface, electrostatic interactions in the transient complex become repulsive and are thus predicted to retard association. Together these results demonstrate that the transient-complex theory is predictive of electrostatic rate enhancement and can help parameterize PB calculations. (c) 2007 Wiley-Liss, Inc.

Ice formation on kaolinite: Insights from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sosso, Gabriele C.; Tribello, Gareth A.; Zen, Andrea; Pedevilla, Philipp; Michaelides, Angelos

2016-12-01

The formation of ice affects many aspects of our everyday life as well as important technologies such as cryotherapy and cryopreservation. Foreign substances almost always aid water freezing through heterogeneous ice nucleation, but the molecular details of this process remain largely unknown. In fact, insight into the microscopic mechanism of ice formation on different substrates is difficult to obtain even if state-of-the-art experimental techniques are used. At the same time, atomistic simulations of heterogeneous ice nucleation frequently face extraordinary challenges due to the complexity of the water-substrate interaction and the long time scales that characterize nucleation events. Here, we have investigated several aspects of molecular dynamics simulations of heterogeneous ice nucleation considering as a prototypical ice nucleating material the clay mineral kaolinite, which is of relevance in atmospheric science. We show via seeded molecular dynamics simulations that ice nucleation on the hydroxylated (001) face of kaolinite proceeds exclusively via the formation of the hexagonal ice polytype. The critical nucleus size is two times smaller than that obtained for homogeneous nucleation at the same supercooling. Previous findings suggested that the flexibility of the kaolinite surface can alter the time scale for ice nucleation within molecular dynamics simulations. However, we here demonstrate that equally flexible (or non flexible) kaolinite surfaces can lead to very different outcomes in terms of ice formation, according to whether or not the surface relaxation of the clay is taken into account. We show that very small structural changes upon relaxation dramatically alter the ability of kaolinite to provide a template for the formation of a hexagonal overlayer of water molecules at the water-kaolinite interface, and that this relaxation therefore determines the nucleation ability of this mineral.

Controlling morphology in swelling-induced wrinkled surfaces

NASA Astrophysics Data System (ADS)

Breid, Derek Ronald

Wrinkles represent a pathway towards the spontaneous generation of ordered surface microstructure for applications in numerous fields. Examples of highly complex ordered wrinkle structures abound in Nature, but the ability to harness this potential for advanced material applications remains limited. This work focuses on understanding the relationship between the patterns on a wrinkled surface and the experimental conditions under which they form. Because wrinkles form in response to applied stresses, particular attention is given to the nature of the stresses in a wrinkling surface. The fundamental insight gained was then utilized to account for observed wrinkle formation phenomena within more complex geometric and kinetic settings. In order to carefully control and measure the applied stresses on a wrinkling film, a swelling-based system was developed using poly(dimethylsiloxane) (PDMS), surface-oxidized with a UV-ozone treatment. The swelling of the oxidized surface upon exposure to an ethanol vapor atmosphere was characterized using beam-bending experiments, allowing quantitative measurements of the applied stress. The wrinkle morphologies were characterized as a function of the overstress, defined as the ratio of the applied swelling stress to the critical buckling stress of the material. A transition in the dominant morphology of the wrinkled surfaces from dimple patterns to ridge patterns was observed at an overstress value of ˜2. The pattern dependence of wrinkles on the ratio of the principal stresses was examined by fabricating samples with a gradient prestress. When swollen, these samples exhibited a smooth morphological transition from non-equibiaxial to equibiaxial patterns, with prestrains as low as 2.5% exhibiting non-equibiaxial characteristics. This transition was seen both in samples with low and high overstresses. To explore the impact of these stress states in more complex geometries, wrinkling hemispherical surfaces with radii of curvature ranging from 50--1000 μm were fabricated using the same material system. Upon wrinkling, the hemispheres formed complex hierarchical assemblies reminiscent of naturally occurring structures. The curvature of a surface exhibited a correlation with its critical buckling stress, independent of other factors. This enables the surface curvature to be used as an independent control over the dimple-to-ridge transition which occurs as a function of overstress. As in the flat buckling surfaces, this transition was shown to occur at an overstress value of ˜2. Surface curvature was also shown to improve the observed hexagonal ordering of the dimple arrays, resulting in the formation of regular "golf ball" structures. Geometric effects in finite flat plates were also examined. Using circular masks during the oxidation process, plates with radii ranging from 0.4--8.6 mm were created. Upon wrinkling, a dimple-to-ridge transition was observed with increasing plate size, with the morphological switch occurring at a radius of ˜2 mm. This observed transition was not found to be due to the inherent mechanics of plates of different sizes, but instead to a reduction in the oxide conversion due to shadowing or stagnation caused by the masking process, which lowered the applied overstress. The shape of the finite plate was found to have little impact on the resulting wrinkle morphologies. Kinetic aspects of wrinkling were qualitatively characterized by observing the wrinkling process over the course of swelling. Wrinkling was observed to frontally propagate across the surface, and the ordering of the patterns which developed showed a qualitative correlation with the degree of uniformity in the advancing wrinkle front. Swelling with different solvents was found to lead to the formation of different patterns, based on the swelling kinetics of the UVO-treated PDMS upon exposure to each solvent.

Preparation, characterization and binding behaviors of host-guest inclusion complexes of metoclopramide hydrochloride with α- and β-cyclodextrin molecules

NASA Astrophysics Data System (ADS)

Barman, Siti; Barman, Biraj Kumar; Roy, Mahendra Nath

2018-03-01

The supramolecular interaction of metoclopramide hydrochloride (MP) with α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD) has been inspected by ultraviolet-visible (UV-vis) light, infra-red (IR) light, fluorescence and 1H NMR spectroscopy. The formation of an inclusion complex greatly affects the physical-chemical properties of the guest molecules, such as solubility, chemical reactivity and the spectroscopic and electrochemical properties. Thus the changes in the spectral properties and physico-chemical properties confirm the inclusion complex formation. Surface tension, conductivity studies and Job's plot indicate a 1: 1 stoichiometry of the MP:CD host-guest inclusion complexes. The binding/association constants have been evaluated by both UV-Vis and fluorescence spectroscopic study indicating a higher degree of encapsulation for β-cyclodextrin (β-CD). Furthermore, the negative value of thermodynamic parameter (ΔG°) of the host-guest system suggests that the inclusion process proceeded spontaneously at 298.15 K. Based on the NMR data, the plausible mode of interaction of MP:α-CD and MP:β-CD complexes were proposed, which suggested that lipophilic aromatic ring of the MP entered into the cavity of CDs from the wider side, with the amide (sbnd CONH) and methoxy (-OMe) residues inside the CD cavity.

Rethinking stratigraphy and site formation of the Pleistocene deposit at Cueva Negra del Estrecho del Río Quípar (Caravaca de la Cruz, Spain)

NASA Astrophysics Data System (ADS)

Angelucci, Diego E.; Anesin, Daniela; López Martínez, Mariano; Haber Uriarte, María; Rodríguez Estrella, Tomás; Walker, Michael J.

2013-11-01

Cueva Negra del Estrecho del Río Quípar (Caravaca de la Cruz, Murcia, Spain), hereinafter Cueva Negra, is a key-site for understanding the early peopling of Europe. Since 1990, systematic excavation has revealed an intriguing assemblage of lithic and faunal remains, and hominin teeth. It was deposited 0.99-0.78 Ma according to palaeomagnetic and biostratigraphical data; pollen data indicate warm moist conditions. Recently, possible evidence of thermal alteration was detected in a deep part of the deposit. We report here on our revision of the Cueva Negra stratigraphy, and offer information on site formation processes, based on new field observations and preliminary data from soil micromorphology. The Cueva Negra succession comprises three main stratigraphical complexes. Complex 1 is late Holocene. Complexes 2 and 3 are Pleistocene and are formed mainly of alluvial sediment, with subordinate inputs from the cave walls. Complexes 2 and 3 were accumulated almost without interruption, being separated by an erosive surface truncating a thin alluvial soil developed at the top of Complex 3. Our initial micromorphological findings indicate that anthropic inputs are mostly in derived positions, very likely having undergone inward displacement from the mouth of the rock-shelter.

Organic iron (III) complexing ligands during an iron enrichment experiment in the western subarctic North Pacific

NASA Astrophysics Data System (ADS)

Kondo, Yoshiko; Takeda, Shigenobu; Nishioka, Jun; Obata, Hajime; Furuya, Ken; Johnson, William Keith; Wong, C. S.

2008-06-01

Complexation of iron (III) with natural organic ligands was investigated during a mesoscale iron enrichment experiment in the western subarctic North Pacific (SEEDS II). After the iron infusions, ligand concentrations increased rapidly with subsequent decreases. While the increases of ligands might have been partly influenced by amorphous iron colloids formation (12-29%), most in-situ increases were attributable to the <200 kDa fraction. Dilution of the fertilized patch may have contributed to the rapid decreases of the ligands. During the bloom decline, ligand concentration increased again, and the high concentrations persisted for 10 days. The conditional stability constant was not different between inside and outside of the fertilized patch. These results suggest that the chemical speciation of the released iron was strongly affected by formation of the ligands; the production of ligands observed during the bloom decline will strongly impact the iron cycle and bioavailability in the surface water.

Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

PubMed

Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

2015-04-21

Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.

On the formation of molecules and solid-state compounds from the AGB to the PN phases

NASA Astrophysics Data System (ADS)

García-Hernández, D. A.; Manchado, A.

2016-07-01

During the asymptoyic giant branch (AGB) phase, different elements are dredge- up to the stellar surface depending on progenitor mass and metallicity. When the mass loss increases at the end of the AGB, a circumstellar dust shell is formed, where different (C-rich or O-rich) molecules and solid-state compounds are formed. These are further processed in the transition phase between AGB stars and planetary nebulae (PNe) to create more complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors in C-rich environments and oxides and crystalline silicates in O-rich ones). We present an observational review of the different molecules and solid-state materials that are formed from the AGB to the PN phases. We focus on the formation routes of complex fullerene (and fullerene-based) molecules as well as on the level of dust processing depending on metallicity.

Improved adhesion of Ni films on X-ray damaged polytetrafluoroethylene

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1981-01-01

The considered investigation shows that the adhesion of evaporated Ni on polytetrafluoroethylene (PTFE) is enhanced by irradiating the PTFE surface prior to evaporation. Evidence obtained with the aid of X-ray photoelectron spectroscopy is presented concerning the association of the enhanced adhesion with an interfacial chemical reaction. Evaporated Ni clearly adheres better to the X-ray damaged PTFE surface than to the undamaged surface. There is evidence that the improved adhesion is not related to the Ni-C bond, but rather to the NiF2. A possible mechanism which may be consistent with the data is the formation of a F-Ni-C complex, where C is a member of the polymer chain.

Surface-modified TiO2 powders with phenol derivatives: A comparative DFT and experimental study

NASA Astrophysics Data System (ADS)

Sredojević, Dušan N.; Kovač, Tijana; Džunuzović, Enis; Ðorđević, Vesna; Grgur, Branimir N.; Nedeljković, Jovan M.

2017-10-01

The charge transfer complex formation between TiO2 powder and variety of phenol derivatives (phenol, 4-nitrophenol, 4-bromophenol, 4-tert-butylphenol, hydroquinone) was achieved. The red-shift of optical absorption was observed upon surface modification of TiO2 powders with phenol derivatives. The influence of substituent functional groups in para position on the optical band gap and conduction band edge of inorganic/organic hybrids was studied using reflection spectroscopy and cyclic voltammetry. The experimental findings were supported by density functional theory calculations. The measured reflection spectra of surface-modified TiO2 powders with phenol derivatives were compared with calculated electronic excitation spectra of corresponding model systems.

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Brief Communication: Mapping river ice using drones and structure from motion

NASA Astrophysics Data System (ADS)

Alfredsen, Knut; Haas, Christian; Tuhtan, Jeffrey A.; Zinke, Peggy

2018-02-01

In cold climate regions, the formation and break-up of river ice is important for river morphology, winter water supply, and riparian and instream ecology as well as for hydraulic engineering. Data on river ice is therefore significant, both to understand river ice processes directly and to assess ice effects on other systems. Ice measurement is complicated due to difficult site access, the inherent complexity of ice formations, and the potential danger involved in carrying out on-ice measurements. Remote sensing methods are therefore highly useful, and data from satellite-based sensors and, increasingly, aerial and terrestrial imagery are currently applied. Access to low cost drone systems with quality cameras and structure from motion software opens up a new possibility for mapping complex ice formations. Through this method, a georeferenced surface model can be built and data on ice thickness, spatial distribution, and volume can be extracted without accessing the ice, and with considerably fewer measurement efforts compared to traditional surveying methods. A methodology applied to ice mapping is outlined here, and examples are shown of how to successfully derive quantitative data on ice processes.

NSF- and SNARE-mediated membrane fusion is required for nuclear envelope formation and completion of nuclear pore complex assembly in Xenopus laevis egg extracts.

PubMed

Baur, Tina; Ramadan, Kristijan; Schlundt, Andreas; Kartenbeck, Jürgen; Meyer, Hemmo H

2007-08-15

Despite the progress in understanding nuclear envelope (NE) reformation after mitosis, it has remained unclear what drives the required membrane fusion and how exactly this is coordinated with nuclear pore complex (NPC) assembly. Here, we show that, like other intracellular fusion reactions, NE fusion in Xenopus laevis egg extracts is mediated by SNARE proteins that require activation by NSF. Antibodies against Xenopus NSF, depletion of NSF or the dominant-negative NSF(E329Q) variant specifically inhibited NE formation. Staging experiments further revealed that NSF was required until sealing of the envelope was completed. Moreover, excess exogenous alpha-SNAP that blocks SNARE function prevented membrane fusion and caused accumulation of non-flattened vesicles on the chromatin surface. Under these conditions, the nucleoporins Nup107 and gp210 were fully recruited, whereas assembly of FxFG-repeat-containing nucleoporins was blocked. Together, we define NSF- and SNARE-mediated membrane fusion events as essential steps during NE formation downstream of Nup107 recruitment, and upstream of membrane flattening and completion of NPC assembly.

Features of the complexation of octadecane-2,4-dione and lanthanide ions in Langmuir monolayers

NASA Astrophysics Data System (ADS)

Sokolov, M. E.; Repina, I. N.; Raitman, O. A.; Kolokolov, F. A.; Panyushkin, V. T.

2016-05-01

Monolayers of octadecane-2,4-dione on the surfaces of EuCl3 and TbCl3 solutions in the concentration range of 1 × 10-4 to 5 × 10-3 M at pH 5.8 are studied. It is found that the limiting area of octadecane-2,4-dione molecule in a monolayer dependence on Eu3+ and Tb3+ concentration is of extreme nature. The formation of complex compounds in the ligand monolayer is postulated, and structures are proposed for these compounds at different concentrations of metal ions.

The census of complex organic molecules in the solar-type protostar IRAS16293-2422

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

Jaber, Ali A.; Ceccarelli, C.; Kahane, C.

2014-08-10

Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (≳30-40 K) and released in the gas phase at dust temperatures of ≳100 K. However, recent detections of COMs in ≲20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we presentmore » a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (≲30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10{sup –10}. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.« less

The Census of Complex Organic Molecules in the Solar-type Protostar IRAS16293-2422

NASA Astrophysics Data System (ADS)

Jaber, Ali A.; Ceccarelli, C.; Kahane, C.; Caux, E.

2014-08-01

Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (gsim30-40 K) and released in the gas phase at dust temperatures of gsim100 K. However, recent detections of COMs in lsim20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we present a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (lsim30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10-10. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.

Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Chuang, K.-J.; Ioppolo, S.; Qasim, D.; van Dishoeck, E. F.; Linnartz, H.

2017-06-01

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, I.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH2CH(OH)CH2OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH2CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.

Novel Insights into the Proteus mirabilis Crystalline Biofilm Using Real-Time Imaging

PubMed Central

Wilks, Sandra A.; Fader, Mandy J.; Keevil, C. William

2015-01-01

The long-term use of indwelling catheters results in a high risk from urinary tract infections (UTI) and blockage. Blockages often occur from crystalline deposits, formed as the pH rises due to the action of urease-producing bacteria; the most commonly found species being Proteus mirabilis. These crystalline biofilms have been found to develop on all catheter materials with P. mirabilis attaching to all surfaces and forming encrustations. Previous studies have mainly relied on electron microscopy to describe this process but there remains a lack of understanding into the stages of biofilm formation. Using an advanced light microscopy technique, episcopic differential interference contrast (EDIC) microscopy combined with epifluorescence (EF), we describe a non-destructive, non-contact, real-time imaging method used to track all stages of biofilm development from initial single cell attachment to complex crystalline biofilm formation. Using a simple six-well plate system, attachment of P. mirabilis (in artificial urine) to sections of silicone and hydrogel latex catheters was tracked over time (up to 24 days). Using EDIC and EF we show how initial attachment occurred in less than 1 h following exposure to P. mirabilis. This was rapidly followed by an accumulation of an additional material (indicated to be carbohydrate based using lectin staining) and the presence of highly elongated, motile cells. After 24 h exposure, a layer developed above this conditioning film and within 4 days the entire surface (of both catheter materials) was covered with diffuse crystalline deposits with defined crystals embedded. Using three-dimensional image reconstruction software, cells of P. mirabilis were seen covering the crystal surfaces. EDIC microscopy could resolve these four components of the complex crystalline biofilm and the close relationship between P. mirabilis and the crystals. This real-time imaging technique permits study of this complex biofilm development with no risk of artefacts due to sample manipulation. A full understanding of the stages and components involved in crystalline encrustation formation will aid in the development of new protocols to manage and ultimately prevent catheter blockage. PMID:26516766

Novel Insights into the Proteus mirabilis Crystalline Biofilm Using Real-Time Imaging.

PubMed

Wilks, Sandra A; Fader, Mandy J; Keevil, C William

2015-01-01

The long-term use of indwelling catheters results in a high risk from urinary tract infections (UTI) and blockage. Blockages often occur from crystalline deposits, formed as the pH rises due to the action of urease-producing bacteria; the most commonly found species being Proteus mirabilis. These crystalline biofilms have been found to develop on all catheter materials with P. mirabilis attaching to all surfaces and forming encrustations. Previous studies have mainly relied on electron microscopy to describe this process but there remains a lack of understanding into the stages of biofilm formation. Using an advanced light microscopy technique, episcopic differential interference contrast (EDIC) microscopy combined with epifluorescence (EF), we describe a non-destructive, non-contact, real-time imaging method used to track all stages of biofilm development from initial single cell attachment to complex crystalline biofilm formation. Using a simple six-well plate system, attachment of P. mirabilis (in artificial urine) to sections of silicone and hydrogel latex catheters was tracked over time (up to 24 days). Using EDIC and EF we show how initial attachment occurred in less than 1 h following exposure to P. mirabilis. This was rapidly followed by an accumulation of an additional material (indicated to be carbohydrate based using lectin staining) and the presence of highly elongated, motile cells. After 24 h exposure, a layer developed above this conditioning film and within 4 days the entire surface (of both catheter materials) was covered with diffuse crystalline deposits with defined crystals embedded. Using three-dimensional image reconstruction software, cells of P. mirabilis were seen covering the crystal surfaces. EDIC microscopy could resolve these four components of the complex crystalline biofilm and the close relationship between P. mirabilis and the crystals. This real-time imaging technique permits study of this complex biofilm development with no risk of artefacts due to sample manipulation. A full understanding of the stages and components involved in crystalline encrustation formation will aid in the development of new protocols to manage and ultimately prevent catheter blockage.

Tribological properties of multifunctional coatings with Shape Memory Effect in abrasive wear

NASA Astrophysics Data System (ADS)

Blednova, Zh. M.; Dmitrenko, D. V.; Balaev, E. U. O.

2018-01-01

The article gives research results of the abrasive wear process on samples made of Steel 1045, U10 and with applied composite surface layer "Nickel-Multicomponent material with Shape Memory Effect (SME) based on TiNi". For the tests we have chosen TiNiZr, which is in the martensite state and TiNiHfCu, which is in the austenitic state at the test temperature. The formation of the surface layer was carried out by high-speed oxygen-fuel deposition in a protective atmosphere of argon. In the wear test, Al2O3 corundum powder was used as an abrasive. It is shown that the wear rate of samples with a composite surface layer of multicomponent materials with SME is significantly reduced in comparison with the base, which is explained by reversible phase transformations of the surface layer with SME. After carrying out the additional surface plastic deformation (SPD), the resistance of the laminated composition to abrasion wear has greatly enhanced, due to the reinforcing effect of the SPD. It is recommended for products working in conditions of abrasive wear and high temperatures to use the complex formation technology of the surface composition "steel-nickel-material with high-temperature SME", including preparation of the substrate surface and the deposited material, high-speed spraying in the protective atmosphere of argon, followed by SPD.

Hijacking Complement Regulatory Proteins for Bacterial Immune Evasion.

PubMed

Hovingh, Elise S; van den Broek, Bryan; Jongerius, Ilse

2016-01-01

The human complement system plays an important role in the defense against invading pathogens, inflammation and homeostasis. Invading microbes, such as bacteria, directly activate the complement system resulting in the formation of chemoattractants and in effective labeling of the bacteria for phagocytosis. In addition, formation of the membrane attack complex is responsible for direct killing of Gram-negative bacteria. In turn, bacteria have evolved several ways to evade complement activation on their surface in order to be able to colonize and invade the human host. One important mechanism of bacterial escape is attraction of complement regulatory proteins to the microbial surface. These molecules are present in the human body for tight regulation of the complement system to prevent damage to host self-surfaces. Therefore, recruitment of complement regulatory proteins to the bacterial surface results in decreased complement activation on the microbial surface which favors bacterial survival. This review will discuss recent advances in understanding the binding of complement regulatory proteins to the bacterial surface at the molecular level. This includes, new insights that have become available concerning specific conserved motives on complement regulatory proteins that are favorable for microbial binding. Finally, complement evasion molecules are of high importance for vaccine development due to their dominant role in bacterial survival, high immunogenicity and homology as well as their presence on the bacterial surface. Here, the use of complement evasion molecules for vaccine development will be discussed.

Hijacking Complement Regulatory Proteins for Bacterial Immune Evasion

PubMed Central

Hovingh, Elise S.; van den Broek, Bryan; Jongerius, Ilse

2016-01-01

The human complement system plays an important role in the defense against invading pathogens, inflammation and homeostasis. Invading microbes, such as bacteria, directly activate the complement system resulting in the formation of chemoattractants and in effective labeling of the bacteria for phagocytosis. In addition, formation of the membrane attack complex is responsible for direct killing of Gram-negative bacteria. In turn, bacteria have evolved several ways to evade complement activation on their surface in order to be able to colonize and invade the human host. One important mechanism of bacterial escape is attraction of complement regulatory proteins to the microbial surface. These molecules are present in the human body for tight regulation of the complement system to prevent damage to host self-surfaces. Therefore, recruitment of complement regulatory proteins to the bacterial surface results in decreased complement activation on the microbial surface which favors bacterial survival. This review will discuss recent advances in understanding the binding of complement regulatory proteins to the bacterial surface at the molecular level. This includes, new insights that have become available concerning specific conserved motives on complement regulatory proteins that are favorable for microbial binding. Finally, complement evasion molecules are of high importance for vaccine development due to their dominant role in bacterial survival, high immunogenicity and homology as well as their presence on the bacterial surface. Here, the use of complement evasion molecules for vaccine development will be discussed. PMID:28066340

Rat Muc4 (sialomucin complex) reduces binding of anti-ErbB2 antibodies to tumor cell surfaces, a potential mechanism for herceptin resistance.

PubMed

Price-Schiavi, Shari A; Jepson, Scott; Li, Peter; Arango, Maria; Rudland, Philip S; Yee, Lisa; Carraway, Kermit L

2002-06-20

Muc4 (also called sialomucin complex), the rat homolog of human MUC4, is a heterodimeric glycoprotein complex that consists of a peripheral O-glycosylated mucin subunit, ASGP-1, tightly but noncovalently linked to a N-glycosylated transmembrane subunit, ASGP-2. The complex is expressed in a number of normal, vulnerable epithelial tissues, including mammary gland, uterus, colon, cornea and trachea. Muc4/SMC is also overexpressed or aberrantly expressed on a number of human tumors including breast tumors. Overexpression of Muc4/SMC has been shown to block cell-cell and cell-matrix interactions, protect tumor cells from immune surveillance and promote metastasis. In addition, as a ligand for ErbB2, Muc4/SMC can potentiate phosphorylation of ErbB2 and potentially alter signals generated from this receptor. Using A375 human melanoma cells and MCF7 human breast adenocarcinoma cells stably transfected with tetracycline regulatable Muc4, we have investigated whether overexpression of Muc4/SMC can repress antibody binding to cell surface-expressed ErbB2. Overexpression of Muc4/SMC does not affect the level of ErbB2 expression in either cell line, but it does reduce binding of a number of anti-ErbB2 antibodies, including Herceptin. Interestingly, overexpression of ErbB2 does not block binding of other unrelated antibodies of the same isotype, suggesting that the reduction in ErbB2 antibody binding is due to complex formation of Muc4/SMC and ErbB2. Furthermore, capping of Muc4/SMC with anti-Muc4/SMC antibodies reduces antibody binding to ErbB2 instead of increasing binding, again suggesting that reduced antibody binding to ErbB2 is due to steric hindrance from complex formation of Muc4/SMC and ErbB2. Thus, overexpression of Muc4/SMC on tumor cells may have both prognostic and therapeutic relevance. Copyright 2002 Wiley-Liss, Inc.

Chabazite and dolomite formation in a dolocrete profile: An example of a complex alkaline paragenesis in Lanzarote, Canary Islands

NASA Astrophysics Data System (ADS)

Alonso-Zarza, Ana M.; Bustamante, Leticia; Huerta, Pedro; Rodríguez-Berriguete, Álvaro; Huertas, María José

2016-05-01

This paper studies the weathering and soil formation processes operating on detrital sediments containing alkaline volcanic rock fragments of the Mirador del Río dolocrete profile. The profile consists of a lower horizon of removilised weathered basalts, an intermediate red sandy mudstones horizon with irregular carbonate layers and a topmost horizon of amalgamated carbonate layers with root traces. Formation occurred in arid to semiarid climates, giving place to a complex mineralogical association, including Mg-carbonates and chabazite, rarely described in cal/dolocretes profiles. Initial vadose weathering processes occurred in the basalts and in directly overlying detrital sediments, producing (Stage 1) red-smectites and dolomicrite. Dominant phreatic (Stage 2) conditions allowed precipitation of coarse-zoned dolomite and chabazite filling porosities. In Stages 3 and 4, mostly pedogenic, biogenic processes played an important role in dolomite and calcite accumulation in the profile. Overall evolution of the profile and its mineralogical association involved initial processes dominated by alteration of host rock, to provide silica and Mg-rich alkaline waters, suitable for chabazite and dolomite formation, without a previous carbonate phase. Dolomite formed both abiogenically and biogenically, but without a previous carbonate precursor and in the absence of evaporites. Dominance of calcite towards the profile top is the result of Mg/Ca decrease in the interstitial meteoric waters due to decreased supply of Mg from weathering, and increased supply of Ca in aeolian dust. Meteoric origin of the water is confirmed by C and O isotope values, which also indicate lack of deep sourced CO2. The dolocrete studied and its complex mineral association reveal the complex interactions that occur at surface during weathering and pedogenesis of basalt-sourced rocks.

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

Co-Binding of Pharmaceutical Compounds at Mineral Surfaces: Molecular Investigations of Dimer Formation at Goethite/Water Interfaces.

PubMed

Xu, Jing; Marsac, Rémi; Costa, Dominique; Cheng, Wei; Wu, Feng; Boily, Jean-François; Hanna, Khalil

2017-08-01

The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demonstrates this important possibility for the case of two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) bound at goethite (α-FeOOH) used as a model mineral surface. Our multidisciplinary study, which makes use of batch sorption experiments, vibration spectroscopy and periodic density functional theory calculations, reveals enhanced binding of the otherwise weakly bound NFA caused by unforeseen intermolecular interactions with mineral-bound NA. This enhancement is ascribed to the formation of a NFA-NA dimer whose energetically favored formation (-0.5 eV compared to free molecules) is predominantly driven by van der Waals interactions. A parallel set of efforts also showed that no cobinding occurred with sulfamethoxazole (SMX) because of the lack of molecular interactions with coexisting contaminants. As such, this article raises the importance of recognizing drug cobinding, and lack of cobinding, for predicting and developing policies on the fate of complex mixtures of antibiotics and anti-inflammatory agents in nature.

Recognition of the DNA sequence by an inorganic crystal surface

PubMed Central

Sampaolese, Beatrice; Bergia, Anna; Scipioni, Anita; Zuccheri, Giampaolo; Savino, Maria; Samorì, Bruno; De Santis, Pasquale

2002-01-01

The sequence-dependent curvature is generally recognized as an important and biologically relevant property of DNA because it is involved in the formation and stability of association complexes with proteins. When a DNA tract, intrinsically curved for the periodical recurrence on the same strand of A-tracts phased with the B-DNA periodicity, is deposited on a flat surface, it exposes to that surface either a T- or an A-rich face. The surface of a freshly cleaved mica crystal recognizes those two faces and preferentially interacts with the former one. Statistical analysis of scanning force microscopy (SFM) images provides evidence of this recognition between an inorganic crystal surface and nanoscale structures of double-stranded DNA. This finding could open the way toward the use of the sequence-dependent adhesion to specific crystal faces for nanotechnological purposes. PMID:12361979

Carbon solids in oxygen-deficient explosives (LA-UR-13-21151)

NASA Astrophysics Data System (ADS)

Peery, Travis

2013-06-01

The phase behavior of excess carbon in oxygen-deficient explosives has a significant effect on detonation properties and product equations of state. Mixtures of fuel oil in ammonium nitrate (ANFO) above a stoichiometric ratio demonstrate that even small amounts of graphite, on the order of 5% by mole fraction, can substantially alter the Chapman-Jouget (CJ) state properties, a central ingredient in modeling the products equation of state. Similar effects can be seen for Composition B, which borders the carbon phase boundary between graphite and diamond. Nano-diamond formation adds complexity to the product modeling because of surface adsorption effects. I will discuss these carbon phase issues in our equation of state modeling of detonation products, including our statistical mechanics description of carbon clustering and surface chemistry to properly treat solid carbon formation. This work is supported by the Advanced Simulation and Computing Program, under the NNSA.

Structural and Functional Analysis of the Interaction Between the Nucleoporin Nup98 and the mRNA Export Facto Rae1

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

Y Ren; H Seo; G Blobel

The export of mRNAs is a multistep process, involving the packaging of mRNAs into messenger ribonucleoprotein particles (mRNPs), their transport through nuclear pore complexes, and mRNP remodeling events prior to translation. Ribonucleic acid export 1 (Rae1) and Nup98 are evolutionarily conserved mRNA export factors that are targeted by the vesicular stomatitis virus matrix protein to inhibit host cell nuclear export. Here, we present the crystal structure of human Rae1 in complex with the Gle2-binding sequence (GLEBS) of Nup98 at 1.65 {angstrom} resolution. Rae1 forms a seven-bladed {beta}-propeller with several extensive surface loops. The Nup98 GLEBS motif forms an {approx}50-{angstrom}-long hairpinmore » that binds with its C-terminal arm to an essentially invariant hydrophobic surface that extends over the entire top face of the Rae1 {beta}-propeller. The C-terminal arm of the GLEBS hairpin is necessary and sufficient for Rae1 binding, and we identify a tandem glutamate element in this arm as critical for complex formation. The Rae1 {center_dot} Nup98{sup GLEBS} surface features an additional conserved patch with a positive electrostatic potential, and we demonstrate that the complex possesses single-stranded RNA-binding capability. Together, these data suggest that the Rae1 {center_dot} Nup98 complex directly binds to the mRNP at several stages of the mRNA export pathway.« less

Methylmercury photodegradation in surface water of the Florida Everglades: importance of dissolved organic matter-methylmercury complexation.

PubMed

Tai, Chao; Li, Yanbin; Yin, Yongguang; Scinto, Leonard J; Jiang, Guibin; Cai, Yong

2014-07-01

Photodegradation is the major pathway of methylmercury (MeHg) degradation in many surface waters. However, the mechanism of MeHg photodegradation is still not completely understood. Dissolved organic matter (DOM) is expected to play a critical role in MeHg photodegradation. By using several techniques, including N2/O2 purging and the addition of stable isotope (Me(201)Hg), scavengers, competing ligands, and a singlet oxygen ((1)O2) generator, the role played by MeHg-DOM complexation in MeHg photodegradation of Everglades surface water was investigated. DOM appeared to be involved in MeHg photodegradation via the formation MeHg-DOM complexes based on three findings: (1) MeHg was quickly photodegraded in solutions containing DOM extracts; (2) degradation of MeHg did not occur in deionized water; and (3) addition of competing complexation reagents (dithiothreitol-DTT) dramatically prohibited the photodegradation of MeHg in Everglades water. Further experiments indicated that free radicals/reactive oxygen species, including hydroxyl radical (·OH), (1)O2, triplet excited state of DOM ((3)DOM*), and hydrated electron (e(-)aq), played a minor role in MeHg photodegradation in Everglades water, based on the results of scavenger addition, (1)O2 generator addition and N2/O2 purging. A pathway, involving direct photodegradation of MeHg-DOM complexes via intramolecular electron transfer, is proposed as the dominant mechanism for MeHg photodegradation in Everglades water.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

2004-02-01

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.

3D Structure and Interaction of p24β and p24δ Golgi Dynamics Domains: Implication for p24 Complex Formation and Cargo Transport.

PubMed

Nagae, Masamichi; Hirata, Tetsuya; Morita-Matsumoto, Kana; Theiler, Romina; Fujita, Morihisa; Kinoshita, Taroh; Yamaguchi, Yoshiki

2016-10-09

The p24 family consists of four subfamilies (p24α, p24β, p24γ, and p24δ), and the proteins are thought to form hetero-oligomeric complexes for efficient transport of cargo proteins from the endoplasmic reticulum to the Golgi apparatus. The proteins possess a conserved luminal Golgi dynamics (GOLD) domain, whose functions are largely unknown. Here, we present structural and biochemical studies of p24β1 and p24δ1 GOLD domains. Use of GOLD domain-deleted mutants revealed that the GOLD domain of p24δ1 is required for proper p24 hetero-oligomeric complex formation and efficient transport of GPI-anchored proteins. The p24β1 and p24δ1 GOLD domains share a common β-sandwich fold with a characteristic intrasheet disulfide bond. The GOLD domain of p24δ1 crystallized as dimers, allowing the analysis of a homophilic interaction site. Surface plasmon resonance and solution NMR analyses revealed that p24β1 and p24δ1 GOLD domains interact weakly (K d = ~10 -4 M). Bi-protein titration provided interaction site maps. We propose that the heterophilic interaction of p24 GOLD domains contributes to the formation of the p24 hetero-oligomeric complex and to efficient cargo transport. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interactions of Histophilus somni with Host Cells.

PubMed

Behling-Kelly, Erica; Rivera-Rivas, Jose; Czuprynski, Charles J

2016-01-01

Histophilus somni resides as part of the normal microflora in the upper respiratory tract of healthy cattle. From this site, the organism can make its way into the lower respiratory tract, where it is one of the important bacterial agents of the respiratory disease complex. If H. somni cells disseminate to the bloodstream, they frequently result in thrombus formation. A series of in vitro investigations have examined potential mechanisms that might contribute to such thrombus formation. Earlier work showed that H. somni can stimulate some bovine endothelial cells to undergo apoptosis. More recent studies indicate that H. somni stimulates endothelial cell tissue factor activity and disrupts intercellular junctions. The net effect is to enhance procoagulant activity on the endothelium surface and to make the endothelial monolayer more permeable to molecules, leukocytes, and perhaps H. somni cells. H. somni also activates bovine platelets, which also can enhance tissue factor activity on the endothelium surface. When exposed to H. somni, bovine neutrophils and mononuclear phagocytes form extracellular traps in vitro. Ongoing research is investigating how the interplay among endothelial cells, platelets, and leukocytes might contribute to the thrombus formation seen in infected cattle.

Ullmann-like reactions for the synthesis of complex two-dimensional materials

NASA Astrophysics Data System (ADS)

Quardokus, Rebecca C.; Tewary, V. K.; DelRio, Frank W.

2016-11-01

Engineering two-dimensional materials through surface-confined synthetic techniques is a promising avenue for designing new materials with tailored properties. Developing and understanding reaction mechanisms for surface-confined synthesis of two-dimensional materials requires atomic-level characterization and chemical analysis. Beggan et al (2015 Nanotechnology 26 365602) used scanning tunneling microscopy and x-ray photoelectron spectroscopy to elucidate the formation mechanism of surface-confined Ullmann-like coupling of thiophene substituted porphyrins on Ag(111). Upon surface deposition, bromine is dissociated and the porphyrins couple with surface adatoms to create linear strands and hexagonally packed molecules. Annealing the sample results in covalently-bonded networks of thienylporphyrin derivatives. A deeper understanding of surface-confined Ullmann-like coupling has the potential to lead to precision-engineered nano-structures through synthetic techniques. Contribution of the National Institute of Standards and Technology, not subject to copyright in the United States of America.

Biofouling on polymeric heat exchanger surfaces with E. coli and native biofilms.

PubMed

Pohl, S; Madzgalla, M; Manz, W; Bart, H J

2015-01-01

The biofouling affinity of different polymeric surfaces (polypropylene, polysulfone, polyethylene terephthalate, and polyether ether ketone) in comparison to stainless steel (SS) was studied for the model bacterium Escherichia coli K12 DSM 498 and native biofilms originating from Rhine water. The biofilm mass deposited on the polymer surfaces was minimized by several magnitudes compared to SS. The cell count and the accumulated biomass of E. coli on the polymer surfaces showed an opposing linear trend. The promising low biofilm formation on the polymers is attributed to the combination of inherent surface properties (roughness, surface energy and hydrophobicity) when compared to SS. The fouling characteristics of E. coli biofilms show good conformity with the more complex native biofilms investigated. The results can be utilized for the development of new polymer heat exchangers when using untreated river water as coolant or for other processes needing antifouling materials.

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Stearns, C. A.

1979-01-01

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.

Amine functionalized graphene oxide/CNT nanocomposite for ultrasensitive electrochemical detection of trinitrotoluene.

PubMed

Sablok, Kavita; Bhalla, Vijayender; Sharma, Priyanka; Kaushal, Roohi; Chaudhary, Shilpa; Suri, C Raman

2013-03-15

Binding of electron-deficient trinitrotoluene (TNT) to the electron rich amine groups on a substrate form specific charge-transfer Jackson-Meisenheimer (JM) complex. In the present work, we report formation of specific JM complex on amine functionalized reduced graphene oxide/carbon nanotubes- (a-rGO/CNT) nanocomposite leading to sensitive detection of TNT. The CNT were dispersed using graphene oxide that provides excellent dispersion by attaching to CNT through its hydrophobic domains and solubilizes through the available OH and COOH groups on screen printed electrode (SPE). The GO was reduced electrochemically to form reduced graphene that remarkably increases electrochemical properties owing to the intercalation of high aspect CNT on graphene flakes as shown by TEM micrograph. The surface amine functionalization of dropcasted and rGO/CNT was carried out using a bi-functional cross linker ethylenediamine. The extent of amine functionalization on modified electrodes was confirmed using energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and confocal microscopy. The FTIR and Raman spectra further suggested the formation of JM complex between amine functionalized electrodes and TNT leading to a shift in peak intensity together with peak broadening. The a-rGO/CNT nanocomposite prepared electrode surface leads to ultra-trace detection of TNT upto 0.01 ppb with good reproducibility (n=3). The a-rGO/CNT sensing platform could be an alternate for sensitive detection of TNT explosive for various security and environmental applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

PubMed

Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

2015-11-01

Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

Surface morphology of molybdenum silicide films upon low-energy ion beam sputtering.

PubMed

Gago, R; Jaafar, M; Palomares, F J

2018-07-04

The surface morphology of molybdenum silicide (Mo x Si 1-x ) films has been studied after low-energy Ar + ion beam sputtering (IBS) to explore eventual pattern formation on compound targets and, simultaneously, gather information about the mechanisms behind silicide-assisted nanopatterning of silicon surfaces by IBS. For this purpose, Mo x Si 1-x films with compositions below, equal and above the MoSi 2 stoichiometry (x  =  0.33) have been produced by magnetron sputtering, as assessed by Rutherford backscattering spectrometry (RBS). The surface morphology of silicon and silicide films before and after IBS has been imaged by atomic force microscopy (AFM), comprising conditions where typical nanodot or ripple patterns emerge on the former. In the case of irradiated Mo x Si 1-x surfaces, AFM shows a marked surface smoothing at normal incidence with and without additional Mo incorporation (the former results in nanodot patterns on Si). The morphological analysis also provides no evidence of ion-induced phase separation in irradiated Mo x Si 1-x . Contrary to silicon, Mo x Si 1-x surfaces also do not display ripple formation for (impurity free) oblique irradiations, except at grazing incidence conditions where parallel ripples emerge in a more evident fashion than in the Si counterpart. By means of RBS, irradiated Mo x Si 1-x films with 1 keV Ar + at normal incidence have also been used to measure experimentally the (absolute) sputtering yield and rate of Si and Mo x Si 1-x materials. The analysis reveals that, under the present working conditions, the erosion rate of silicides is larger than for silicon, supporting simulations from the TRIDYN code. This finding questions the shielding effect from silicide regions as roughening mechanism in metal-assisted nanopatterning of silicon. On the contrary, the results highlight the relevance of in situ silicide formation. Ripple formation on Mo x Si 1-x under grazing incidence is also attributed to the dominance of sputtering effects under this geometry. In conclusion, our work provides some insights into the complex morphological evolution of compound surfaces and solid experimental evidences regarding the mechanisms behind silicide-assisted nanopatterning.

Dimer formation through domain swapping in the crystal structure of the Grb2-SH2-Ac-pYVNV complex.

PubMed

Schiering, N; Casale, E; Caccia, P; Giordano, P; Battistini, C

2000-11-07

Src homology 2 (SH2) domains are key modules in intracellular signal transduction. They link activated cell surface receptors to downstream targets by binding to phosphotyrosine-containing sequence motifs. The crystal structure of a Grb2-SH2 domain-phosphopeptide complex was determined at 2.4 A resolution. The asymmetric unit contains four polypeptide chains. There is an unexpected domain swap so that individual chains do not adopt a closed SH2 fold. Instead, reorganization of the EF loop leads to an open, nonglobular fold, which associates with an equivalent partner to generate an intertwined dimer. As in previously reported crystal structures of canonical Grb2-SH2 domain-peptide complexes, each of the four hybrid SH2 domains in the two domain-swapped dimers binds the phosphopeptide in a type I beta-turn conformation. This report is the first to describe domain swapping for an SH2 domain. While in vivo evidence of dimerization of Grb2 exists, our SH2 dimer is metastable and a physiological role of this new form of dimer formation remains to be demonstrated.

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

"Soft docking": matching of molecular surface cubes.

PubMed

Jiang, F; Kim, S H

1991-05-05

Molecular recognition is achieved through the complementarity of molecular surface structures and energetics with, most commonly, associated minor conformational changes. This complementarity can take many forms: charge-charge interaction, hydrogen bonding, van der Waals' interaction, and the size and shape of surfaces. We describe a method that exploits these features to predict the sites of interactions between two cognate molecules given their three-dimensional structures. We have developed a "cube representation" of molecular surface and volume which enables us not only to design a simple algorithm for a six-dimensional search but also to allow implicitly the effects of the conformational changes caused by complex formation. The present molecular docking procedure may be divided into two stages. The first is the selection of a population of complexes by geometric "soft docking", in which surface structures of two interacting molecules are matched with each other, allowing minor conformational changes implicitly, on the basis of complementarity in size and shape, close packing, and the absence of steric hindrance. The second is a screening process to identify a subpopulation with many favorable energetic interactions between the buried surface areas. Once the size of the subpopulation is small, one may further screen to find the correct complex based on other criteria or constraints obtained from biochemical, genetic, and theoretical studies, including visual inspection. We have tested the present method in two ways. First is a control test in which we docked the components of a molecular complex of known crystal structure available in the Protein Data Bank (PDB). Two molecular complexes were used: (1) a ternary complex of dihydrofolate reductase, NADPH and methotrexate (3DFR in PDB) and (2) a binary complex of trypsin and trypsin inhibitor (2PTC in PDB). The components of each complex were taken apart at an arbitrary relative orientation and then docked together again. The results show that the geometric docking alone is sufficient to determine the correct docking solutions in these ideal cases, and that the cube representation of the molecules does not degrade the docking process in the search for the correct solution. The second is the more realistic experiment in which we docked the crystal structures of uncomplexed molecules and then compared the structures of docked complexes with the crystal structures of the corresponding complexes. This is to test the capability of our method in accommodating the effects of the conformational changes in the binding sites of the molecules in docking.(ABSTRACT TRUNCATED AT 400 WORDS)

Mercury's Weather-Beaten Surface: Understanding Mercury in the Context of Lunar and Asteroid Space Weathering Studies

NASA Technical Reports Server (NTRS)

Dominque, Deborah L.; Chapman, Clark R.; Killen, Rosemary M.; Zurbuchen, Thomas H.; Gilbert, Jason A.; Sarantos, Menelaos; Benna, Mehdi; Slavin, James A.; Orlando, Thomas M.; Schriver, David;

Modeling laser-induced periodic surface structures: Finite-difference time-domain feedback simulations

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

Skolski, J. Z. P., E-mail: j.z.p.skolski@utwente.nl; Vincenc Obona, J.; Römer, G. R. B. E.

2014-03-14

A model predicting the formation of laser-induced periodic surface structures (LIPSSs) is presented. That is, the finite-difference time domain method is used to study the interaction of electromagnetic fields with rough surfaces. In this approach, the rough surface is modified by “ablation after each laser pulse,” according to the absorbed energy profile, in order to account for inter-pulse feedback mechanisms. LIPSSs with a periodicity significantly smaller than the laser wavelength are found to “grow” either parallel or orthogonal to the laser polarization. The change in orientation and periodicity follow from the model. LIPSSs with a periodicity larger than the wavelengthmore » of the laser radiation and complex superimposed LIPSS patterns are also predicted by the model.« less

The human immunodeficiency virus type 1 (HIV-1) CD4 receptor and its central role in promotion of HIV-1 infection.

PubMed Central

Bour, S; Geleziunas, R; Wainberg, M A

1995-01-01

Interactions between the viral envelope glycoprotein gp120 and the cell surface receptor CD4 are responsible for the entry of human immunodeficiency virus type 1 (HIV-1) into host cells in the vast majority of cases. HIV-1 replication is commonly followed by the disappearance or receptor downmodulation of cell surface CD4. This potentially renders cells nonsusceptible to subsequent infection by HIV-1, as well as by other viruses that use CD4 as a portal of entry. Disappearance of CD4 from the cell surface is mediated by several different viral proteins that act at various stages through the course of the viral life cycle, and it occurs in T-cell lines, peripheral blood CD4+ lymphocytes, and monocytes of both primary and cell line origin. At the cell surface, gp120 itself and in the form of antigen-antibody complexes can trigger cellular pathways leading to CD4 internalization. Intracellularly, the mechanisms leading to CD4 downmodulation by HIV-1 are multiple and complex; these include degradation of CD4 by Vpu, formation of intracellular complexes between CD4 and the envelope precursor gp160, and internalization by the Nef protein. Each of the above doubtless contributes to the ultimate depletion of cell surface CD4, although the relative contribution of each mechanism and the manner in which they interact remain to be definitively established. PMID:7708013

Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

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

Powell, Brian; Kaplan, Daniel I; Arai, Yuji

2016-12-29

This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influencedmore » by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.« less

Thermodynamics, interfacial pressure isotherms and dilational rheology of mixed protein-surfactant adsorption layers.

PubMed

Fainerman, V B; Aksenenko, E V; Krägel, J; Miller, R

2016-07-01

Proteins and their mixtures with surfactants are widely used in many applications. The knowledge of their solution bulk behavior and its impact on the properties of interfacial layers made great progress in the recent years. Different mechanisms apply to the formation process of protein/surfactant complexes for ionic and non-ionic surfactants, which are governed mainly by electrostatic and hydrophobic interactions. The surface activity of these complexes is often remarkably different from that of the individual protein and has to be considered in respective theoretical models. At very low protein concentration, small amounts of added surfactants can change the surface activity of proteins remarkably, even though no strongly interfacial active complexes are observed. Also small added amounts of non-ionic surfactants change the surface activity of proteins in the range of small bulk concentrations or surface coverages. The modeling of the equilibrium adsorption behavior of proteins and their mixtures with surfactants has reached a rather high level. These models are suitable also to describe the high frequency limits of the dilational viscoelasticity of the interfacial layers. Depending on the nature of the protein/surfactant interactions and the changes in the interfacial layer composition rather complex dilational viscoelasticities can be observed and described by the available models. The differences in the interfacial behavior, often observed in literature for studies using different experimental methods, are at least partially explained by a depletion of proteins, surfactants and their complexes in the range of low concentrations. A correction of these depletion effects typically provides good agreement between the data obtained with different methods, such as drop and bubble profile tensiometry. Copyright © 2015 Elsevier B.V. All rights reserved.

Micro-mechanisms of Surface Defects Induced on Aluminum Alloys during Plastic Deformation at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Gali, Olufisayo A.

Near-surface deformed layers developed on aluminum alloys significantly influence the corrosion and tribological behavior as well as reduce the surface quality of the rolled aluminum. The evolution of the near-surface microstructures induced on magnesium containing aluminum alloys during thermomechanical processing has been investigated with the aim generating an understanding of the influence of individual forming parameters on its evolution and examine the microstructure of the roll coating induced on the mating steel roll through material transfer during rolling. The micro-mechanisms related to the various features of near-surface microstructure developed during tribological conditions of the simulated hot rolling process were identified. Thermomechanical processing experiments were performed with the aid of hot rolling (operating temperature: 550 to 460 °C, 4, 10 and 20 rolling pass schedules) and hot forming (operating temperature: 350 to 545 °C, strain rate: 4 x 10-2 s-1) tribo-simulators. The surface, near-surface features and material transfer induced during the elevated temperature plastic deformation were examined and characterized employing optical interferometry, SEM/EDS, FIB and TEM. Near-surface features characterized on the rolled aluminum alloys included; cracks, fractured intermetallic particles, aluminum nano-particles, oxide decorated grain boundaries, rolled-in oxides, shingles and blisters. These features were related to various individual rolling parameters which included, the work roll roughness, which induced the formation of shingles, rolling marks and were responsible for the redistribution of surface oxide and the enhancements of the depth of the near-surface damage. The enhanced stresses and strains experienced during rolling were related to the formation and propagation of cracks, the nanocrystalline structure of the near-surface layers and aluminum nano-particles. The mechanism of the evolution of the near-surface microstructure were determined to include grain boundary sliding which induced the cracks at the surface and subsurface of the alloy, magnesium diffusion to free surfaces, crack propagation from shear stresses and the shear strains inducing the nanocrystalline grain structure, the formation of shingles by the shear deformation of micro-wedges induced by the work roll grooves, and the deformation of this oxide covered micro-wedges inducing the rolled-in oxides. Magnesium diffusion to free surfaces was identified as inducing crack healing due to the formation of MgO within cracks and was responsible for the oxide decorated grain boundaries. An examination of the roll coating revealed a complex layered microstructure that was induced through tribo-chemical and mechanical entrapment mechanisms. The microstructure of the roll coating suggested that the work roll material and the rolled aluminum alloy were essential in determining its composition and structure. Subsequent hot forming processes revealed the rich oxide-layer of the near-surface microstructure was beneficial for reducing the coefficient of friction during tribological contact with the steel die. Damage to the microstructure include cracks induced from grain boundary sliding of near-surface grains and the formation of oxide fibres within cracks of the near-surface deformed layers.

Mechanisms of antimony adsorption onto soybean stover-derived biochar in aqueous solutions.

PubMed

Vithanage, Meththika; Rajapaksha, Anushka Upamali; Ahmad, Mahtab; Uchimiya, Minori; Dou, Xiaomin; Alessi, Daniel S; Ok, Yong Sik

2015-03-15

Limited mechanistic knowledge is available on the interaction of biochar with trace elements (Sb and As) that exist predominantly as oxoanions. Soybean stover biochars were produced at 300 °C (SBC300) and 700 °C (SBC700), and characterized by BET, Boehm titration, FT-IR, NMR and Raman spectroscopy. Bound protons were quantified by potentiometric titration, and two acidic sites were used to model biochar by the surface complexation modeling based on Boehm titration and NMR observations. The zero point of charge was observed at pH 7.20 and 7.75 for SBC300 and SBC700, respectively. Neither antimonate (Sb(V)) nor antimonite (Sb(III)) showed ionic strength dependency (0.1, 0.01 and 0.001 M NaNO3), indicating inner sphere complexation. Greater adsorption of Sb(III) and Sb(V) was observed for SBC300 having higher -OH content than SBC700. Sb(III) removal (85%) was greater than Sb(V) removal (68%). Maximum adsorption density for Sb(III) was calculated as 1.88 × 10(-6) mol m(-2). The Triple Layer Model (TLM) successfully described surface complexation of Sb onto soybean stover-derived biochar at pH 4-9, and suggested the formation of monodentate mononuclear and binuclear complexes. Spectroscopic investigations by Raman, FT-IR and XPS further confirmed strong chemisorptive binding of Sb to biochar surfaces. Copyright © 2014 Elsevier Ltd. All rights reserved.

Removal of phosphate from eutrophic lakes through adsorption by in situ formation of magnesium hydroxide from diatomite.

PubMed

Xie, Fazhi; Wu, Fengchang; Liu, Guijian; Mu, Yunsong; Feng, Chenglian; Wang, Huanhua; Giesy, John P

2014-01-01

Since in situ formation of Mg(OH)2 can efficiently sorb phosphate (PO4) from low concentrations in the environment, a novel dispersed magnesium oxide nanoflake-modified diatomite adsorbent (MOD) was developed for use in restoration of eutrophic lakes by removal of excess PO4. Various adsorption conditions, such as pH, temperature and contact time were investigated. Overall, sorption capacities increased with increasing temperature and contact time, and decreased with increasing pH. Adsorption of PO4 was well described by both the Langmuir isotherm and pseudo second-order models. Theoretical maximum sorption capacity of MOD for PO4 was 44.44-52.08 mg/g at experimental conditions. Characterization of PO4 adsorbed to MOD by use of X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and solid state (31)P nuclear magnetic resonance revealed that electrostatic attraction, surface complexation and chemical conversion in situ were the major forces in adsorption of PO4. Mg(OH)2 formed in situ had a net positive charge on the surface of the MOD that could adsorb PO4(3-) and HPO4(2-) anion to form surface complex and gradually convert to Mg3(PO4)2 and MgHPO4. Efficiency of removal of PO4 was 90% when 300 mg MOD/L was added to eutrophic lake water. Results presented here demonstrated the potential use of the MOD for restoration of eutrophic lakes by removal of excess PO4.

Chemical complexity induced by efficient ice evaporation in the Barnard 5 molecular cloud

NASA Astrophysics Data System (ADS)

Taquet, V.; Wirström, E. S.; Charnley, S. B.; Faure, A.; López-Sepulcre, A.; Persson, C. M.

2017-10-01

Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. Here we present the detection of the complex organic molecules (COMs) acetaldehyde (CH3CHO) and methyl formate (CH3OCHO), as well as formic acid (HCOOH) and ketene (CH2CO), and the tentative detection of di-methyl ether (CH3OCH3) towards the "methanol hotspot" of Barnard 5 located between two dense cores using the single dish OSO 20 m, IRAM 30 m, and NRO 45 m telescopes. The high energy cis-conformer of formic acid is detected, suggesting that formic acid is mostly formed at the surface of interstellar grains and then evaporated. The detection of multiple transitions for each species allows us to constrain their abundances through LTE and non-LTE methods. All the considered COMs show similar abundances between 1 and 10% relative to methanol depending on the assumed excitation temperature. The non-detection of glycolaldehyde, an isomer of methyl formate, with a [glycolaldehyde]/[methyl formate] abundance ratio lower than 6%, favours gas phase formation pathways triggered by methanol evaporation. According to their excitation temperatures derived in massive hot cores, formic acid, ketene, and acetaldehyde have been designated as "lukewarm" COMs whereas methyl formate and di-methyl ether were defined as "warm" species. Comparison with previous observations of other types of sources confirms that lukewarm and warm COMs show similar abundances in low-density cold gas whereas the warm COMs tend to be more abundant than the lukewarm species in warm protostellar cores. This abundance evolution suggests either that warm COMs are indeed mostly formed in protostellar environments and/or that lukewarm COMs are efficiently depleted by increased hydrogenation efficiency around protostars.

Change of the binding mode of the DNA/proflavine system induced by ethanol.

PubMed

García, Begoña; Leal, José M; Ruiz, Rebeca; Biver, Tarita; Secco, Fernando; Venturini, M

2010-07-01

The equilibria and kinetics of the binding of proflavine to poly(dG-dC).poly(dG-dC) and poly(dA-dT).poly(dA-dT) were investigated in ethanol/water mixtures using spectrophotometric, circular dichroism, viscometric, and T-jump methods. All methods concur in showing that two modes of interaction are operative: intercalation and surface binding. The latter mode is favored by increasing ethanol and/or the proflavine content. Both static and kinetic experiments show that, concerning the poly(dG-dC).poly(dG-dC)/proflavine system, intercalation largely prevails up to 20% EtOH. For higher EtOH levels surface binding becomes dominant. Concerning the poly(dA-dT).poly(dA-dT)/proflavine system, melting experiments show that addition of proflavine stabilizes the double stranded structure, but the effect is reduced in the presence of EtOH. The DeltaH degrees and DeltaS degrees values of the melting process, measured at different concentrations of added proflavine, are linearly correlated, revealing the presence of the enthalpy-entropy compensation phenomenon (EEC). The nonmonotonicity of the "entropic term" of the EEC reveals the transition between the two binding modes. T-jump experiments show two relaxation effects, but at the highest levels of EtOH (>25%) the kinetic curves become monophasic, confirming the prevalence of the surface complex. A branched mechanism is proposed where diffusion controlled formation of a precursor complex occurs in the early stage of the binding process. This evolves toward the surface and/or the intercalated complex according to two rate-determining parallel steps. CD spectra suggest that, in the surface complex, proflavine is bound to DNA in the form of an aggregate.

Identifying and Quantifying Chemical Forms of Sediment-Bound Ferrous Iron.

NASA Astrophysics Data System (ADS)

Kohler, M.; Kent, D. B.; Bekins, B. A.; Cozzarelli, I.; Ng, G. H. C.

2015-12-01

Aqueous Fe(II) produced by dissimilatory iron reduction comprises only a small fraction of total biogenic Fe(II) within an aquifer. Most biogenic Fe(II) is bound to sediments on ion exchange sites; as surface complexes and, possibly, surface precipitates; or incorporated into solid phases (e.g., siderite, magnetite). Different chemical forms of sediment-bound Fe(II) have different reactivities (e.g., with dissolved oxygen) and their formation or destruction by sorption/desorption and precipitation/dissolution is coupled to different solutes (e.g., major cations, H+, carbonate). We are quantifying chemical forms of sediment-bound Fe(II) using previously published extractions, novel extractions, and experimental studies (e.g., Fe isotopic exchange). Sediments are from Bemidji, Minnesota, where biodegradation of hydrocarbons from a burst oil pipeline has driven extensive dissimilatory Fe(III) reduction, and sites potentially impacted by unconventional oil and gas development. Generally, minimal Fe(II) was mobilized from ion exchange sites (batch desorption with MgCl2 and repeated desorption with NH4Cl). A < 2mm sediment fraction from the iron-reducing zone at Bemidji had 1.8umol/g Fe(II) as surface complexes or carbonate phases (sodium acetate at pH 5) of which ca. 13% was present as surface complexes (FerroZine extractions). Total bioavailable Fe(III) and biogenic Fe(II) (HCl extractions) was 40-50 umole/g on both background and iron-reducing zone sediments . Approximately half of the HCl-extractable Fe from Fe-reducing zone sediments was Fe(II) whereas 12 - 15% of Fe extracted from background sediments was present as Fe(II). One-third to one-half of the total biogenic Fe(II) extracted from sediments collected from a Montana prairie pothole located downgradient from a produced-water disposal pit was present as surface-complexed Fe(II).

Dust input in the formation of rock varnish from the Dry Valleys (Antarctica)

NASA Astrophysics Data System (ADS)

Zerboni, A.; Guglielmin, M.

2017-12-01

Rock varnish is a glossy, yellowish to dark brown coating that covers geomorphically stable, aerially exposed rock surfaces and landforms in warm and cold arid lands. In warm deserts, rock varnish consists of clay minerals, Mn-Fe oxides/hydroxides, and Si+alkalis dust; it occasionally containis sulphates, phosphates, and organic remains. In Antarctica, rock varnish developed on a variety of bedrocks and has been described being mostly formed of Si, Al, Fe, and sulphates, suggesting a double process in its formation, including biomineralization alternated to dust accretion. We investigated rock coatings developed on sandstones outcropping in the Dry Valleys of Antarctica and most of the samples highlithed an extremely complex varnish structure, alternating tihn layer of different chemical compostion. Optical microscope evidenced the occurrence of highly birefringent minerals, occasionally thinly laminated and consisitng of Si and Al-rich minerals (clays). These are interlayered by few micron-thick dark lenses and continous layers. The latter are well evident under the scanning electron microscope and chemical analysis confirmed that they consist of different kinds of sulphates; jarosite is the most represented species, but gypsum crystals were also found. Fe-rich hypocoatings and intergranula crusts were also detected, sometimes preserving the shape of the hyphae they have replaced. Moreover, small weathering pits on sandstone surface display the occurrence of an amorphous, dark Mn/Fe-rich rock varnish. The formation of rock varnish in the Dry Valleys is a complex process, which required the accretion of airborne dust of variable composition and subsequent recrystallization of some constituent, possibly promoted by microorganisms. In particualr, the formation of sulphates seems to preserve the memory of S-rich dust produced by volcanic eruptions. On the contrary, the formation of Mn-rich varnish should be in relation with the occurrence of higher environmental humidity within weathering pits. Rock varnish in the Dry Valleys represents a potential tool to reconstruct past water availability and changes in the aeolian fallout.

Aromatic, Alphatic, Enigmatic: The Chemistry of Titan

NASA Astrophysics Data System (ADS)

Horst, Sarah

2017-10-01

The extraordinary complexity of Titan’s atmospheric chemistry far surpasses that of any other solar system atmosphere. With its thick N2 atmosphere and stable bodies of liquid on its surface, Titan also possesses many physical processes that are similar to those that occur on Earth. The connection between Titan’s surface and atmosphere is unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan’s atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan’s atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. I will review our current understanding of chemistry on Titan forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I will conclude with some of the questions that remain after Cassini-Huygens.

On-Surface Synthesis and Reactivity of Functional Organic and Metal-Organic Adsorbates at Metal Surfaces by Vibrational Spectroscopy

NASA Astrophysics Data System (ADS)

Williams, Christopher Glen

Surface self-assembly is a promising way to introduce functionality to a surface through design at the molecular level. These self-assembled species allow for new on-surface type reactions to be observed and studied. The experiments described in this thesis demonstrate that the molecules used in self-assembly can potentially lead to interesting synthesis pathways and can be used to explore previously under-researched reaction pathways and surface molecular architecture activity or stability. Alkanes are an unreactive species typically used for driving molecular assembly in surface structures. However, with molecular design, alkanes are capable of reacting on surfaces not typically associated with alkane reactivity. Utilizing high-resolution electron energy loss spectroscopy (HREELS) and octaethylporphyrin, we could observe that dehydrogenation is possible on Cu(100) and Ag(111) surfaces at 500 and 610 K respectively. HREELS revealed that after the dehydrogenation, the molecule undergoes an intramolecular C-C bond formation leading to a tetrabenzo-porphyrin structure. Controls with deposited tetrabenzo-porphyrin were performed to verify the structure. This work provides the first example of dehydrocyclization on Cu(100) and Ag(111) to be analyzed by vibrational spectroscopy. Alkyl species in the 1,3,5-tris-(3,5-diethylphenyl)benzene molecule also undergo a dehydrogenation on Cu(100) and Au(111) at 450 and 500 K. The design of this molecule does not let the intramolecular dehydrocyclization reaction take place, but instead the dehydrogenation leads to intermolecular C-C bond formation between molecular species as noted by the formation of extended structure across the surface. Controls with triphenyl-benzene were done to help characterize the peaks in the spectra and observe varying reactivity when the ethyl groups are absent. The fabrication of uniform single-site metal centers at surfaces is important for higher selectivity in next-generation heterogeneous catalysts. We accomplished this by metal coordination to redox non-innocent dipyridyl-tetrazine ligands. We utilize HREELS to observe a surface confined redox process of dipyridyl-tetrazine with V, Fe, Ag, and Pt. With the formation of the V-dipyridyl-tetrazine species, we are able to see that oxygen exposures to the surface results in a more selective vanadyl species formation as opposed to the multiple binding conformations observed with metallic vanadium nanoparticles. This thesis also reveals that the metal substrate used does not play a passive role with the metal-organic complex. Instead, we are the first to characterize a replacement of the coordinating metal species with atoms from the Ag(111) substrate. This replacement results in the redox reaction between the coordinating metal species and the substrate metal.

Surface modification of TiO{sub 2} nanoparticles with carotenoids. EPR study

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

Konovalova, T.A.; Kispert, L.D.; Konovalov, V.V.

1999-06-03

Among the semiconductors, titanium dioxide is the most suitable for many environmental applications. EPR measurements demonstrate efficient charge separation on carotenoid-modified titanium dioxide nanoparticles (7 nm). Strong complexation of carotenoids containing terminal carboxy groups ({minus}CO{sub 2}H) with the TiO{sub 2} surface leads to electron transfer from the adsorbed carotenoid molecule to the surface trapping site. For these systems, EPR signals of the carotenoid radical cations Car{sup {sm_bullet}+} and the electrons trapped on the TiO{sub 2} are observed before irradiation (77 K). Their UV-visible spectra show an absorption band with a maximum near 650 nm that is characteristic of the trappedmore » electrons. Surface modification of the TiO{sub 2} by other carotenoids results in the formation of a complex with an optical absorption band near 545 nm. These systems form charge-separated pairs [Car{sup {sm_bullet}+}{hor_ellipsis}TiO{sub 2}(e{sup {minus}}{sub tr}){sub surf}. TiO{sub 2}(e{sup {minus}}{sub tr}){sub latt}] only upon 365--600 nm illumination at 77 K. Complexation of the TiO{sub 2} colloids with carotenoids enhances spatial charge separation, shifts the absorption threshold into the visible region, and thus greatly improves the reducing ability of the semiconductor. Photoreduction of acceptor molecules such as 2,5-dichloro-1,4-benzoquinone, nitrobenzene, and oxygen is demonstrated.« less

Adsorption of MCPA on goethite and humic acid-coated goethite.

PubMed

Iglesias, A; López, R; Gondar, D; Antelo, J; Fiol, S; Arce, F

2010-03-01

Anionic pesticides are adsorbed on the mineral oxide fraction of the soil surface but considerably less on the organic fraction, so that the presence of organic matter causes a decrease in the amount of pesticide adsorbed, and may affect the mechanism of adsorption. In the present study we investigated the adsorption of the weak acid pesticide MCPA on the surface of goethite and of humic acid-coated goethite, selected as models of the mineral oxide fraction and organic components present in soil systems. Adsorption of the anionic form of the pesticide on goethite fitted an S-type isotherm and the amount adsorbed increased as the ionic strength decreased and the pH of the medium decreased. Application of the charge distribution multi site complexation model (CD-MUSIC model) enabled interpretation of the results, which suggested the formation of inner and outer sphere complexes between the pesticide and the singly-coordinated surface sites of goethite. Less pesticide was adsorbed on the humic acid-coated goethite than on the bare goethite and the pattern fitted an L-type isotherm, which indicates a change in the mechanism of adsorption. Simplified calculations with the CD-MUSIC model enabled interpretation of the results, which suggested that the pesticide molecules form the same type of surface complexes as in the previous case. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

A Coffee Ring Aptasensor for Rapid Protein Detection

PubMed Central

Wen, Jessica T.; Ho, Chih-Ming; Lillehoj, Peter B.

2013-01-01

We introduce a new biosensing platform for rapid protein detection that combines one of the simplest methods for biomolecular concentration, coffee ring formation, with a sensitive aptamer-based optical detection scheme. In this approach, aptamer beacons are utilized for signal transduction where a fluorescence signal is emitted in the presence of the target molecule. Signal amplification is achieved by concentrating aptamer-target complexes within liquid droplets, resulting in the formation of coffee ring “spots”. Surfaces with various chemical coatings were utilized to investigate the correlation between surface hydrophobicity, concentration efficiency and signal amplification. Based on our results, we found that the increase in coffee ring diameter with larger droplet volumes is independent of surface hydrophobicity. Furthermore, we show that highly hydrophobic surfaces produce enhanced particle concentration, via coffee ring formation, resulting in signal intensities 6-fold greater than those on hydrophilic surfaces. To validate this biosensing platform for the detection of clinical samples, we detected α-thrombin in human serum and 4x diluted whole blood. Based on our results, coffee ring spots produced detection signals 40x larger than samples in liquid droplets. Additionally, this biosensor exhibits a lower limit of detection of 2 ng/mL (54 pM) in serum, and 4 ng/mL (105 pM) in blood. Based on its simplicity and high performance, this platform demonstrates immense potential as an inexpensive diagnostic tool for the detection of disease biomarkers, particularly for use in developing countries that lack the resources and facilities required for conventional biodetection practices. PMID:23540796

From Aβ Filament to Fibril: Molecular Mechanism of Surface-Activated Secondary Nucleation from All-Atom MD Simulations.

PubMed

Schwierz, Nadine; Frost, Christina V; Geissler, Phillip L; Zacharias, Martin

2017-02-02

Secondary nucleation pathways in which existing amyloid fibrils catalyze the formation of new aggregates and neurotoxic oligomers are of immediate importance for the onset and progression of Alzheimer's disease. Here, we apply extensive all-atom molecular dynamics simulations in explicit water to study surface-activated secondary nucleation pathways at the extended lateral β-sheet surface of a preformed Aβ 9-40 filament. Calculation of free-energy profiles allows us to determine binding free energies and conformational intermediates for nucleation complexes consisting of 1-4 Aβ peptides. In addition, we combine the free-energy profiles with position-dependent diffusion profiles to extract complementary kinetic information and macroscopic growth rates. Single monomers bind to the β-sheet surface in a disordered, hydrophobically collapsed conformation, whereas dimers and larger oligomers can retain a cross-β conformation resembling a more ordered fibril structure. The association processes during secondary nucleation follow a dock/lock mechanism consisting of a fast initial encounter phase (docking) and a slow structural rearrangement phase (locking). The major driving forces for surface-activated secondary nucleation are the release of a large number of hydration water molecules and the formation of hydrophobic interface contacts, the latter being in contrast to the elongation process at filament tips, which is dominated by the formation of stable and highly specific interface hydrogen bonds. The calculated binding free energies and the association rates for the attachment of Aβ monomers and oligomers to the extended lateral β-sheet surface of the filament seed are higher compared to those for elongation at the filament tips, indicating that secondary nucleation pathways can become important once a critical concentration of filaments has formed.

Identification of primary and secondary UBA footprints on the surface of ubiquitin in cell-mimicking crowded solution.

PubMed

Munari, Francesca; Bortot, Andrea; Zanzoni, Serena; D'Onofrio, Mariapina; Fushman, David; Assfalg, Michael

2017-04-01

Despite significant advancements in our understanding of ubiquitin-mediated signaling, the influence of the intracellular environment on the formation of transient ubiquitin-partner complexes remains poorly explored. In our work, we introduce macromolecular crowding as a first level of complexity toward the imitation of a cellular environment in the study of such interactions. Using NMR spectroscopy, we find that the stereospecific complex of ubiquitin and the ubiquitin-associated domain (UBA) is minimally perturbed by the crowding agent Ficoll. However, in addition to the primary canonical recognition patch on ubiquitin, secondary patches are identified, indicating that in cell-mimicking crowded solution, UBA contacts ubiquitin at multiple sites. © 2017 Federation of European Biochemical Societies.

Study of interactions between anionic exopolysaccharides produced by newly isolated probiotic bacteria and sodium caseinate.

PubMed

Abid, Yousra; Joulak, Ichrak; Ben Amara, Chedia; Casillo, Angela; Attia, Hamadi; Gharsallaoui, Adem; Azabou, Samia

2018-07-01

The present study aims to evaluate the interactions between four exopolysaccharides (EPS) produced by probiotic bacteria and sodium caseinate (Cas) in order to simulate their behavior in dairy products. Complexation between the produced EPS samples and Cas was investigated as a function of polysaccharide to protein ratio. The highest turbidity and average size of complexes were formed at an EPS/Cas ratio of 3 (corresponding to 1 g/L of EPS and 0.33 g/L of Cas) as a result of the combination of individual complexes to form aggregates. Zeta potential measurements and Cas surface hydrophobicity results suggested that complex formation occurred essentially through electrostatic attractions with a possible contribution of hydrophobic interaction for EPS-GM which was produced by Bacillus tequilensis-GM. Afterwards, the effect of pH on the complexation between biopolymers was studied when EPS and Cas concentrations were maintained constant at 1 and 0.33 g/L, respectively. pH was adjusted to 3.0 and 3.5, respectively. Results showed that the highest amount and sizes of EPS/Cas complexes were formed at pH 3.5 and that EPS-GM enabled to obtain the biggest and highest amount of aggregates. Therefore, the obtained results support the fact that the simultaneous presence of EPS and Cas in dairy products results in complexes formation via electrostatic interactions depending on EPS/Cas ratio and pH of the medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Insights into the Hendra virus NTAIL-XD complex: Evidence for a parallel organization of the helical MoRE at the XD surface stabilized by a combination of hydrophobic and polar interactions.

PubMed

Erales, Jenny; Beltrandi, Matilde; Roche, Jennifer; Maté, Maria; Longhi, Sonia

2015-08-01

The Hendra virus is a member of the Henipavirus genus within the Paramyxoviridae family. The nucleoprotein, which consists of a structured core and of a C-terminal intrinsically disordered domain (N(TAIL)), encapsidates the viral genome within a helical nucleocapsid. N(TAIL) partly protrudes from the surface of the nucleocapsid being thus capable of interacting with the C-terminal X domain (XD) of the viral phosphoprotein. Interaction with XD implies a molecular recognition element (MoRE) that is located within N(TAIL) residues 470-490, and that undergoes α-helical folding. The MoRE has been proposed to be embedded in the hydrophobic groove delimited by helices α2 and α3 of XD, although experimental data could not discriminate between a parallel and an antiparallel orientation of the MoRE. Previous studies also showed that if the binding interface is enriched in hydrophobic residues, charged residues located close to the interface might play a role in complex formation. Here, we targeted for site directed mutagenesis two acidic and two basic residues within XD and N(TAIL). ITC studies showed that electrostatics plays a crucial role in complex formation and pointed a parallel orientation of the MoRE as more likely. Further support for a parallel orientation was afforded by SAXS studies that made use of two chimeric constructs in which XD and the MoRE were covalently linked to each other. Altogether, these studies unveiled the multiparametric nature of the interactions established within this complex and contribute to shed light onto the molecular features of protein interfaces involving intrinsically disordered regions. Copyright © 2015 Elsevier B.V. All rights reserved.

The evolution of the Dogger Bank, North Sea: A complex history of terrestrial, glacial and marine environmental change

NASA Astrophysics Data System (ADS)

Cotterill, Carol J.; Phillips, Emrys; James, Leo; Forsberg, Carl Fredrik; Tjelta, Tor Inge; Carter, Gareth; Dove, Dayton

2017-09-01

This paper presents a summary of the results of a detailed multidisciplinary study of the near surface geology of the Dogger Bank in the southern central North Sea, forming part of a site investigation for a major windfarm development undertaken by the Forewind consortium. It has revealed that the Dogger Bank is internally complex rather than comprising a simple ;layer cake; of the Quaternary sediments as previously thought. Regional and high-resolution seismic surveys have enabled a revised stratigraphic framework to be established for the upper part of this sequence which comprises the Eem (oldest), Dogger Bank, Bolders Bank formations and Botney Cut Formation (youngest), overlain by a typically thin Holocene sequence. Detailed mapping of key horizons identified on the high-resolution seismic profiles has led to the recognition of a series of buried palaeo-landsystems which are characterised by a range of features including; glacial, glacifluvial and fluvial channels, a large-scale glacitectonic thrust-moraine complex with intervening ice-marginal basins, a lacustrine basin and marine ravinement surfaces. Interpretation of these buried landscapes has enabled the development of an environmental change model to explain the evolution of the Dogger Bank. This evolution was driven by the complex interplay between climate change, ice sheet dynamics and sea level change associated with the growth and subsequent demise of the British and Irish and Fennoscandian ice sheets during the Weichselian glaciation. Following the decay of these ice sheets the Dogger Bank entered a period of significant climatic and environmental flux which saw a terrestrial landscape being progressively inundated as sea levels rose during the Holocene.

Gas-Phase Analysis of the Complex of Fibroblast GrowthFactor 1 with Heparan Sulfate: A Traveling Wave Ion Mobility Spectrometry (TWIMS) and Molecular Modeling Study

NASA Astrophysics Data System (ADS)

Zhao, Yuejie; Singh, Arunima; Xu, Yongmei; Zong, Chengli; Zhang, Fuming; Boons, Geert-Jan; Liu, Jian; Linhardt, Robert J.; Woods, Robert J.; Amster, I. Jonathan

2017-01-01

Fibroblast growth factors (FGFs) regulate several cellular developmental processes by interacting with cell surface heparan proteoglycans and transmembrane cell surface receptors (FGFR). The interaction of FGF with heparan sulfate (HS) is known to induce protein oligomerization, increase the affinity of FGF towards its receptor FGFR, promoting the formation of the HS-FGF-FGFR signaling complex. Although the role of HS in the signaling pathways is well recognized, the details of FGF oligomerization and formation of the ternary signaling complex are still not clear, with several conflicting models proposed in literature. Here, we examine the effect of size and sulfation pattern of HS upon FGF1 oligomerization, binding stoichiometry and conformational stability, through a combination of ion mobility (IM) and theoretical modeling approaches. Ion mobility-mass spectrometry (IMMS) of FGF1 in the presence of several HS fragments ranging from tetrasaccharide (dp4) to dodecasaccharide (dp12) in length was performed. A comparison of the binding stoichiometry of variably sulfated dp4 HS to FGF1 confirmed the significance of the previously known high-affinity binding motif in FGF1 dimerization, and demonstrated that certain tetrasaccharide-length fragments are also capable of inducing dimerization of FGF1. The degree of oligomerization was found to increase in the presence of dp12 HS, and a general lack of specificity for longer HS was observed. Additionally, collision cross-sections (CCSs) of several FGF1-HS complexes were calculated, and were found to be in close agreement with experimental results. Based on the (CCSs) a number of plausible binding modes of 2:1 and 3:1 FGF1-HS are proposed.

Characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems.

PubMed

Bryant, M; Ward, M; Farrar, R; Freeman, R; Brummitt, K; Nolan, J; Neville, A

2014-04-01

This study presents the characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems. Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FI-IR) were utilised in order to assess the surface morphology of retrieved Metal-on-Metal Total Hip Replacements and surface chemistry of the films found on the surface. Gross slip, plastic deformation and directionality of the surface were extensively seen on the proximal surfaces of the retrievals. A more corrosive phenomenon was observed in the distal regions of the stem, demonstrating a seemingly intergranular attack. Tribochemical reactions were seen to occur within the stem-cement interfaces with tribofilms being observed on the femoral stem and counterpart PMMA bone cement. XPS, TEM-EDX and FT-IR analyses demonstrated that the films present in the stem surfaces were a complex mixture of chromium oxide and amorphous organic material. A comparison between current experimental and clinical literature has been conducted and findings from this study demonstrate that the formation and chemistry of films are drastically influenced by the type of wear or degradation mechanism. Films formed in the stem-cement interface are thought to further influence the biological environment outside the stem-cement interface due to the formation of Cr and O rich films within the interface whilst Co is free to migrate away. © 2013 Elsevier Ltd. All rights reserved.

Co-crystal formation between two organic solids on the surface of Titan

NASA Astrophysics Data System (ADS)

Cable, M. L.; Vu, T. H.; Maynard-Casely, H. E.; Hodyss, R. P.

2017-12-01

Laboratory experiments of Titan molecular materials, informed by modeling, can help us to understand the complex and dynamic surface processes occurring on this moon at cryogenic temperatures. We previously demonstrated that two common organic materials on Titan, ethane and benzene, form a unique and stable co-crystalline structure at Titan surface temperatures. We have now characterized a second co-crystal that is stable on Titan, this time between two solids: acetylene and ammonia. The co-crystal forms within minutes at Titan surface temperature, as evidenced by new Raman spectral features in the lattice vibration and C-H bending regions. In addition, a red shift of the C-H stretching mode suggests that the acetylene-ammonia co-crystal is stabilized by a network of C-H···N interactions. Thermal stability studies indicate that this co-crystal remains intact to >110 K, and experiments with liquid methane and ethane reveal the co-crystal to be resistant to fluvial or pluvial exposure. Non-covalently bound structures such as these co-crystals point to far more complex surface interactions than previously believed on Titan. New physical and mechanical properties (deformation, plasticity, density, etc.), differences in storage of key species (i.e., ethane versus methane), variations in surface transport and new chemical gradients can all result in diverse surface features and chemistries of astrobiological interest.

Episodic plate separation and fracture infill on the surface of Europa

USGS Publications Warehouse

Sullivan, R.; Greeley, R.; Homan, K.; Klemaszewski, J.; Belton, M.J.S.; Carr, M.H.; Chapman, C.R.; Tufts, R.; Head, J. W.; Pappalardo, R.; Moore, J.; Thomas, P.

1998-01-01

Images obtained by the Voyager spacecraft revealed dark, wedge-shaped bands on Europa that were interpreted as evidence that surface plates, 50- 100 km across, moved and rotated relative to each other. This implied that they may be mechanically decoupled from the interior by a layer of warm ice or liquid water. Here we report similar features seen in higher resolution images (420 metres per pixel) obtained by the Galileo spacecraft that reveal new details of wedge-band formation. In particular, the interior of one dark band shows bilateral symmetry of parallel lineaments and pit complexes which indicates that plate separation occurred in discrete episodes from a central axis. The images also show that this style of tectonic activity involved plates < 10 km across. Although this tectonic style superficially resembles aspects of similar activity on Earth, such as sea-floor spreading and the formation of ice leads in polar seas, there are significant differences in the underlying physical mechanisms: the wedge-shaped bands on Europa most probably formed when lower material (ice or water) rose to fill the fractures that widened in response to regional surface stresses.

Cysteine as a green corrosion inhibitor for Cu37Zn brass in neutral and weakly alkaline sulphate solutions.

PubMed

Radovanović, Milan B; Petrović, Marija B; Simonović, Ana T; Milić, Snežana M; Antonijević, Milan M

2013-07-01

The aim of this study was to investigate electrochemical properties of brass in neutral and weakly alkaline solutions in the presence of cysteine as a nontoxic and ecological corrosion inhibitor. Potentiodynamic measurements, open circuit potential measurements, as well as chronoamperometric measurements were the methods used during investigation of the inhibitory effect of cysteine on the corrosion behaviour of brass. Potentiodynamic measurements showed that cysteine behaves as a mixed-type inhibitor in the investigated media. Based on polarization curves for brass in a weakly alkaline solution of sodium sulphate at varying cysteine concentrations, an interaction occurs between Cu(+) ions and the inhibitor, resulting in the formation of a protective complex on the electrode surface. The results of chronoamperometric measurements confirm the results obtained by potentiodynamic measurements. Optical microphotography of the brass surface also confirms the formation of a protective film in the presence of a 1 × 10(-4) mol/dm(3) cysteine. Adsorption of cysteine on the brass surface proceeds according to the Langmuir adsorption isotherm.

Experimental design, modeling and optimization of polyplex formation between DNA oligonucleotides and branched polyethylenimine.

PubMed

Clima, Lilia; Ursu, Elena L; Cojocaru, Corneliu; Rotaru, Alexandru; Barboiu, Mihail; Pinteala, Mariana

2015-09-28

The complexes formed by DNA and polycations have received great attention owing to their potential application in gene therapy. In this study, the binding efficiency between double-stranded oligonucleotides (dsDNA) and branched polyethylenimine (B-PEI) has been quantified by processing of the images captured from the gel electrophoresis assays. The central composite experimental design has been employed to investigate the effects of controllable factors on the binding efficiency. On the basis of experimental data and the response surface methodology, a multivariate regression model has been constructed and statistically validated. The model has enabled us to predict the binding efficiency depending on experimental factors, such as concentrations of dsDNA and B-PEI as well as the initial pH of solution. The optimization of the binding process has been performed using simplex and gradient methods. The optimal conditions determined for polyplex formation have yielded a maximal binding efficiency close to 100%. In order to reveal the mechanism of complex formation at the atomic-scale, a molecular dynamic simulation has been carried out. According to the computation results, B-PEI amine hydrogen atoms have interacted with oxygen atoms from dsDNA phosphate groups. These interactions have led to the formation of hydrogen bonds between macromolecules, stabilizing the polyplex structure.

The effect of butterfly scales on flight efficiency and leading edge vortex formation

NASA Astrophysics Data System (ADS)

Lang, Amy; Wilroy, Jacob; Wahidi, Redha; Slegers, Nathan; Heilman, Micahel; Cranford, Jacob

2016-11-01

It is hypothesized that the scales on a butterfly wing lead to increased flight efficiency. Recent testing of live butterflies tracked their motion over 246 flights for 11 different specimens. Results show a 37.8 percent mean decrease in flight efficiency and a flapping amplitude reduction of 6.7 percent once the scales were removed. This change could be largely a result of how the leading edge vortex (LEV) interacts with the wing. To simplify this complex flow problem, an experiment was designed to focus on the alteration of 2-D vortex development with a variation in surface patterning. Specifically, the secondary vorticity generated by the LEV interacting at the patterned surface was studied, as well as the subsequent effect on the LEV's growth rate and peak circulation. For this experiment butterfly inspired grooves were created using additive manufacturing and were attached to a flat plate with a chordwise orientation, thus increasing plate surface area. The vortex generated by the grooved plate was then compared to a smooth case as the plate translated vertically through a tow tank at Re = 1500, 3000, and 6000. Using DPIV, the vortex formation was documented and a maximum vortex formation time of 4.22 was found based on the flat plate travel distance and chord length. Results indicate that the patterned surface slows down the growth of the vortex which corroborates the flight test results. Funding from NSF CBET Fluid Dynamcis is gratefully acknowledged.

An initial event in the insect innate immune response: structural and biological studies of interactions between β-1,3-glucan and the N-terminal domain of β-1,3-glucan recognition protein.

PubMed

Dai, Huaien; Hiromasa, Yasuaki; Takahashi, Daisuke; VanderVelde, David; Fabrick, Jeffrey A; Kanost, Michael R; Krishnamoorthi, Ramaswamy

2013-01-08

In response to invading microorganisms, insect β-1,3-glucan recognition protein (βGRP), a soluble receptor in the hemolymph, binds to the surfaces of bacteria and fungi and activates serine protease cascades that promote destruction of pathogens by means of melanization or expression of antimicrobial peptides. Here we report on the nuclear magnetic resonance (NMR) solution structure of the N-terminal domain of βGRP (N-βGRP) from Indian meal moth (Plodia interpunctella), which is sufficient to activate the prophenoloxidase (proPO) pathway resulting in melanin formation. NMR and isothermal calorimetric titrations of N-βGRP with laminarihexaose, a glucose hexamer containing β-1,3 links, suggest a weak binding of the ligand. However, addition of laminarin, a glucose polysaccharide (~6 kDa) containing β-1,3 and β-1,6 links that activates the proPO pathway, to N-βGRP results in the loss of NMR cross-peaks from the backbone (15)N-(1)H groups of the protein, suggesting the formation of a large complex. Analytical ultracentrifugation (AUC) studies of formation of the N-βGRP-laminarin complex show that ligand binding induces self-association of the protein-carbohydrate complex into a macro structure, likely containing six protein and three laminarin molecules (~102 kDa). The macro complex is quite stable, as it does not undergo dissociation upon dilution to submicromolar concentrations. The structural model thus derived from this study for the N-βGRP-laminarin complex in solution differs from the one in which a single N-βGRP molecule has been proposed to bind to a triple-helical form of laminarin on the basis of an X-ray crystallographic structure of the N-βGRP-laminarihexaose complex [Kanagawa, M., Satoh, T., Ikeda, A., Adachi, Y., Ohno, N., and Yamaguchi, Y. (2011) J. Biol. Chem. 286, 29158-29165]. AUC studies and phenoloxidase activation measurements conducted with the designed mutants of N-βGRP indicate that electrostatic interactions involving Asp45, Arg54, and Asp68 between the ligand-bound protein molecules contribute in part to the stability of the N-βGRP-laminarin macro complex and that a decreased stability is accompanied by a reduced level of activation of the proPO pathway. An increased level of β-1,6 branching in laminarin also results in destabilization of the macro complex. These novel findings suggest that ligand-induced self-association of the βGRP-β-1,3-glucan complex may form a platform on a microbial surface for recruitment of downstream proteases, as a means of amplification of the initial signal of pathogen recognition for the activation of the proPO pathway.

Curiosity Trek

NASA Image and Video Library

2015-12-10

The Mars Science Laboratory, Curiosity, continues its exciting traverse of Mars. In an image acquired in September, it was exploring the boundary between two rock units: the light-toned Murray Formation and the overlying and darker-toned Stimson unit. We can clearly see the rover in a complex terrain marked by tonally varied rocks, which on the surface, can correspond to the contact between rock units and dark sand. http://photojournal.jpl.nasa.gov/catalog/PIA20211

Post-Self-Assembly Cross-Linking to Integrate Molecular Nanofibers with Copolymers in Oscillatory Hydrogels

DTIC Science & Technology

2013-05-09

The BZ reaction provides a model system to mimic a variety of complex processes, such as biological morphogenesis, in monodisperse microemulsions .15...surfaces, ion-exchange resins, membranes, and microemulsions . For example, in addition to minimizing the hydrodynamic effects and formation of bubbles...Reaction-Diffusion Microemulsions Reveals Three-Dimensional Tu- ring Patterns. Science (Washington, DC, U.S.) 2011, 331, 1309−1312. (16) Agladze, K. I

Research and Development in support of the Surface Chemistry Branch. Volume 1

DTIC Science & Technology

1988-06-01

reactions could occur in the melt and/or gas phase-and (2) formation of HCN from RDX pyrolysis followed by hydrolysis with atmospheric/RDX decomposition ...interest is the development of electrochemically active transition metal complexes for the catalytic conversion/ decomposition of dissolved gases, such...impregnated charcoals for the collection and catalytic decomposition of toxic vapors (2), and the evaluation of Navy shipboard environments (3). For the

Protein Corona Influences Cell-Biomaterial Interactions in Nanostructured Tissue Engineering Scaffolds.

PubMed

Serpooshan, Vahid; Mahmoudi, Morteza; Zhao, Mingming; Wei, Ke; Sivanesan, Senthilkumar; Motamedchaboki, Khatereh; Malkovskiy, Andrey V; Gladstone, Andrew B; Cohen, Jeffrey E; Yang, Phillip C; Rajadas, Jayakumar; Bernstein, Daniel; Woo, Y Joseph; Ruiz-Lozano, Pilar

2015-07-22

Biomaterials are extensively used to restore damaged tissues, in the forms of implants (e.g. tissue engineered scaffolds) or biomedical devices (e.g. pacemakers). Once in contact with the physiological environment, nanostructured biomaterials undergo modifications as a result of endogenous proteins binding to their surface. The formation of this macromolecular coating complex, known as 'protein corona', onto the surface of nanoparticles and its effect on cell-particle interactions are currently under intense investigation. In striking contrast, protein corona constructs within nanostructured porous tissue engineering scaffolds remain poorly characterized. As organismal systems are highly dynamic, it is conceivable that the formation of distinct protein corona on implanted scaffolds might itself modulate cell-extracellular matrix interactions. Here, we report that corona complexes formed onto the fibrils of engineered collagen scaffolds display specific, distinct, and reproducible compositions that are a signature of the tissue microenvironment as well as being indicative of the subject's health condition. Protein corona formed on collagen matrices modulated cellular secretome in a context-specific manner ex-vivo , demonstrating their role in regulating scaffold-cellular interactions. Together, these findings underscore the importance of custom-designing personalized nanostructured biomaterials, according to the biological milieu and disease state. We propose the use of protein corona as in situ biosensor of temporal and local biomarkers.

Computational and theoretical approaches for studies of a lipid recognition protein on biological membranes

PubMed Central

Yamamoto, Eiji

2017-01-01

Many cellular functions, including cell signaling and related events, are regulated by the association of peripheral membrane proteins (PMPs) with biological membranes containing anionic lipids, e.g., phosphatidylinositol phosphate (PIP). This association is often mediated by lipid recognition modules present in many PMPs. Here, I summarize computational and theoretical approaches to investigate the molecular details of the interactions and dynamics of a lipid recognition module, the pleckstrin homology (PH) domain, on biological membranes. Multiscale molecular dynamics simulations using combinations of atomistic and coarse-grained models yielded results comparable to those of actual experiments and could be used to elucidate the molecular mechanisms of the formation of protein/lipid complexes on membrane surfaces, which are often difficult to obtain using experimental techniques. Simulations revealed some modes of membrane localization and interactions of PH domains with membranes in addition to the canonical binding mode. In the last part of this review, I address the dynamics of PH domains on the membrane surface. Local PIP clusters formed around the proteins exhibit anomalous fluctuations. This dynamic change in protein-lipid interactions cause temporally fluctuating diffusivity of proteins, i.e., the short-term diffusivity of the bound protein changes substantially with time, and may in turn contribute to the formation/dissolution of protein complexes in membranes. PMID:29159013

Substrate Binding and Catalytic Mechanism of Human Choline Acetyltransferase

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

Kim,A.; Rylett, J.; Shilton, B.

2006-01-01

Choline acetyltransferase (ChAT) catalyzes the synthesis of the neurotransmitter acetylcholine from choline and acetyl-CoA, and its presence is a defining feature of cholinergic neurons. We report the structure of human ChAT to a resolution of 2.2 {angstrom} along with structures for binary complexes of ChAT with choline, CoA, and a nonhydrolyzable acetyl-CoA analogue, S-(2-oxopropyl)-CoA. The ChAT-choline complex shows which features of choline are important for binding and explains how modifications of the choline trimethylammonium group can be tolerated by the enzyme. A detailed model of the ternary Michaelis complex fully supports the direct transfer of the acetyl group from acetyl-CoAmore » to choline through a mechanism similar to that seen in the serine hydrolases for the formation of an acyl-enzyme intermediate. Domain movements accompany CoA binding, and a surface loop, which is disordered in the unliganded enzyme, becomes localized and binds directly to the phosphates of CoA, stabilizing the complex. Interactions between this surface loop and CoA may function to lower the K{sub M} for CoA and could be important for phosphorylation-dependent regulation of ChAT activity.« less

Advanced Engineering Strategies for Periodontal Complex Regeneration.

PubMed

Park, Chan Ho; Kim, Kyoung-Hwa; Lee, Yong-Moo; Seol, Yang-Jo

2016-01-18

The regeneration and integration of multiple tissue types is critical for efforts to restore the function of musculoskeletal complex. In particular, the neogenesis of periodontal constructs for systematic tooth-supporting functions is a current challenge due to micron-scaled tissue compartmentalization, oblique/perpendicular orientations of fibrous connective tissues to the tooth root surface and the orchestration of multiple regenerated tissues. Although there have been various biological and biochemical achievements, periodontal tissue regeneration remains limited and unpredictable. The purpose of this paper is to discuss current advanced engineering approaches for periodontal complex formations; computer-designed, customized scaffolding architectures; cell sheet technology-based multi-phasic approaches; and patient-specific constructs using bioresorbable polymeric material and 3-D printing technology for clinical application. The review covers various advanced technologies for periodontal complex regeneration and state-of-the-art therapeutic avenues in periodontal tissue engineering.

Method and Apparatus for Automated Isolation of Nucleic Acids from Small Cell Samples

NASA Technical Reports Server (NTRS)

Sundaram, Shivshankar; Prabhakarpandian, Balabhaskar; Pant, Kapil; Wang, Yi

2014-01-01

RNA isolation is a ubiquitous need, driven by current emphasis on microarrays and miniaturization. With commercial systems requiring 100,000 to 1,000,000 cells for successful isolation, there is a growing need for a small-footprint, easy-to-use device that can harvest nucleic acids from much smaller cell samples (1,000 to 10,000 cells). The process of extraction of RNA from cell cultures is a complex, multi-step one, and requires timed, asynchronous operations with multiple reagents/buffers. An added complexity is the fragility of RNA (subject to degradation) and its reactivity to surface. A novel, microfluidics-based, integrated cartridge has been developed that can fully automate the complex process of RNA isolation (lyse, capture, and elute RNA) from small cell culture samples. On-cartridge cell lysis is achieved using either reagents or high-strength electric fields made possible by the miniaturized format. Traditionally, silica-based, porous-membrane formats have been used for RNA capture, requiring slow perfusion for effective capture. In this design, high efficiency capture/elution are achieved using a microsphere-based "microfluidized" format. Electrokinetic phenomena are harnessed to actively mix microspheres with the cell lysate and capture/elution buffer, providing important advantages in extraction efficiency, processing time, and operational flexibility. Successful RNA isolation was demonstrated using both suspension (HL-60) and adherent (BHK-21) cells. Novel features associated with this development are twofold. First, novel designs that execute needed processes with improved speed and efficiency were developed. These primarily encompass electric-field-driven lysis of cells. The configurations include electrode-containing constructs, or an "electrode-less" chip design, which is easy to fabricate and mitigates fouling at the electrode surface; and the "fluidized" extraction format based on electrokinetically assisted mixing and contacting of microbeads in a shape-optimized chamber. A secondary proprietary feature is in the particular layout integrating these components to perform the desired operation of RNA isolation. Apart from a novel functional capability, advantages of the innovation include reduced or eliminated use of toxic reagents, and operator-independent extraction of RNA.

Surface salt bridges modulate DNA wrapping by the type II DNA-binding protein TF1.

PubMed

Grove, Anne

2003-07-29

The histone-like protein HU is involved in compaction of the bacterial genome. Up to 37 bp of DNA may be wrapped about some HU homologues in a process that has been proposed to depend on a linked disruption of surface salt bridges that liberates cationic side chains for interaction with the DNA. Despite significant sequence conservation between HU homologues, binding sites from 9 to 37 bp have been reported. TF1, an HU homologue that is encoded by Bacillus subtilis bacteriophage SPO1, has nM affinity for 37 bp preferred sites in DNA with 5-hydroxymethyluracil (hmU) in place of thymine. On the basis of electrophoretic mobility shift assays, we show that TF1-DNA complex formation is associated with a net release of only approximately 0.5 cations. The structure of TF1 suggests that Asp13 can form a dehydrated surface salt bridge with Lys23; substitution of Asp13 with Ala increases the net release of cations to approximately 1. These data are consistent with complex formation linked to disruption of surface salt bridges. Substitution of Glu90 with Ala, which would expose Lys87 predicted to contact DNA immediately distal to a proline-mediated DNA kink, causes an increase in affinity and an abrogation of the preference for hmU-containing DNA. We propose that hmU preference is due to finely tuned interactions at the sites of kinking that expose a differential flexibility of hmU- and T-containing DNA. Our data further suggest that the difference in binding site size for HU homologues is based on a differential ability to stabilize the DNA kinks.

Thermodynamics and kinetics of RNA tertiary structure formation in the junctionless hairpin ribozyme.

PubMed

White, Neil A; Hoogstraten, Charles G

2017-09-01

The hairpin ribozyme consists of two RNA internal loops that interact to form the catalytically active structure. This docking transition is a rare example of intermolecular formation of RNA tertiary structure without coupling to helix annealing. We have used temperature-dependent surface plasmon resonance (SPR) to characterize the thermodynamics and kinetics of RNA tertiary structure formation for the junctionless form of the ribozyme, in which loops A and B reside on separate molecules. We find docking to be strongly enthalpy-driven and to be accompanied by substantial activation barriers for association and dissociation, consistent with the structural reorganization of both internal loops upon complex formation. Comparisons with the parallel analysis of a ribozyme variant carrying a 2'-O-methyl modification at the self-cleavage site and with published data in other systems reveal a surprising diversity of thermodynamic signatures, emphasizing the delicate balance of contributions to the free energy of formation of RNA tertiary structure. Copyright © 2017 Elsevier B.V. All rights reserved.

Simulated formation and flow of microemulsions during surfactant flushing of contaminated soil.

PubMed

Ouyan, Ying; Cho, Jong Soo; Mansell, Robert S

2002-01-01

Contamination of groundwater resources by non-aqueous phase liquids (NAPLs) has become an issue of increasing environmental concern. This study investigated the formation and flow of microemulsions during surfactant flushing of NAPL-contaminated soil using the finite difference model UTCHEM, which was verified with our laboratory experimental data. Simulation results showed that surfactant flushing of NAPLs (i.e., trichloroethylene and tetrachloroethylene) from the contaminated soils was an emulsion-driven process. Formation of NAPL-in-water microemulsions facilitated the removal of NAPLs from contaminated soils. Changes in soil saturation pressure were used to monitor the mobilization and entrapment of NAPLs during surface flushing process. In general, more NAPLs were clogged in soil pores when the soil saturation pressure increased. Effects of aquifer salinity on the formation and flow of NAPL-in-water microemulsions were significant. This study suggests that the formation and flow of NAPL-in-water microemulsions through aquifer systems are complex physical-chemical phenomena that are critical to effective surfactant flushing of contaminated soils.

Triggers for β-sheet formation at the hydrophobic-hydrophilic interface: high concentration, in-plane orientational order, and metal ion complexation.

PubMed

Hoernke, Maria; Falenski, Jessica A; Schwieger, Christian; Koksch, Beate; Brezesinski, Gerald

2011-12-06

Amyloid formation plays a causative role in neurodegenerative diseases such as Alzheimer's disease or Parkinson's disease. Soluble peptides form β-sheets that subsequently rearrange into fibrils and deposit as amyloid plaques. Many parameters trigger and influence the onset of the β-sheet formation. Early stages are recently discussed to be cell-toxic. Aiming at understanding various triggers such as interactions with hydrophobic-hydrophilic interfaces and metal ion complexation and their interplay, we investigated a set of model peptides at the air-water interface. We are using a general approach to a variety of diseases such as Alzheimer's disease, Parkinson's disease, and type II diabetes that are connected to amyloid formation. Surface sensitive techniques combined with film balance measurements have been used to assess the conformation of the peptides and their orientation at the air-water interface (IR reflection-absorption spectroscopy). Additionally, the structures of the peptide layers were characterized by grazing incidence X-ray diffraction and X-ray reflectivity. The peptides adsorb to the air-water interface and immediately adopt an α-helical conformation. This helical intermediate transforms into β-sheets upon further triggering. The factors that result in β-sheet formation are dependent on the peptide sequence. In general, the interface has the strongest effect on peptide conformation compared to high concentrations or metal ions. Metal ions are able to prevent aggregation in bulk but not at the interface. At the interface, metal ion complexation has only minor effects on the peptide secondary structure, influencing the in-plane structure that is formed in two dimensions. At the air-water interface, increased concentrations or a parallel arrangement of the α-helical intermediates are the most effective triggers. This study reveals the role of various triggers for β-sheet formation and their complex interplay. Our main finding is that the hydrophobic-hydrophilic interface largely governs the conformation of peptides. Therefore, the present study implies that special care is needed when interpreting data that may be affected by different amounts or types of interfaces during experimentation. © 2011 American Chemical Society

Origin of dislocation luminescence centers and their reorganization in p-type silicon crystal subjected to plastic deformation and high temperature annealing.

PubMed

Pavlyk, Bohdan; Kushlyk, Markiyan; Slobodzyan, Dmytro

2017-12-01

Changes of the defect structure of silicon p-type crystal surface layer under the influence of plastic deformation and high temperature annealing in oxygen atmosphere were investigated by deep-level capacitance-modulation spectroscopy (DLCMS) and IR spectroscopy of molecules and atom vibrational levels. Special role of dislocations in the surface layer of silicon during the formation of its energy spectrum and rebuilding the defective structure was established. It is shown that the concentration of linear defects (N ≥ 10 4  cm -2 ) enriches surface layer with electrically active complexes (dislocation-oxygen, dislocation-vacancy, and dislocation-interstitial atoms of silicon) which are an effective radiative recombination centers.

Adsorption of natural dissolved organic matter at the oxide/water interface

USGS Publications Warehouse

Davis, James A.

1982-01-01

Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.

COMETARY SCIENCE. 67P/Churyumov-Gerasimenko surface properties as derived from CIVA panoramic images.

PubMed

Bibring, J-P; Langevin, Y; Carter, J; Eng, P; Gondet, B; Jorda, L; Le Mouélic, S; Mottola, S; Pilorget, C; Poulet, F; Vincendon, M

2015-07-31

The structure and composition of cometary constituents, down to their microscopic scale, are critical witnesses of the processes and ingredients that drove the formation and evolution of planetary bodies toward their present diversity. On board Rosetta's lander Philae, the Comet Infrared and Visible Analyser (CIVA) experiment took a series of images to characterize the surface materials surrounding the lander on comet 67P/Churyumov-Gerasimenko. Images were collected twice: just after touchdown, and after Philae finally came to rest, where it acquired a full panorama. These images reveal a fractured surface with complex structure and a variety of grain scales and albedos, possibly constituting pristine cometary material. Copyright © 2015, American Association for the Advancement of Science.

Effect of Natural Organic Matter on Plutonium Sorption to Goethite

DOE PAGES

Conroy, Nathan A.; Zavarin, Mavrik; Kersting, Annie B.; ...

2016-11-21

For this research, the effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mg C·L –1 and 50 mg C·L –1 natural organic matter (NOM), 10 –9–10 –10 M 238Pu, and 0.1 g·L –1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increasedmore » Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. In conclusion, the results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.« less

Ionic residues of human serum transferrin affect binding to the transferrin receptor and iron release.

PubMed

Steere, Ashley N; Miller, Brendan F; Roberts, Samantha E; Byrne, Shaina L; Chasteen, N Dennis; Smith, Valerie C; MacGillivray, Ross T A; Mason, Anne B

2012-01-17

Efficient delivery of iron is critically dependent on the binding of diferric human serum transferrin (hTF) to its specific receptor (TFR) on the surface of actively dividing cells. Internalization of the complex into an endosome precedes iron removal. The return of hTF to the blood to continue the iron delivery cycle relies on the maintenance of the interaction between apohTF and the TFR after exposure to endosomal pH (≤6.0). Identification of the specific residues accounting for the pH-sensitive nanomolar affinity with which hTF binds to TFR throughout the cycle is important to fully understand the iron delivery process. Alanine substitution of 11 charged hTF residues identified by available structures and modeling studies allowed evaluation of the role of each in (1) binding of hTF to the TFR and (2) TFR-mediated iron release. Six hTF mutants (R50A, R352A, D356A, E357A, E367A, and K511A) competed poorly with biotinylated diferric hTF for binding to TFR. In particular, we show that Asp356 in the C-lobe of hTF is essential to the formation of a stable hTF-TFR complex: mutation of Asp356 in the monoferric C-lobe hTF background prevented the formation of the stoichiometric 2:2 (hTF:TFR monomer) complex. Moreover, mutation of three residues (Asp356, Glu367, and Lys511), whether in the diferric or monoferric C-lobe hTF, significantly affected iron release when in complex with the TFR. Thus, mutagenesis of charged hTF residues has allowed identification of a number of residues that are critical to formation of and release of iron from the hTF-TFR complex.

Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation

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

Hazawa, Masaharu; Tomiyama, Kenichi; Saotome-Nakamura, Ai

Highlights: • Radiation increases cellular uptake of exosomes. • Radiation induces colocalization of CD29 and CD81. • Exosomes selectively bind the CD29/CD81 complex. • Radiation increases the cellular uptake of exosomes through CD29/CD81 complex formation. - Abstract: Exosomes mediate intercellular communication, and mesenchymal stem cells (MSC) or their secreted exosomes affect a number of pathophysiologic states. Clinical applications of MSC and exosomes are increasingly anticipated. Radiation therapy is the main therapeutic tool for a number of various conditions. The cellular uptake mechanisms of exosomes and the effects of radiation on exosome–cell interactions are crucial, but they are not well understood.more » Here we examined the basic mechanisms and effects of radiation on exosome uptake processes in MSC. Radiation increased the cellular uptake of exosomes. Radiation markedly enhanced the initial cellular attachment to exosomes and induced the colocalization of integrin CD29 and tetraspanin CD81 on the cell surface without affecting their expression levels. Exosomes dominantly bound to the CD29/CD81 complex. Knockdown of CD29 completely inhibited the radiation-induced uptake, and additional or single knockdown of CD81 inhibited basal uptake as well as the increase in radiation-induced uptake. We also examined possible exosome uptake processes affected by radiation. Radiation-induced changes did not involve dynamin2, reactive oxygen species, or their evoked p38 mitogen-activated protein kinase-dependent endocytic or pinocytic pathways. Radiation increased the cellular uptake of exosomes through CD29/CD81 complex formation. These findings provide essential basic insights for potential therapeutic applications of exosomes or MSC in combination with radiation.« less

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide-natural organic matter complexes.

PubMed

Yan, Jinlong; Jiang, Tao; Yao, Ying; Wang, Jun; Cai, Yuanli; Green, Nelson W; Wei, Shiqiang

2017-05-01

The phosphorus (P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid (HA) complexes were analyzed using the ultrafiltration method in this study. With an initial P concentration of 20mg/L (I=0.01mol/L and pH=7), it was shown that the colloid (1kDa-0.45μm) component of P accounted for 10.6%, 11.6%, 6.5%, and 4.0% of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite (FH), goethite (GE), ferrihydrite-humic acid complex (FH-HA), goethite-humic acid complex (GE-HA), respectively. The <1kDa component of P was still the predominant fraction in the supernatant, and underestimated colloidal P accounted for 2.2%, 55.1%, 45.5%, and 38.7% of P adsorption onto the solid surface of FH, FH-HA, GE and GE-HA, respectively. Thus, the colloid P could not be neglected. Notably, it could be interpreted that Fe 3+ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant. And colloidal adsorbent particles co-existing in the supernatant were another important reason for it. Additionally, dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant. Ultimately, we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P, even when considering other contaminants such as organic pollutants, heavy metal ions, and arsenate at the sediment/soil-water interface in the real environment. Copyright © 2016. Published by Elsevier B.V.

Effect of Natural Organic Matter on Plutonium Sorption to Goethite

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

Conroy, Nathan A.; Zavarin, Mavrik; Kersting, Annie B.

For this research, the effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mg C·L –1 and 50 mg C·L –1 natural organic matter (NOM), 10 –9–10 –10 M 238Pu, and 0.1 g·L –1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increasedmore » Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. In conclusion, the results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.« less

The Mysteries and Curiosities of Mars: A Tour of Unusual and Unexplained Terrains

NASA Astrophysics Data System (ADS)

Kerber, L.

2017-12-01

The large amount of data available from orbiting satellites around Mars has provided a wealth of information about the Martian surface and geological history. The published literature tends to focus on regions of Mars for which there are ready explanations; however, many regions of Mars remain mysterious. In this contribution, we present some of the strangest and least explained terrains on Mars: The Taffy Terrain: This complex terrain, consisting of swirling layers with variably sized bands, is present mostly at the bottom of Hellas Basin, but versions of it can also be found on the floor of Melas Chasma and in the Medusae Fossae Formation near Apollinaris Sulci. While little has been written about the taffy terrain, hypotheses include "glacial features" and salt domes. The taffy terrain bears some resemblance to submarine salt domes in the Gulf of Mexico, glacial deposits with mixed ash and ice in Iceland, or chalk formations in Egypt's White Desert. The Fishscale Terrain: At the northern edge of Lucus Planum, the friable Medusae Fossae Formation transitions into a chaos-like terrain with hundreds of mesas forming a pattern like the scales of a fish. While chaos terrains are mysterious in general, this morphologically fresh, near-equatorial chaos is especially unusual. Polygonal Ridges in Gordii Dorsum: Also a part of the Medusae Fossae Formation, the ridges in Gordii Dorsum represent a negative image of the fishscale terrain—a intricate lattice of slender black ridges. These are thought to form via the embayment of the fishscale terrain with lava and the subsequent erosion of the original mesas. Horseshoe Features: These geomorphological features look like inverted barchan dunes, but they are actually pits eroded into the surface of the Medusae Fossae Formation. Channels surrounding Elysium Mons: These channel systems are among the most complex on Mars, but they appear on a young Amazonian lava surface. The channels cut through topography, anastomose, and create streamlined islands. Strange flows around cones: Some rootless cones in Cerberus Palus have unusual flows coming out of them. Possible hypotheses include lava or mudflows. Sinus Meridiani: This region is host to arcuate ridge lattices, circular mesas with concentric patterns, and straight, subparallel ridges, similar to other ridges found near the South Pole.

The Interaction of Streptococcal Enolase with Canine Plasminogen: The Role of Surfaces in Complex Formation

PubMed Central

Balhara, Vinod; Deshmukh, Sasmit S.; Kálmán, László; Kornblatt, Jack A.

2014-01-01

The enolase from Streptococcus pyogenes (Str enolase F137L/E363G) is a homo-octamer shaped like a donut. Plasminogen (Pgn) is a monomeric protein composed of seven discrete separated domains organized into a lock washer. The enolase is known to bind Pgn. In past work we searched for conditions in which the two proteins would bind to one another. The two native proteins in solution would not bind under any of the tried conditions. We found that if the structures were perturbed binding would occur. We stated that only the non-native Str enolase or Pgn would interact such that we could detect binding. We report here the results of a series of dual polarization interferometry (DPI) experiments coupled with atomic force microscopy (AFM), isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and fluorescence. We show that the critical condition for forming stable complexes of the two native proteins involves Str enolase binding to a surface. Surfaces that attract Str enolase are a sufficient condition for binding Pgn. Under certain conditions, Pgn adsorbed to a surface will bind Str enolase. PMID:24520380

Manipulating the Surface Chemistry of Quantum Dots for Sensitive Ratiometric Fluorescence Detection of Sulfur Dioxide.

PubMed

Li, Huihui; Zhu, Houjuan; Sun, Mingtai; Yan, Yehan; Zhang, Kui; Huang, Dejian; Wang, Suhua

2015-08-11

Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.

Adsorption of protein GlnB of Herbaspirillum seropedicae on Si(111) investigated by AFM and XPS.

PubMed

Lubambo, A F; Benelli, E M; Klein, J; Schreiner, W; Camargo, P C

2006-01-01

The protein GlnB-Hs (GlnB of Herbaspirillum seropedicae) in diazotroph micro-organisms signalizes levels of nitrogen, carbon, and energy for a series of proteins involved in the regulation of expression and control of the activity of nitrogenase complex that converts atmospheric nitrogen in ammonia, resulting in biological nitrogen fixation. Its structure has already been determined by X-ray diffraction, revealing a trimer of (36 kDa) with lateral cavities having hydrophilic boundaries. The interactions of GlnB-Hs with the well-known Si(111) surface were investigated for different incubation times, protein concentrations in initial solution, deposition conditions, and substrate initial state. The protein solution was deposited on Si(111) and dried under controlled conditions. An atomic force microscope operating in dynamic mode shows images of circular, linear, and more complex donut-shaped protein arrangement, and also filament types of organization, which vary from a few nanometers to micrometers. Apparently, the filament formation was favored because of protein surface polarity when in contact with the silicon surface, following some specific orientation. The spin-coating technique was successfully used to obtain more uniform surface covering.