Sample records for surface dna-monomer complexes

  1. Predictive Surface Complexation Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Sverjensky, Dimitri A. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Earth and Planetary Sciences


    Surface complexation plays an important role in the equilibria and kinetics of processes controlling the compositions of soilwaters and groundwaters, the fate of contaminants in groundwaters, and the subsurface storage of CO2 and nuclear waste. Over the last several decades, many dozens of individual experimental studies have addressed aspects of surface complexation that have contributed to an increased understanding of its role in natural systems. However, there has been no previous attempt to develop a model of surface complexation that can be used to link all the experimental studies in order to place them on a predictive basis. Overall, my research has successfully integrated the results of the work of many experimentalists published over several decades. For the first time in studies of the geochemistry of the mineral-water interface, a practical predictive capability for modeling has become available. The predictive correlations developed in my research now enable extrapolations of experimental studies to provide estimates of surface chemistry for systems not yet studied experimentally and for natural and anthropogenically perturbed systems.

  2. Machining of Complex Sculptured Surfaces

    CERN Document Server


    The machining of complex sculptured surfaces is a global technological topic in modern manufacturing with relevance in both industrialized and emerging in countries particularly within the moulds and dies sector whose applications include highly technological industries such as the automotive and aircraft industry. Machining of Complex Sculptured Surfaces considers new approaches to the manufacture of moulds and dies within these industries. The traditional technology employed in the manufacture of moulds and dies combined conventional milling and electro-discharge machining (EDM) but this has been replaced with  high-speed milling (HSM) which has been applied in roughing, semi-finishing and finishing of moulds and dies with great success. Machining of Complex Sculptured Surfaces provides recent information on machining of complex sculptured surfaces including modern CAM systems and process planning for three and five axis machining as well as explanations of the advantages of HSM over traditional methods ra...

  3. Complex multiplication of abelian surfaces

    NARCIS (Netherlands)

    Streng, Theodorus Cornelis


    The theory of complex multiplication makes it possible to construct certain class fields and abelian varieties. The main theme of this thesis is making these constructions explicit for the case where the abelian varieties have dimension 2. Chapter I is an introduction to complex

  4. Computational Complexity of Combinatorial Surfaces

    NARCIS (Netherlands)

    Vegter, Gert; Yap, Chee K.


    We investigate the computational problems associated with combinatorial surfaces. Specifically, we present an algorithm (based on the Brahana-Dehn-Heegaard approach) for transforming the polygonal schema of a closed triangulated surface into its canonical form in O(n log n) time, where n is the

  5. Holographic subregion complexity for singular surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bakhshaei, Elaheh [Isfahan University of Technology, Department of Physics, Isfahan (Iran, Islamic Republic of); Mollabashi, Ali [Institute for Research in Fundamental Sciences (IPM), School of Physics, Tehran (Iran, Islamic Republic of); Shirzad, Ahmad [Isfahan University of Technology, Department of Physics, Isfahan (Iran, Islamic Republic of); Institute for Research in Fundamental Sciences (IPM), School of Particles and Accelerators, Tehran (Iran, Islamic Republic of)


    Recently holographic prescriptions were proposed to compute the quantum complexity of a given state in the boundary theory. A specific proposal known as 'holographic subregion complexity' is supposed to calculate the complexity of a reduced density matrix corresponding to a static subregion. We study different families of singular subregions in the dual field theory and find the divergence structure and universal terms of holographic subregion complexity for these singular surfaces. We find that there are new universal terms, logarithmic in the UV cut-off, due to the singularities of a family of surfaces including a kink in (2 + 1) dimensions and cones in even dimensional field theories. We also find examples of new divergent terms such as squared logarithm and negative powers times the logarithm of the UV cut-off parameter. (orig.)

  6. Surface complexation of antimony on kaolinite. (United States)

    Rakshit, Sudipta; Sarkar, Dibyendu; Datta, Rupali


    Geochemical fate of antimony (Sb) - a similar oxyanion as arsenic (As) - in a variety of environment is largely unexplored. Kaolinite is an important, naturally occurring clay mineral in soils and aquifers and is known to control the fate of several contaminants via a multitude of geochemical processes, primarily adsorption. Here we report adsorption of antimony on kaolinite as a function of solution chemistry: initial antimony concentration, pH, ionic strength, and a competing anion. A surface complexation modeling (SCM) approach was undertaken to understand the potential mechanistic implications of sorption envelope data. In the SCM, a multicomponent additive approach, in which kaolinite is assumed to be a (1:1) mixture of quartz (≡SiOH) and gibbsite (≡AlOH), was tested. Results indicated that ionic strength has a minimal effect on antimony adsorption. For the lower initial antimony concentration (4.11 μM), the additive model with binuclear surface complexes on quartz and gibbsite showed a better fit at pH3.5. However, the additive model with binuclear surface complex on quartz and mononuclear surface complex on gibbsite showed an excellent fit of the data. Phosphate greatly influenced antimony adsorption on kaolinite at both low and high antimony loadings, indicating competition for available surface sites. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Surface-complexation models for sorption onto heterogeneous surfaces

    International Nuclear Information System (INIS)

    Harvey, K.B.


    This report provides a description of the discrete-logK spectrum model, together with a description of its derivation, and of its place in the larger context of surface-complexation modelling. The tools necessary to apply the discrete-logK spectrum model are discussed, and background information appropriate to this discussion is supplied as appendices. (author)


    Directory of Open Access Journals (Sweden)

    A. V. Kovalchuk


    Full Text Available The method of complex surface hardening of steel detailswas designed. The method is a compound of two processes of hardening: chemical heat treatment and physical vapor deposition (PVD of the coating. The result, achieved in this study is much higher, than in other work on this topic and is cumulative. The method designed can be used in mechanical engineering, medicine, energetics and is perspective for military and space technologies.

  9. The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson-Crick Pairs. (United States)

    Raeber, Alexandra E; Wong, Bryan M


    We present a detailed analysis of several time-dependent DFT (TD-DFT) methods, including conventional hybrid functionals and two types of nonempirically tuned range-separated functionals, for predicting a diverse set of electronic excitations in DNA nucleobase monomers and dimers. This large and extensive set of excitations comprises a total of 50 different transitions (for each tested DFT functional) that includes several n → π and π → π* valence excitations, long-range charge-transfer excitations, and extended Rydberg transitions (complete with benchmark calculations from high-level EOM-CCSD(T) methods). The presence of localized valence excitations as well as extreme long-range charge-transfer excitations in these systems poses a serious challenge for TD-DFT methods that allows us to assess the importance of both short- and long-range exchange contributions for simultaneously predicting all of these various transitions. In particular, we find that functionals that do not have both short- and full long-range exchange components are unable to predict the different types of nucleobase excitations with the same accuracy. Most importantly, the current study highlights the importance of both short-range exchange and a nonempirically tuned contribution of long-range exchange for accurately predicting the diverse excitations in these challenging nucleobase systems.

  10. Integrated manufacturing of complex freeform surfaces (United States)

    Niehaus, Frank; Huttenhuis, Stephan; Pisarski, Alex


    Innovative freeform optical systems such as head-up displays or LED headlights often require high quality and high volume optics. Injection molded polymer optics offer a cost effective solution. However, mold manufacturing for this process is extremely challenging as the machining of freeform surfaces is currently characterized by several independent production steps which can limit surface accuracy. By integrating diamond turning, milling, and metrology onto a single platform, the UPC 400 improves surface accuracy. Advanced software for machining and measurement data further reduces surface inaccuracies. This combination makes the UPC 400 efficient for prototyping free-form optics and manufacturing high precision molds.

  11. Marked fatgraph complexes and surface automorphisms

    DEFF Research Database (Denmark)

    Kuno, Yusuke; Penner, Robert; Turaev, Vladimir


    Combinatorial aspects of the Torelli-Johnson-Morita theory of surface automorphisms are extended to certain subgroups of the mapping class groups. These subgroups are defined relative to a specified homomorphism from the fundamental group of the surface onto an arbitrary group $K$. For $K$ abelia...


    Directory of Open Access Journals (Sweden)

    S. S. Tyshchenko


    Full Text Available Purpose. The paper focuses on ensuring the rational choice of parameters of the mating surfaces of parts when designing process equipment based on the methods of artificial intelligence. Methodology. The paper considers the geometric model of a ruled developed surface, the conditions of existence of such a surface and provides a generalized algorithm for surface plotting regardless of the type of the working element or the machine-building product. One of the most common technical surfaces are the ruled ones, among which a special position is occupied by developed surfaces (thanks to their differential-parametric properties: surface tangent plane is n contact along the rectilinear generator and does not change its position in space when changing the point of contact; surfaces can be produced by bending sheet metal. These provisions enable a product manufacturer to save significant material and energy means, therefore, the development of geometric models of such surfaces is an important task. Findings. We analyzed the geometrical model of the developed surface which is incident to two guides. Experimental studies have shown the applicationprospectivity of semi-digger moldboards on moldboard plows, particularly on the double-deck ones. Taking into account the operating speed of the plow 2.8 m/s, the plant residues plowing percentage for plow with semi-digger moldboards is 98.9%, and with the digger ones – 96.1%. Originality. According to results: 1 the approaches to solving the problem of recognition of wear conditions of the tested interface, depicted by its conceptual model, were elaborated; 2 the corresponding algorithms of the computational procedures were built; 3 the mathematical model that determines the effect of the parameters of the contacting surfaces on their performance properties – linear wear rate during the normal wear and tear was developed; 4 for this model the theoretical prerequisite of use for the random mating study were

  13. Surface nucleation in complex rheological systems (United States)

    Herfurth, J.; Ulrich, J.


    Forced nucleation induced by suitable foreign seeds is an important tool to control the production of defined crystalline products. The quality of a surface provided by seed materials represents an important variable in the production of crystallizing layers that means for the nucleation process. Parameters like shape and surface structure, size and size distribution of the seed particles as well as the ability to hold up the moisture (the solvent), can have an influence on the nucleation process of different viscous supersaturated solutions. Here the properties of different starch powders as seeds obtained from corn, potato, rice, tapioca and wheat were tested. It could be found, that the best nucleation behavior of a sugar solution could be reached with the use of corn starch as seed material. Here the surface of the crystallized sugar layer is smooth, crystallization time is short (<3 h) and the shape of the product is easily reproducible. Beneficial properties of seed materials are therefore an edged, uneven surface, small particle sizes as well as low moisture content at ambient conditions within the seed materials.

  14. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad


    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  15. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the samples was ...

  16. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    Abstract. The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the ...

  17. Removal of arsenate by ferrihydrite via surface complexation and surface precipitation

    International Nuclear Information System (INIS)

    Jiang, Xiuli; Peng, Changjun; Fu, Dun; Chen, Zheng; Shen, Liang; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng


    Graphical abstract: - Highlights: • Surface complexation and surface precipitation of As on ferrihydrite happen at pH 3–6. • The formation of surface precipitation enhanced As(V) adsorption. • The dissolved Fe 3+ had a good linear relationship with the amount of arsenate re-adsorption. - Abstract: In this study, macroscopic and spectroscopic experimental methods accurately modeled the sorption process of arsenate on ferrihydrite. EXAFS, X-ray diffraction and infrared (IR) spectroscopy indicated that the behavior of As(V) adsorption onto ferrihydrite took place mainly via surface complexation and surface precipitation at acidic pH (3.0–6.0), while the surface precipitation was dominated at longer time intervals and higher Fe 3+ concentration. The macroscopic competitive adsorption experiment between arsenate with phosphate indicated two types of adsorption sites existing on the surface of ferrihydrite, i.e., non-exchangeable sites, which are responsible for a rapid surface complex formation; and exchangeable sites for a slow build-up of surface precipitates. In the slow build-up precipitates, the As(V) surface coverage (mmol/g) exhibited a good linear relationship (R 2 = 0.952) with the amount of dissolved Fe 3+ . Three steps are involved during the process of surface precipitation, i.e., (1) an initial uptake of As(V) via surface complexation; (2) re-adsorption of Fe 3+ leaching from ferrihydrite on the surface complex; and (3) As(V) adsorption via surface complexation again and finally forming the surface precipitate.

  18. Compact complex surfaces with geometric structures related to split quaternions

    International Nuclear Information System (INIS)

    Davidov, Johann; Grantcharov, Gueo; Mushkarov, Oleg; Yotov, Miroslav


    We study the problem of existence of geometric structures on compact complex surfaces that are related to split quaternions. These structures, called para-hypercomplex, para-hyperhermitian and para-hyperkähler, are analogs of the hypercomplex, hyperhermitian and hyperkähler structures in the definite case. We show that a compact 4-manifold carries a para-hyperkähler structure iff it has a metric of split signature together with two parallel, null, orthogonal, pointwise linearly independent vector fields. Every compact complex surface admitting a para-hyperhermitian structure has vanishing first Chern class and we show that, unlike the definite case, many of these surfaces carry infinite-dimensional families of such structures. We provide also compact examples of complex surfaces with para-hyperhermitian structures which are not locally conformally para-hyperkähler. Finally, we discuss the problem of non-existence of para-hyperhermitian structures on Inoue surfaces of type S 0 and provide a list of compact complex surfaces which could carry para-hypercomplex structures.

  19. Compact complex surfaces with geometric structures related to split quaternions

    Energy Technology Data Exchange (ETDEWEB)

    Davidov, Johann, E-mail: [Institute of Mathematics and Informatics, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); ' L. Karavelov' Civil Engineering Higher School, 175 Suhodolska Str., 1373 Sofia (Bulgaria); Grantcharov, Gueo, E-mail: [Department of Mathematics and Statistics, Florida International University, Miami, FL 33199 (United States); Mushkarov, Oleg, E-mail: [Institute of Mathematics and Informatics, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Yotov, Miroslav, E-mail: [Department of Mathematics and Statistics, Florida International University, Miami, FL 33199 (United States)


    We study the problem of existence of geometric structures on compact complex surfaces that are related to split quaternions. These structures, called para-hypercomplex, para-hyperhermitian and para-hyperkaehler, are analogs of the hypercomplex, hyperhermitian and hyperkaehler structures in the definite case. We show that a compact 4-manifold carries a para-hyperkaehler structure iff it has a metric of split signature together with two parallel, null, orthogonal, pointwise linearly independent vector fields. Every compact complex surface admitting a para-hyperhermitian structure has vanishing first Chern class and we show that, unlike the definite case, many of these surfaces carry infinite-dimensional families of such structures. We provide also compact examples of complex surfaces with para-hyperhermitian structures which are not locally conformally para-hyperkaehler. Finally, we discuss the problem of non-existence of para-hyperhermitian structures on Inoue surfaces of type S{sup 0} and provide a list of compact complex surfaces which could carry para-hypercomplex structures.

  20. Surface Complexation of Calcium Minerals in Aqueous Solution. (United States)

    Wu; Forsling; Holmgren


    The complexation of Alizarin Red S (ARS) at the surface of hydrous fluorite particles has been investigated by means of potentiometric titrations, adsorption experiments, and zeta-potential measurements in 0.1 mol dm(-3) KCl ionic medium at 25.0 degrees C, as well as by UV/visible specular reflectance, FT-IR, and FT-Raman spectroscopy. Chemical reaction models describing the equilibria of ARS (HA(2-)) at the aqueous fluorite surfaces ( identical withX) have been established as follows: Experimental data were evaluated using the computer program FITEQL on the basis of a constant capacitance model for the electric double layer. Surface complexation mechanisms involving the R-SO(3)(-), R-beta-OH, and R-alpha-OH active groups of the ARS molecule are proposed to describe coordination to the fluorite surface. Copyright 2000 Academic Press.

  1. Surface complexation modeling of americium sorption onto volcanic tuff. (United States)

    Ding, M; Kelkar, S; Meijer, A


    Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways. Published by Elsevier Ltd.

  2. Surface-complexation modelling for describing adsorption of ...

    African Journals Online (AJOL)


    Jun 8, 2013 ... Adsorption of dissolved phosphate onto synthetic hydrous ferric oxide (HFO) was measured in the laboratory as a function of pH, ionic strength, and phosphate relative concentration. Experimental data were used to constrain optimal values of surface complexation reactions using a geochemical modeling ...

  3. Hirshfeld surface analysis of new organotin(IV)-phosphoramide complexes

    Czech Academy of Sciences Publication Activity Database

    Pourayoubi, M.; Bayraq, S.S.; Tarahhomi, A.; Nečas, M.; Fejfarová, Karla; Dušek, Michal


    Roč. 751, SI (2014), s. 508-518 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : organotin(IV)-phosphoramide complexes * Hirshfeld surfaces * two-dimensional fingerprint plots * crystal packing Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.173, year: 2014

  4. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao-Rong [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); University of Chinese Academy of Sciences, 100049 Beijing (China); Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); Changchun University of Science and Technology, 130022 Changchun (China); Pan, Ge-Bo, E-mail: [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China)


    Graphical abstract: GaN surface was etched by 0.3 M EDTA-2Na. The proposed complexation dissolution mechanism can be applicable to almost all neutral etchants under the prerequisite of strong light and electric field. - Highlights: • GaN surface was etched by EDTA-2Na. • GaN may be dissolved into EDTA-2Na by forming Ga–EDTA complex. • We propose the complexation dissolution mechanism for the first time. - Abstract: Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 10{sup 9} per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga–EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

  5. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

    International Nuclear Information System (INIS)

    Zhang, Miao-Rong; Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui; Pan, Ge-Bo


    Graphical abstract: GaN surface was etched by 0.3 M EDTA-2Na. The proposed complexation dissolution mechanism can be applicable to almost all neutral etchants under the prerequisite of strong light and electric field. - Highlights: • GaN surface was etched by EDTA-2Na. • GaN may be dissolved into EDTA-2Na by forming Ga–EDTA complex. • We propose the complexation dissolution mechanism for the first time. - Abstract: Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 10 9 per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga–EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

  6. Surface active complexes formed between keratin polypeptides and ionic surfactants. (United States)

    Pan, Fang; Lu, Zhiming; Tucker, Ian; Hosking, Sarah; Petkov, Jordan; Lu, Jian R


    Keratins are a group of important proteins in skin and hair and as biomaterials they can provide desirable properties such as strength, biocompatibility, and moisture regaining and retaining. The aim of this work is to develop water-soluble keratin polypeptides from sheep wool and then explore how their surface adsorption behaves with and without surfactants. Successful preparation of keratin samples was demonstrated by identification of the key components from gel electrophoresis and the reproducible production of gram scale samples with and without SDS (sodium dodecylsulphate) during wool fibre dissolution. SDS micelles could reduce the formation of disulphide bonds between keratins during extraction, reducing inter-molecular crosslinking and improving keratin polypeptide solubility. However, Zeta potential measurements of the two polypeptide batches demonstrated almost identical pH dependent surface charge distributions with isoelectric points around pH 3.5, showing complete removal of SDS during purification by dialysis. In spite of different solubility from the two batches of keratin samples prepared, very similar adsorption and aggregation behavior was revealed from surface tension measurements and dynamic light scattering. Mixing of keratin polypeptides with SDS and C 12 TAB (dodecyltrimethylammonium bromide) led to the formation of keratin-surfactant complexes that were substantially more effective at reducing surface tension than the polypeptides alone, showing great promise in the delivery of keratin polypeptides via the surface active complexes. Neutron reflection measurements revealed the coexistence of surfactant and keratin polypeptides at the interface, thus providing the structural support to the observed surface tension changes associated with the formation of the surface active complexes. Copyright © 2016. Published by Elsevier Inc.

  7. Retrieving complex surface impedances from statistical absorption coefficients

    DEFF Research Database (Denmark)

    Mondet, Boris Jean-Francois; Brunskog, Jonas; Jeong, Cheol-Ho


    coefficients, prior information about the absorber of interest can be used as constraints, which is shown to help determine the correct impedance from absorption coefficient. Further stability and sensitivity investigations indicate that the method presented constitutes an efficient solution to convert sound......In room acoustic simulations the surface materials are commonly represented with energy parameters, such as the absorption and scattering coefficients, which do not carry phase information. This paper presents a method to transform statistical absorption coefficients into complex surface impedances...... that the impedance found has a physical meaning and respects causality in the time domain. Known material models, such as Miki’s and Maa’s models, are taken as references to assess the validity of the suggested model. Due to the non-uniqueness of retrieving complex-valued impedances from real-valued absorption...

  8. Self-Organization during Friction in Complex Surface Engineered Tribosystems

    Directory of Open Access Journals (Sweden)

    Ben D. Beake


    Full Text Available Self-organization during friction in complex surface engineered tribosystems is investigated. The probability of self-organization in these complex tribosystems is studied on the basis of the theoretical concepts of irreversible thermodynamics. It is shown that a higher number of interrelated processes within the system result in an increased probability of self-organization. The results of this thermodynamic model are confirmed by the investigation of the wear performance of a novel Ti0.2Al0.55Cr0.2Si0.03Y0.02N/Ti0.25Al0.65Cr0.1N (PVD coating with complex nano-multilayered structure under extreme tribological conditions of dry high-speed end milling of hardened H13 tool steel.

  9. Exploring complex networks via topological embedding on surfaces. (United States)

    Aste, Tomaso; Gramatica, Ruggero; Di Matteo, T


    We demonstrate that graphs embedded on surfaces are a powerful and practical tool to generate, to characterize, and to simulate networks with a broad range of properties. Any network can be embedded on a surface with sufficiently high genus and therefore the study of topologically embedded graphs is non-restrictive. We show that the local properties of the network are affected by the surface genus which determines the average degree, which influences the degree distribution, and which controls the clustering coefficient. The global properties of the graph are also strongly affected by the surface genus which is constraining the degree of interwovenness, changing the scaling properties of the network from large-world kind (small genus) to small- and ultrasmall-world kind (large genus). Two elementary moves allow the exploration of all networks embeddable on a given surface and naturally introduce a tool to develop a statistical mechanics description for these networks. Within such a framework, we study the properties of topologically embedded graphs which dynamically tend to lower their energy towards a ground state with a given reference degree distribution. We show that the cooling dynamics between high and low "temperatures" is strongly affected by the surface genus with the manifestation of a glass-like transition occurring when the distance from the reference distribution is low. We prove, with examples, that topologically embedded graphs can be built in a way to contain arbitrary complex networks as subgraphs. This method opens a new avenue to build geometrically embedded networks on hyperbolic manifolds.

  10. Surface Complexation Modelling in Metal-Mineral-Bacteria Systems (United States)

    Johnson, K. J.; Fein, J. B.


    The reactive surfaces of bacteria and minerals can determine the fate, transport, and bioavailability of aqueous heavy metal cations. Geochemical models are instrumental in accurately accounting for the partitioning of the metals between mineral surfaces and bacteria cell walls. Previous research has shown that surface complexation modelling (SCM) is accurate in two-component systems (metal:mineral and metal:bacteria); however, the ability of SCMs to account for metal distribution in mixed metal-mineral-bacteria systems has not been tested. In this study, we measure aqueous Cd distributions in water-bacteria-mineral systems, and compare these observations with predicted distributions based on a surface complexation modelling approach. We measured Cd adsorption in 2- and 3-component batch adsorption experiments. In the 2-component experiments, we measured the extent of adsorption of 10 ppm aqueous Cd onto either a bacterial or hydrous ferric oxide sorbent. The metal:bacteria experiments contained 1 g/L (wet wt.) of B. subtilis, and were conducted as a function of pH; the metal:mineral experiments were conducted as a function of both pH and HFO content. Two types of 3-component Cd adsorption experiments were also conducted in which both mineral powder and bacteria were present as sorbents: 1) one in which the HFO was physically but not chemically isolated from the system using sealed dialysis tubing, and 2) others where the HFO, Cd and B. subtilis were all in physical contact. The dialysis tubing approach enabled the direct determination of the concentration of Cd on each sorbing surface, after separation and acidification of each sorbent. The experiments indicate that both bacteria and mineral surfaces can dominate adsorption in the system, depending on pH and bacteria:mineral ratio. The stability constants, determined using the data from the 2-component systems, along with those for other surface and aqueous species in the systems, were used with FITEQL to

  11. A 2-D model for friction of complex anisotropic surfaces (United States)

    Costagliola, Gianluca; Bosia, Federico; Pugno, Nicola M.


    The friction force observed at macroscale is the result of interactions at various lower length scales that are difficult to model in a combined manner. For this reason, simplified approaches are required, depending on the specific aspect to be investigated. In particular, the dimensionality of the system is often reduced, especially in models designed to provide a qualitative description of frictional properties of elastic materials, e.g. the spring-block model. In this paper, we implement for the first time a two dimensional extension of the spring-block model, applying it to structured surfaces and investigating by means of numerical simulations the frictional behaviour of a surface in the presence of features like cavities, pillars or complex anisotropic structures. We show how friction can be effectively tuned by appropriate design of such surface features.

  12. Energetic Surface Smoothing of Complex Metal-Oxide Thin Films

    International Nuclear Information System (INIS)

    Willmott, P.R.; Herger, R.; Schlepuetz, C.M.; Martoccia, D.; Patterson, B.D.


    A novel energetic smoothing mechanism in the growth of complex metal-oxide thin films is reported from in situ kinetic studies of pulsed laser deposition of La 1-x Sr x MnO 3 on SrTiO 3 , using x-ray reflectivity. Below 50% monolayer coverage, prompt insertion of energetic impinging species into small-diameter islands causes them to break up to form daughter islands. This smoothing mechanism therefore inhibits the formation of large-diameter 2D islands and the seeding of 3D growth. Above 50% coverage, islands begin to coalesce and their breakup is thereby suppressed. The energy of the incident flux is instead rechanneled into enhanced surface diffusion, which leads to an increase in the effective surface temperature of ΔT≅500 K. These results have important implications on optimal conditions for nanoscale device fabrication using these materials

  13. Zinc surface complexes on birnessite: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Kideok D.; Refson, Keith; Sposito, Garrison


    Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.

  14. Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS) (United States)

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


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

  15. Reliability of surface EMG measurements from the suprahyoid muscle complex

    DEFF Research Database (Denmark)

    Kothari, Mohit; Stubbs, Peter William; Pedersen, Asger Roer


    of using the suprahyoid muscle complex (SMC) using surface electromyography (sEMG) to assess changes to neural pathways by determining the reliability of measurements in healthy participants over days. Methods: Seventeen healthy participants were recruited. Measurements were performed twice with one week...... between sessions. Single pulse (at 120% and 140% of the resting motor threshold (rMT)) and paired pulse (2 ms and 15 ms paired pulse) transcranial magnetic stimulation (TMS) were used to elicit MEPs in the SMC which were recorded using sEMG. Results: ≈50% of participants (range: 42%-58%; depending...... on stimulus type/intensity) had significantly different MEP values between day 1 and day 2 for single pulse and paired pulse TMS. A large stimulus artefact resulted in MEP responses that could not be assessed in four participants. Conclusions: The assessment of the SMC using sEMG following TMS was poorly...

  16. Surface complexation model of uranyl sorption on Georgia kaolinite (United States)

    Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.


    The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

  17. Ternary Complexation on Bacterial Surfaces: Implications for Subsurface Anion Transport (United States)

    Maclean, L. C.; Higginbottom, C. M.; Fowle, D. A.


    The physical, chemical, and biological controls on contaminant mobilities in aquatic ecosystems must be determined to establish the threat that contamination poses to the environment. Quantitative models of contaminant mobilities are required as a prerequisite to guide remediation efforts and to prioritize the potential hazard to the ecosystem of each contaminated site. It is well established that mineral surface adsorption is an important control on contaminant mobilities, and many studies have utilized thermodynamics to quantify metal/organic adsorption in order to yield predictive models of contaminant transport. However, these models of contaminant transport may not be representative of the reactions which control contaminant mobilities as most mineral surfaces are coated with organic acids, bacteria, and extracellular polymers. Numerous laboratory studies have demonstrated that bacterial cell walls have a high affinity for binding metal cations, and field studies indicate that a significant proportion of bacteria cells and associated extracellular matrices are coated with small scale hydrous metal oxides. The small size of bacteria, and in many cases the nanoscale of their associated mineral phases, suggests these bacteria-mineral composites may represent a large proportion of surface area exposed to fluid flow. Therefore, due to the affinity of bacterial cell walls for cations and biominerals, bacteria may also have a significant impact on anionic contaminant mobility in many natural systems. The extent of metal-bacteria adsorption reactions varies drastically as a function of pH and solution chemistry. Current adsorption models have focused on the interactions of positively charged metal cations with bacterial surfaces, however in many oxidizing environments metals such as Cr exist as anions or anionic complexes. We have studied the ability of non-metabolizing cells of the bacterial species Bacillus subtilis and Shewanella putrifaciens to adsorb aqueous Cr

  18. Corrected Debye-Hückel analysis of surface complexation. II. A theory of surface charging. (United States)

    Gunnarsson, Magnus; Abbas, Zareen; Ahlberg, Elisabet; Gobom, Sylvia; Nordholm, Sture


    A theory of surface charging of colloidal particles suspended in an electrolyte solution is presented. The charging at the particle surface is assumed to originate from the adsorption and desorption of protons and is therefore strongly dependent on the acidity of the solution. The surface binding of protons occurs locally at sites of occupancy zero or one that are described by a binding energy u(0) and a three-dimensional vibration of frequency nu. The diffuse screening of ions at the surface is described by the corrected Debye-Hückel analysis assuming linear response. The model contains a capacitor layer close to the charged surface and the finite size of the electrolyte ions is taken into account. The theory has been applied to titrated surface charge data on goethite (alpha-FeOOH) at NaClO(4) background concentrations ranging from 0.01 to 1.0 M. The protonation mechanism used in the modeling of these data corresponds to the 1-pK approach. A very good description of the experimental data was obtained at the highest ionic strength. Close to the pH(pzc) the theory also gave a good description at lower ionic strengths. However, at low salt concentrations and pH values far away from the pH(pzc) the electrostatic potential outside the capacitor layer becomes so high that nonlinear electrostatic effects become important and the theory therefore underestimates the surface charge. These results were compared with model calculations obtained using existing surface complexation models.

  19. Uncertainty analysis of point-by-point sampling complex surfaces using touch probe CMMs DOE for complex surfaces verification with CMM

    DEFF Research Database (Denmark)

    Barini, Emanuele Modesto; Tosello, Guido; De Chiffre, Leonardo


    The paper describes a study concerning point-by-point sampling of complex surfaces using tactile CMMs. A four factor, two level completely randomized factorial experiment was carried out, involving measurements on a complex surface configuration item comprising a sphere, a cylinder and a cone, co...

  20. Adaptive Surface Modeling of Soil Properties in Complex Landforms

    Directory of Open Access Journals (Sweden)

    Wei Liu


    Full Text Available Abstract: Spatial discontinuity often causes poor accuracy when a single model is used for the surface modeling of soil properties in complex geomorphic areas. Here we present a method for adaptive surface modeling of combined secondary variables to improve prediction accuracy during the interpolation of soil properties (ASM-SP. Using various secondary variables and multiple base interpolation models, ASM-SP was used to interpolate soil K+ in a typical complex geomorphic area (Qinghai Lake Basin, China. Five methods, including inverse distance weighting (IDW, ordinary kriging (OK, and OK combined with different secondary variables (e.g., OK-Landuse, OK-Geology, and OK-Soil, were used to validate the proposed method. The mean error (ME, mean absolute error (MAE, root mean square error (RMSE, mean relative error (MRE, and accuracy (AC were used as evaluation indicators. Results showed that: (1 The OK interpolation result is spatially smooth and has a weak bull's-eye effect, and the IDW has a stronger ‘bull’s-eye’ effect, relatively. They both have obvious deficiencies in depicting spatial variability of soil K+. (2 The methods incorporating combinations of different secondary variables (e.g., ASM-SP, OK-Landuse, OK-Geology, and OK-Soil were associated with lower estimation bias. Compared with IDW, OK, OK-Landuse, OK-Geology, and OK-Soil, the accuracy of ASM-SP increased by 13.63%, 10.85%, 9.98%, 8.32%, and 7.66%, respectively. Furthermore, ASM-SP was more stable, with lower MEs, MAEs, RMSEs, and MREs. (3 ASM-SP presents more details than others in the abrupt boundary, which can render the result consistent with the true secondary variables. In conclusion, ASM-SP can not only consider the nonlinear relationship between secondary variables and soil properties, but can also adaptively combine the advantages of multiple models, which contributes to making the spatial interpolation of soil K+ more reasonable.

  1. Complexity in Surfaces of Densest Packings for Families of Polyhedra

    Directory of Open Access Journals (Sweden)

    Elizabeth R. Chen


    Full Text Available Packings of hard polyhedra have been studied for centuries due to their mathematical aesthetic and more recently for their applications in fields such as nanoscience, granular and colloidal matter, and biology. In all these fields, particle shape is important for structure and properties, especially upon crowding. Here, we explore packing as a function of shape. By combining simulations and analytic calculations, we study three two-parameter families of hard polyhedra and report an extensive and systematic analysis of the densest known packings of more than 55 000 convex shapes. The three families have the symmetries of triangle groups (icosahedral, octahedral, tetrahedral and interpolate between various symmetric solids (Platonic, Archimedean, Catalan. We find optimal (maximum packing-density surfaces that reveal unexpected richness and complexity, containing as many as 132 different structures within a single family. Our results demonstrate the importance of thinking about shape not as a static property of an object, in the context of packings, but rather as but one point in a higher-dimensional shape space whose neighbors in that space may have identical or markedly different packings. Finally, we present and interpret our packing results in a consistent and generally applicable way by proposing a method to distinguish regions of packings and classify types of transitions between them.


    Directory of Open Access Journals (Sweden)

    A. A. Sidiropoulos


    Full Text Available The technology of 3D laser scanning is considered as one of the most common methods for heritage documentation. The point clouds that are being produced provide information of high detail, both geometric and thematic. There are various studies that examine techniques of the best exploitation of this information. In this study, an algorithm of pathology localization, such as cracks and fissures, on complex building surfaces is being tested. The algorithm makes use of the points’ position in the point cloud and tries to distinguish them in two groups-patterns; pathology and non-pathology. The extraction of the geometric information that is being used for recognizing the pattern of the points is being accomplished via Principal Component Analysis (PCA in user-specified neighborhoods in the whole point cloud. The implementation of PCA leads to the definition of the normal vector at each point of the cloud. Two tests that operate separately examine both local and global geometric criteria among the points and conclude which of them should be categorized as pathology. The proposed algorithm was tested on parts of the Gazi Evrenos Baths masonry, which are located at the city of Giannitsa at Northern Greece.

  3. Surface complexation models for uranium adsorption in the sub-surface environment

    International Nuclear Information System (INIS)

    Payne, T.E.


    Adsorption experiments with soil component minerals under a range of conditions are being used to develop models of uranium(VI) uptake in the sub-surface environment. The results show that adsorption of U on iron oxides and clay minerals is influenced by chemical factors including the pH, partial pressure of CO 2 , and the presence of ligands such as phosphate. Surface complexation models (SCMs) can be used to simulate U adsorption on these minerals. The SCMs are based on plausible mechanistic assumptions and describe the experimental data more adequately than Kd values or sorption isotherms. It is conceptually possible to simulate U sorption data on complex natural samples by combining SCMs for individual component minerals. This approach was used to develop a SCM for U adsorption to mineral assemblages from Koongarra (Australia), and produced a reasonable description of U uptake. In order to assess the applicability of experimental data to the field situation, in-situ measurements of U distributions between solid and liquid phases were undertaken at the Koongarra U deposit. This field partitioning data showed a satisfactory agreement with laboratory sorption data obtained under comparable conditions. (author)

  4. Surface complexation at calcium mineral-water interfaces


    Wu, Liuming


    Surface reactions occurring at solid-water interfaces in calcium mineral-ligands systems have been studied. Both hydrous apatite and fluorite surfaces show clear amphoteric properties. An ion exchange process between lattice ions of F- on fluorite and OH- ions in bulk solution is discovered. The surface adsorption of Alizarin Red S and sodium oleate are determined. Surface chemical reaction models are established based on acidbase potentiometric titrations, solubility, adsorption and zeta-pot...

  5. Assessment of WRF Surface Layer Formulations Over a Complex Terrain (United States)

    Srivastava, P.; Sharan, M.


    The accurate and efficient estimation of surface turbulent fluxes is crucial to predict an adequate atmospheric evolution by atmospheric models. The Monin-Obukhov similarity theory, which is used to compute these fluxes in numerical models, utilizes the empirical stability correction functions. In the present study, impact of various functional forms of similarity functions on the computation of the surface fluxes under both unstable and stable stratification is analyzed. In addition, this study compares two surface layer parametrization schemes in the Weather Research and Forecasting model over Ranchi (India). The model is run with three nested domains at a high resolution (1 Km) for `five' 4-day periods covering 15 days of Premonsoon season. The two surface layer schemes chosen for the analysis includes MM5 surface layer scheme having Businger-Dyer similarity functions, and revised MM5 scheme utilizing the functions those are valid for full ranges of atmospheric stabilities. The five planetary boundary layer (PBL) schemes are selected to assess the influence of the surface layer schemes on the structure of the boundary layer. The schemes are- Asymmetric Convective Model Version 2 (ACM2), Bougeault-Lacarrere (Boulac), Medium Range Forecast (MRF), Mellor-Yamada-Nakanishi-Niino (MYNN), and Yonsei University (YSU) PBL schemes. The impact of surface layer parametrizations on the near surface diagnostic variables is analyzed and results are compared with the observations.The bias in the 2 m temperature (T2) and 10 m wind speed (U) across the PBL schemes is very small and each PBL scheme is able to reproduce the diurnal variation of T2 irrespective of the surface layer scheme used for the simulations. A relatively higher value nocturnal T2 is predicted with the revised MM5 surface layer scheme as compared to that obtained with the old MM5 scheme, while both the surface layer schemes reproduce almost similar T2 during convective conditions. However, compare to the

  6. Immuno-targeting of Staphylococcus aureus via surface remodeling complexes. (United States)

    Sabulski, Mary J; Pidgeon, Sean E; Pires, Marcos M


    Agents with novel mechanisms of action are needed to complement traditional antibiotics. Towards these goals, we have exploited the surface-homing properties of vancomycin to tag the surface of Gram-positive pathogens with immune cell attractants in two unique modes. First, vancomycin was conjugated to the small molecule hapten 2,4-dinitrophenol (DNP) to promote bacterial opsonization. Second, we built on these results by improving the tagging specificity and mechanism of incorporation by coupling it to a sortase A substrate peptide. We demonstrated, for the first time, that the surface of Staphylococcus aureus ( S. aureus ) can be metabolically labeled in live Caenorhabditis elegans hosts. These constructs represent a class of promising narrow-spectrum agents that target S. aureus for opsonization and establish a new surface labeling modality in live host organisms, which should be a powerful tool in dissecting features of host-pathogen interactions.

  7. Uncertainty analysis of point by point sampling complex surfaces using touch probe CMMs

    DEFF Research Database (Denmark)

    Barini, Emanuele; Tosello, Guido; De Chiffre, Leonardo


    The paper describes a study concerning point by point scanning of complex surfaces using tactile CMMs. A four factors-two level full factorial experiment was carried out, involving measurements on a complex surface configuration item comprising a sphere, a cylinder and a cone, combined in a singl...

  8. Symplectic geometry on moduli spaces of holomorphic bundles over complex surfaces


    Khesin, Boris; Rosly, Alexei


    We give a comparative description of the Poisson structures on the moduli spaces of flat connections on real surfaces and holomorphic Poisson structures on the moduli spaces of holomorphic bundles on complex surfaces. The symplectic leaves of the latter are classified by restrictions of the bundles to certain divisors. This can be regarded as fixing a "complex analogue of the holonomy" of a connection along a "complex analogue of the boundary" in analogy with the real case.

  9. Graph Complexes and the Moduli Space of Riemann Surfaces

    DEFF Research Database (Denmark)

    Egas Santander, Daniela

    In this thesis we compare several combinatorial models for the moduli space of open-closed cobordisms and their compactifications. More precisely, we study Godin's category of admissible fat graphs, Costello's chain complex of black and white graphs, and Bödigheimer's space of radial slit......, that the complex of black and white graphs is a homological model of this mapping class group. Beyond giving new proofs of these results, the methods used give a new interpretation of Costello's model in terms of admissible fat graphs, which is a more classical model of moduli space. This connection could...... potentially allow to transfer constructions in fat graphs to the black and white model. Moreover, we compare Bödigheimer's radial slit configurations and the space of metric admissible fat graphs, producing an explicit homotopy equivalence using a "critical graph" map. This critical graph map descends...

  10. Adsorption of polymer/solvent complexes on silica surfaces

    Czech Academy of Sciences Publication Activity Database

    Grohens, Y.; Carriere, P.; Hamon, L.; Castelein, O.; Holl, Y.; Spěváček, Jiří


    Roč. 166, - (2001), s. 59-70 ISSN 1022-1360. [International Conference on Polymer-solvent Complexes and Intercalates /3./. Besancon, 28.08.2000-30.08.2000] R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : polymer/solvent interactions * stereocomplexes Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.634, year: 2001

  11. Visualization of pool boiling from complex surfaces with internal tunnels

    Directory of Open Access Journals (Sweden)

    Pastuszko Robert


    Full Text Available The paper presents experimental investigations of boiling heat transfer for a system of connected narrow horizontal and vertical tunnels. These extended surfaces, named narrow tunnel structure (NTS, can be applied to electronic element cooling. The experiments were carried out with ethanol at atmospheric pressure. The tunnel external covers were manufactured out of 0.1 mm thick perforated copper foil (hole diameters 0.5 mm, sintered with the mini-fins, formed on the vertical side of the 10 mm high rectangular fins and horizontal inter-fin surface. Visualization studies were conducted with a transparent structured model of joined narrow tunnels limited with the perforated foil. The visualization investigations aimed to formulate assumptions for the boiling model through distinguishing boiling types and defining all phases of bubble growth.

  12. Copper complexation capacity in surface waters of the Venice Lagoon. (United States)

    Delgadillo-Hinojosa, Francisco; Zirino, Alberto; Nasci, Cristina


    Total copper (Cu(T)), copper ion activity (pCu) and the copper complexation capacity (CuCC) were determined in samples of seawater collected in July 2003 from the Venice Lagoon. Cu(T) and CuCC showed considerable spatial variability: Cu(T) ranged from 1.8 to 70.0nM, whereas the CuCC varied from 195 to 573nM. pCu values varied from 11.6 to 12.6 and are consistent with those previously reported in estuarine and coastal areas (10.9-14.1). The range of Cu(T) values compares well with those reported in the past in the lagoon and in the adjacent Adriatic Sea. The highest concentrations of Cu(T) were found in samples collected near the industrial area of Porto Marghera, whereas the lowest were measured near the Chioggia and Malamocco inlets, where an intense tidally-driven renewal of seawater takes place. Although CuCC showed a high degree of spatial variability, the values recorded in the Venice Lagoon are comparable to those reported in other estuarine systems. In addition, CuCC was positively correlated with dissolved organic carbon (DOC), suggesting that organic ligands responsible for Cu complexation are part of the bulk organic matter pool in the lagoon. The CuCC:Cu(T) molar ratio was, on average 55:1, indicating that a large excess of complexation capacity exists in the Venice Lagoon. The high levels of CuCC and the narrow range of pCu indicates the importance of the role played by organic ligands in controlling the free ion Cu concentrations in the lagoon, and as a consequence, regulating its availability and/or toxicity.

  13. Complex Surface Concentration Gradients by Stenciled "Electro Click Chemistry"

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede


    Complex one- or two-dimensional concentration gradients of alkynated molecules are produced on azidized conducting polymer substrates by stenciled "electro click chemistry". The latter describes the local electrochemical generation of catalytically active Cu(I) required to complete a "click...... reaction" between alkynes and azides at room temperature. A stencil on the counter electrode defines the shape and multiplicity of the gradient(s) on the conducting polymer substrate, while the specific reaction conditions control gradient steepness and the maximum concentration deposited. Biologically...

  14. Graph Complexes and the Moduli Space of Riemann Surfaces

    DEFF Research Database (Denmark)

    Egas Santander, Daniela

    potentially allow to transfer constructions in fat graphs to the black and white model. Moreover, we compare Bödigheimer's radial slit configurations and the space of metric admissible fat graphs, producing an explicit homotopy equivalence using a "critical graph" map. This critical graph map descends...... to a homeomorphism between the Unimodular Harmonic compactification and the space of Sullivan diagrams, which are natural compactifications of the space of radial slit configurations and the space of metric admissible fat graphs, respectively. Finally, we use experimental methods to compute the homology of the chain......In this thesis we compare several combinatorial models for the moduli space of open-closed cobordisms and their compactifications. More precisely, we study Godin's category of admissible fat graphs, Costello's chain complex of black and white graphs, and Bödigheimer's space of radial slit...

  15. Chromate Adsorption on Selected Soil Minerals: Surface Complexation Modeling Coupled with Spectroscopic Investigation.

    Czech Academy of Sciences Publication Activity Database

    Veselská, V.; Fajgar, Radek; Číhalová, S.; Bolanz, R.M.; Göttlicher, J.; Steininger, R.; Siddique, J.A.; Komárek, M.


    Roč. 318, NOV 15 (2016), s. 433-442 ISSN 0304-3894 Institutional support: RVO:67985858 Keywords : surface complexation modeling * chromate * soil minerals Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.065, year: 2016

  16. Technology of magnetic abrasive finishing in machining of difficult-to-machine alloy complex surface

    Directory of Open Access Journals (Sweden)

    Fujian MA


    Full Text Available The technology of magnetic abrasive finishing is one of the important finishing technologies. Combining with low-frequency vibration and ultrasonic vibration, it can attain higher precision, quality and efficiency. The characteristics and the related current research of magnetic abrasive finishing, vibration assisted magnetic abrasive finishing and ultrasonic assisted magnetic abrasive finishing are introduced. According to the characteristics of the difficult-to-machine alloy's complex surface, the important problems for further study are presented to realize the finishing of complex surface with the technology of magnetic abrasive finishing, such as increasing the machining efficiency by enhancing the magnetic flux density of machining gap and compounding of magnetic energy and others, establishing of the control function during machining and the process planning method for magnetic abrasive finishing of complex surface under the space geometry restraint of complex surface on magnetic pole, etc.

  17. Surface-Enhanced Raman Scattering of the Complexes of Silver with Adenine and dAMP


    Otto, Cornelis; Hoeben, F.P.; Hoeben, F.P.; Greve, Jan


    The behaviour of adenine and 2'-deoxyadenosine-5'-monophosphate (dAMP) at positive surface potentials of a silver working electrode was investigated using surface-enhanced Raman scattering (SERS). The use of positive potentials in the presence of adenine or dAMP leads to a rapid accumulation of an intense spectrum. It is proposed that complexes of adenine (dAMP) with silver generate the observed spectra. Adenine and dAMP can be distinguished spectroscopically due to various different complexe...

  18. Surface and permeability properties of membranes from polyelectrolyte complexes and polyelectrolyte surfactant complexes

    Czech Academy of Sciences Publication Activity Database

    Schwarz, H. H.; Lukáš, Jaromír; Richau, K.


    Roč. 218, 1-2 (2003), s. 1-9 ISSN 0376-7388 R&D Projects: GA AV ČR KSK4050111 Keywords : polyelectrolyte complex membranes * pervaporation * dehydration of organics Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.081, year: 2003

  19. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.


    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  20. Surface complexation of carbonate on goethite: IR spectroscopy, structure & charge distribution

    NARCIS (Netherlands)

    Hiemstra, T.; Rahnemaie, R.; Riemsdijk, van W.H.


    The adsorption of carbonate on goethite has been evaluated, focussing on the relation between the structure of the surface complex and corresponding adsorption characteristics, like pH dependency and proton co-adsorption. The surface structure of adsorbed CO3-2 has been assessed with (1) a

  1. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    KAUST Repository

    Zhu, Yihan


    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva


    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  3. Differential topology of complex surfaces elliptic surfaces with p g=1 smooth classification

    CERN Document Server

    Morgan, John W


    This book is about the smooth classification of a certain class of algebraicsurfaces, namely regular elliptic surfaces of geometric genus one, i.e. elliptic surfaces with b1 = 0 and b2+ = 3. The authors give a complete classification of these surfaces up to diffeomorphism. They achieve this result by partially computing one of Donalson's polynomial invariants. The computation is carried out using techniques from algebraic geometry. In these computations both thebasic facts about the Donaldson invariants and the relationship of the moduli space of ASD connections with the moduli space of stable bundles are assumed known. Some familiarity with the basic facts of the theory of moduliof sheaves and bundles on a surface is also assumed. This work gives a good and fairly comprehensive indication of how the methods of algebraic geometry can be used to compute Donaldson invariants.

  4. Cell surface expression and function of the macromolecular C1 complex on the surface of human monocytes

    Directory of Open Access Journals (Sweden)

    Kinga K Hosszu


    Full Text Available The synthesis of the subunits of the C1 complex (C1q, C1s, C1r, and its regulator C1 inhibitor (C1-Inh by human monocytes has been previously established. However, surface expression of these molecules by monocytes has not been shown. Using flow cytometry and antigen-capture ELISA, we show here for the first time that, in addition to C1q, PB monocytes and the monocyte-derived U937 cells express C1s and C1r, as well as Factor B and C1-Inh on their surface. C1s and C1r immunoprecipitated with C1q, suggesting that at least some of the C1q on these cells is part of the C1 complex. Furthermore, the C1 complex on U937 cells was able to trigger complement activation via the classical pathway. The presence of C1-Inh may ensure that an unwarranted autoactivation of the C1 complex does not take place. Since C1-Inh closely monitors the activation of the C1 complex in a sterile or infectious inflammatory environment, further elucidation of the role of C1 complex is crucial to dissect its function in monocyte, DC and T cell activities, and its implications in host defense and tolerance.

  5. Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite

    Energy Technology Data Exchange (ETDEWEB)

    Carroll, S; Robers, S; Criscenti, L; O' Day, P


    Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr{sup 2+} and SrOH{sup +} complexes on the {beta}-plane and a monodentate Sr{sup 2+} complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH{sup +} complexes and a tetradentate binuclear Sr{sup 2+} species on the {beta}-plane. The binuclear complex is needed to account for enhanced sorption at high strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr{sup 2+} and SrOH{sup +} carbonate surface complexes on the {beta}-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate

  6. Surface complexation model for strontium sorption to amorphous silica and goethite

    Directory of Open Access Journals (Sweden)

    Criscenti Louise J


    Full Text Available Abstract Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of

  7. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts. (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A


    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  8. Oriented coupling of major histocompatibility complex (MHC) to sensor surfaces using light assisted immobilisation technology

    DEFF Research Database (Denmark)

    Snabe, Torben; Røder, Gustav Andreas; Neves-Petersen, Maria Teresa


    histocompatibility complex (MHC class I) to a sensor surface is presented. The coupling was performed using light assisted immobilisation--a novel immobilisation technology which allows specific opening of particular disulphide bridges in proteins which then is used for covalent bonding to thiol-derivatised surfaces...... via a new disulphide bond. Light assisted immobilisation specifically targets the disulphide bridge in the MHC-I molecule alpha(3)-domain which ensures oriented linking of the complex with the peptide binding site exposed away from the sensor surface. Structural analysis reveals that a similar...

  9. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    International Nuclear Information System (INIS)

    Bertolino, María Candelaria; Granados, Alejandro Manuel


    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  10. The significance of surface complexation reactions in hydrologic systems: a geochemist's perspective (United States)

    Koretsky, C.


    Complexation reactions at the mineral-water interface affect the transport and transformation of metals and organic contaminants, nutrient availability in soils, formation of ore deposits, acidification of watersheds and the global cycling of elements. Such reactions can be understood by quantifying speciation reactions in homogeneous aqueous solutions, characterizing reactive sites at mineral surfaces and developing models of the interactions between aqueous species at solid surfaces. In this paper, the application of thermodynamic principles to quantify aqueous complexation reactions is described. This is followed by a brief overview of a few of the methods that have been used to characterize reactive sites on mineral surfaces. Next, the application of empirical and semi-empirical models of adsorption at the mineral-water interface, including distribution coefficients, simple ion exchange models, and Langmuir and Freundlich isotherms is discussed. Emphasis is placed on the limitations of such models in providing an adequate representation of adsorption in hydrological systems. These limitations arise because isotherms do not account for the structure of adsorbed species, nor do they account for the development of surface charge with adsorption. This is contrasted with more sophisticated models of adsorption, termed 'surface complexation models', which include the constant capacitance model, the diffuse layer model, the triple layer model and the MUSIC model. In these models, speciation reactions between surface functional groups and dissolved species control the variable surface charge build-up and the specific adsorption properties of minerals in aqueous solutions. Next, the influence of mineral surface speciation on the reactivity of adsorbed species and on far from equilibrium dissolution rates of minerals is discussed. Finally, the applicability of microscopic models of surface complexation to field-scale systems is explored and the need to integrate

  11. Effects of electric field on a copper–dioxolene complex adsorbed on a gold surface

    Energy Technology Data Exchange (ETDEWEB)

    Kostyrko, T., E-mail:; Ślusarski, T.


    Highlights: • Cu–dioxolene complex at Au(1 1 1) surface in electric field was studied with a DFT+U method. • Two valence tautomers of the adsorbed Cu–dioxolene complex were described. • Coulomb correlations on Cu make driving force for valence tautomeric transitions. • Electric field of strength of 0.5 V/Å can almost fully ionize the adsorbed complex. - Abstract: A model of a copper–dioxolene complex linked to Au(1 1 1) surface with butanethiol linker is investigated using first-principles methods. It is shown that the complex adsorbed at the surface may appear in various locally stable structural forms differing in electron charge and spin density distribution, the symmetric high spin (HS) one and the twisted low spin (LS) structure. The electric field directed perpendicular to the surface controls the amount of the charge transfer between the complex and the substrate, starting from the zero-field value of Q = +0.18 |e| up to the value of Q = +0.94 |e| for the field strength of E = 0.5 V/Å. The field modifies also the mutual stability of the two structural forms, reducing the energy gap between the more energetically stable LS twisted form and the symmetrical HS one, from a value of Δ ∼ 0.29 eV in absence of the field to Δ ∼ 0.11 eV for the field strength of E = 0.35 V/Å.

  12. Applicability of surface complexation modelling in TVO's studies on sorption of radionuclides

    International Nuclear Information System (INIS)

    Carlsson, T.


    The report focuses on the possibility of applying surface complexation theories to the conditions at a potential repository site in Finland and of doing proper experimental work in order to determine necessary constants for the models. The report provides background information on: (1) what type experiments should be carried out in order to produce data for surface complexation modelling of sorption phenomena under potential Finnish repository conditions, and (2) how to design and perform properly such experiments, in order to gather data, develop models or both. The report does not describe in detail how proper surface complexation experiments or modelling should be carried out. The work contains several examples of information that may be valuable in both modelling and experimental work. (51 refs., 6 figs., 4 tabs.)

  13. Actinides sorption onto hematite. Experimental data, surface complexation modeling and linear free energy relationship

    Energy Technology Data Exchange (ETDEWEB)

    Romanchuk, Anna Y.; Kalmykov, Stephan N. [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry


    The sorption of actinides in different valence states - Am(III), Th(IV), Np(V) and U(VI) onto hematite have been revisited with the special emphasis on the equilibrium constants of formation of surface species. The experimental sorption data have been treated using surface complexation modeling from which the set of new values of equilibrium constants were obtained. Formation of inner sphere monodentate surface species adequately describes the pH-sorption edges for actinide ions indicative the ionic electrostatic nature of bonding with small or no covalency contribution. The linear free energy relationship representing the correlation between the hydrolysis constants and surface complexation constants has been developed for various cations including K(I), Li(I), Na(I), Ag(I), Tl(I), Sr(II), Cu(II), Co(II), La(III), Eu(III), Ga(III), Am(III), Th(IV), Np(V), U(VI). (orig.)

  14. The assembly of rotaxane-like dye/cyclodextrin/surface complexes on aluminium trihydroxide or goethite. (United States)

    Cooper, Rachel J; Camp, Philip J; Gordon, Ross J; Henderson, David K; Henry, Dorothy C R; McNab, Hamish; De Silva, Sonali S; Tackley, Daniel; Tasker, Peter A; Wight, Paul


    Simple azo-dyes carrying phosphonic acid and arsonic acid substituents such as 4-(4-hydroxyphenyl azo)phenylphosphonic acid (5) and 4-(4-hydroxyphenylazo)phenylarsonic acid (6) bind more strongly to high surface area oxides such as aluminium trihydroxide and goethite than their carboxylic and sulfonic acid analogues and the phosphonate-functionalized dyes have been shown to have greater humidity fastness when printed onto commercial alumina-coated papers. Adsorption isotherm measurements provide evidence for the formation of ternary dye/cyclodextrin/surface complexes. Dyes which form such ternary complexes show higher light fastness when printed onto alumina coated papers in an ink formulation containing alpha-cyclodextrin.

  15. Muscle fatigue and contraction intensity modulates the complexity of surface electromyography. (United States)

    Cashaback, Joshua G A; Cluff, Tyler; Potvin, Jim R


    Nonlinear dynamical techniques offer a powerful approach for the investigation of physiological time series. Multiscale entropy analyses have shown that pathological and aging systems are less complex than healthy systems and this finding has been attributed to degraded physiological control processes. A similar phenomenon may arise during fatiguing muscle contractions where surface electromyography signals undergo temporal and spectral changes that arise from the impaired regulation of muscle force production. Here we examine the affect of fatigue and contraction intensity on the short and long-term complexity of biceps brachii surface electromyography. To investigate, we used an isometric muscle fatigue protocol (parsed into three windows) and three contraction intensities (% of maximal elbow joint moment: 40%, 70% and 100%). We found that fatigue reduced the short-term complexity of biceps brachii activity during the last third of the fatiguing contraction. We also found that the complexity of surface electromyography is dependent on contraction intensity. Our results show that multiscale entropy is sensitive to muscle fatigue and contraction intensity and we argue it is imperative that both factors be considered when evaluating the complexity of surface electromyography signals. Our data contribute to a converging body of evidence showing that multiscale entropy can quantify subtle information content in physiological time series. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Toroidal surface complexes of bacteriophage φ12 are responsible for host-cell attachment

    International Nuclear Information System (INIS)

    Leo-Macias, Alejandra; Katz, Garrett; Wei Hui; Alimova, Alexandra; Katz, A.; Rice, William J.; Diaz-Avalos, Ruben; Hu Guobin; Stokes, David L.; Gottlieb, Paul


    Cryo-electron tomography and subtomogram averaging are utilized to determine that the bacteriophage φ12, a member of the Cystoviridae family, contains surface complexes that are toroidal in shape, are composed of six globular domains with six-fold symmetry, and have a discrete density connecting them to the virus membrane-envelope surface. The lack of this kind of spike in a reassortant of φ12 demonstrates that the gene for the hexameric spike is located in φ12's medium length genome segment, likely to the P3 open reading frames which are the proteins involved in viral-host cell attachment. Based on this and on protein mass estimates derived from the obtained averaged structure, it is suggested that each of the globular domains is most likely composed of a total of four copies of P3a and/or P3c proteins. Our findings may have implications in the study of the evolution of the cystovirus species in regard to their host specificity. - Research Highlights: → Subtomogram averaging reveals enhanced detail of a φ12 cystovirus surface protein complex. → The surface protein complex has a toroidal shape and six-fold symmetry. → It is encoded by the medium-size genome segment. → The proteins of the surface complex most likely are one copy of P3a and three copies of P3c.

  17. Colour interceptions, thermal stability and surface morphology of polyester metal complexes

    International Nuclear Information System (INIS)

    Zohdy, M.H.


    Chelating copolymers via grafting of acrylic acid (AAc) and acrylamide (AAm/AAc) comonomer mixture onto polyester micro fiber fabrics (PETMF) using gamma-radiation technique were prepared. The prepared graft chains (PETMF-g-AAc) and (PETMF-g-PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The prepared graft copolymers and their metal complexes were characterized using thermogravimetric analysis (TGA), colour parameters and surface morphology measurements. The colour interception and strength measurements showed that the metal complexation is homogeneously distributed. The results showed that the thermal stability of PETMF was improved after graft copolymerization and metal complexes. Moreover, the degree of grafting enhanced the thermal stability values of the grafted and complexed copolymers up to 25% of magnitude, on the other hand the activation energy of the grafted-copolymer with acrylic acid increased up to 80%. The SEM observation gives further supports to the homogenous distribution of grafting and metal complexation

  18. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

    International Nuclear Information System (INIS)

    Bonten, Luc T.C.; Groenenberg, Jan E.; Meesenburg, Henning; Vries, Wim de


    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: → Surface complexation models can be well applied in field studies. → Soil chemistry under a forest site is adequately modelled using generic parameters. → The model is easily extended with extra elements within the existing framework. → Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

  19. Surface Wind Regionalization over Complex Terrain: Evaluation and Analysis of a High-Resolution WRF Simulation

    NARCIS (Netherlands)

    Jiménez, P.A.; González-Rouco, J.F.; García-Bustamante, E.; Navarro, J.; Montávez, J.P.; Vilà-Guerau de Arellano, J.; Dudhia, J.; Muñoz-Roldan, A.


    This study analyzes the daily-mean surface wind variability over an area characterized by complex topography through comparing observations and a 2-km-spatial-resolution simulation performed with the Weather Research and Forecasting (WRF) model for the period 1992–2005. The evaluation focuses on the

  20. Two new organotin(IV) phosphoryl complexes: crystal structure and Hirshfeld surface analysis.

    Czech Academy of Sciences Publication Activity Database

    Pourayoubi, M.; Saneei, A.; Dušek, Michal; Rostami, S.A.; Crochet, A.; Kučeráková, Monika


    Roč. 12, č. 12 (2015), s. 2093-2103 ISSN 1735-2428 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Hirshfeld surfaces * tin * organotin(IV)-phosphoryl complex * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism

  1. Ab initio potential-energy surface and rovibrational states of the HCN-HCl complex

    NARCIS (Netherlands)

    Avoird, A. van der; Pedersen, T.B.; Dhont, G.S.F.; Fernandez, B.; Koch, H.


    A four-dimensional intermolecular potential-energy surface has been calculated for the HCN-HCl complex, with the use of the coupled cluster method with single and double excitations and noniterative inclusion of triples. Data for more than 13 000 geometries were represented by an angular expansion

  2. Surface complexation of neptunium (V) onto whole cells and cell componets of Shewanella alga

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald Timothy [Los Alamos National Laboratory; Deo, Randhir P [ASU; Rittmann, Bruce E [ASU; Songkasiri, Warinthorn [UNAFFILIATED


    We systematically quantified surface complexation of neptunium(V) onto whole cells of Shewanella alga strain BrY and onto cell wall and extracellular polymeric substances (EPS) of S. alga. We first performed acid and base titrations and used the mathematical model FITEQL with constant-capacitance surface-complexation to determine the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl site associated with amino acids (pK{sub a} {approx} 2.4), a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components at different pHs. Results show that solution pH influenced the speciation of Np(V) and each of the surface functional groups. We used the speciation sub-model of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, NpO{sub 2}{sup +} was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, other carboxyl, and phosphoryl groups were 1.75, 1.75, and 2.5 to 3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH3+, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1 to 3.6. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results point towards the important role of surface complexation in defining key actinide-microbiological interactions in the subsurface.

  3. Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

    Directory of Open Access Journals (Sweden)

    Krishnamoorthy Arumugam


    Full Text Available Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the

  4. Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds (United States)

    Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.


    Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

  5. Infrared spectroscopy of the Ar-C2HD complex: Potential energy surfaces

    International Nuclear Information System (INIS)

    Bemish, R.J.; Miller, R.E.


    The argon-acetylene complex has been studied by a number of experimental and theoretical groups, with the aim in mind of determining an accurate potential energy surface for this system. Both microwave and infrared spectroscopy have provided detailed rotational and vibrational constants for this system. In addition, scattering experiments have been reported and ab initio calculation performed. Even with all of this, there are still some fundamental questions that remain unanswered with regards to the shape of the potential surface. The authors will review some of this work to outline the current situation. In the present study, the authors have obtained high resolution infrared spectra of the Ar-C 2 HD complex with the aim of providing additional molecular constants that could be used to help constrain the potential. Collocation calculations are reported, using a number of potential surfaces, for this and the normal isotopomer. This additional data helps to answer some of these open questions

  6. Quantitative evaluation and modeling of two-dimensional neovascular network complexity: the surface fractal dimension

    International Nuclear Information System (INIS)

    Grizzi, Fabio; Russo, Carlo; Colombo, Piergiuseppe; Franceschini, Barbara; Frezza, Eldo E; Cobos, Everardo; Chiriva-Internati, Maurizio


    Modeling the complex development and growth of tumor angiogenesis using mathematics and biological data is a burgeoning area of cancer research. Architectural complexity is the main feature of every anatomical system, including organs, tissues, cells and sub-cellular entities. The vascular system is a complex network whose geometrical characteristics cannot be properly defined using the principles of Euclidean geometry, which is only capable of interpreting regular and smooth objects that are almost impossible to find in Nature. However, fractal geometry is a more powerful means of quantifying the spatial complexity of real objects. This paper introduces the surface fractal dimension (D s ) as a numerical index of the two-dimensional (2-D) geometrical complexity of tumor vascular networks, and their behavior during computer-simulated changes in vessel density and distribution. We show that D s significantly depends on the number of vessels and their pattern of distribution. This demonstrates that the quantitative evaluation of the 2-D geometrical complexity of tumor vascular systems can be useful not only to measure its complex architecture, but also to model its development and growth. Studying the fractal properties of neovascularity induces reflections upon the real significance of the complex form of branched anatomical structures, in an attempt to define more appropriate methods of describing them quantitatively. This knowledge can be used to predict the aggressiveness of malignant tumors and design compounds that can halt the process of angiogenesis and influence tumor growth

  7. Surface-illuminant ambiguity and color constancy: effects of scene complexity and depth cues. (United States)

    Kraft, James M; Maloney, Shannon I; Brainard, David H


    Two experiments were conducted to study how scene complexity and cues to depth affect human color constancy. Specifically, two levels of scene complexity were compared. The low-complexity scene contained two walls with the same surface reflectance and a test patch which provided no information about the illuminant. In addition to the surfaces visible in the low-complexity scene, the high-complexity scene contained two rectangular solid objects and 24 paper samples with diverse surface reflectances. Observers viewed illuminated objects in an experimental chamber and adjusted the test patch until it appeared achromatic. Achromatic settings made tinder two different illuminants were used to compute an index that quantified the degree of constancy. Two experiments were conducted: one in which observers viewed the stimuli directly, and one in which they viewed the scenes through an optical system that reduced cues to depth. In each experiment, constancy was assessed for two conditions. In the valid-cue condition, many cues provided valid information about the illuminant change. In the invalid-cue condition, some image cues provided invalid information. Four broad conclusions are drawn from the data: (a) constancy is generally better in the valid-cue condition than in the invalid-cue condition: (b) for the stimulus configuration used, increasing image complexity has little effect in the valid-cue condition but leads to increased constancy in the invalid-cue condition; (c) for the stimulus configuration used, reducing cues to depth has little effect for either constancy condition: and (d) there is moderate individual variation in the degree of constancy exhibited, particularly in the degree to which the complexity manipulation affects performance.

  8. A hybrid 3D SEM reconstruction method optimized for complex geologic material surfaces. (United States)

    Yan, Shang; Adegbule, Aderonke; Kibbey, Tohren C G


    Reconstruction methods are widely used to extract three-dimensional information from scanning electron microscope (SEM) images. This paper presents a new hybrid reconstruction method that combines stereoscopic reconstruction with shape-from-shading calculations to generate highly-detailed elevation maps from SEM image pairs. The method makes use of an imaged glass sphere to determine the quantitative relationship between observed intensity and angles between the beam and surface normal, and the detector and surface normal. Two specific equations are derived to make use of image intensity information in creating the final elevation map. The equations are used together, one making use of intensities in the two images, the other making use of intensities within a single image. The method is specifically designed for SEM images captured with a single secondary electron detector, and is optimized to capture maximum detail from complex natural surfaces. The method is illustrated with a complex structured abrasive material, and a rough natural sand grain. Results show that the method is capable of capturing details such as angular surface features, varying surface roughness, and surface striations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Use of polyamfolit complexes of ethyl-amino-crotonate/acrylic acid with surface-active materials for radionuclide extraction

    International Nuclear Information System (INIS)

    Kabdyrakova, A.M.; Artem'ev, O.I.; Protskij, A.V.; Bimendina, L.A.; Yashkarova, M.G.; Orazzhanova, L.K.


    Pentifylline of betaine structure was synthesised on the basis of 3-aminocrotonate and acrylic acid. Polyamfolit composition and its complexes with anionic surface-active material (lauryl sulfate of sodium) were determined. It is revealed that complex formation occurs with [polyamfolit]:[surface active material]=1:1 ratio and is accompanied by significant reduce of system characteristics viscosity. The paper presents results of [polyamfolit]:[surface active material] complex apply experimental investigation for radionuclide directed migration in soil. (author)

  10. Surface glycosylation of polysulfone membrane towards a novel complexing membrane for boron removal. (United States)

    Meng, Jianqiang; Yuan, Jing; Kang, Yinlin; Zhang, Yufeng; Du, Qiyun


    In this study, a novel complexing membrane was synthesized for boron removal from aqueous solution. A glycopolymer, poly(2-gluconamidoethyl methacrylate) (PGAMA), was grafted onto the chloromethylated polysulfone (CMPSF) microporous membrane via surface-initiated ATRP (SIATRP). The glycosylated PSF (GlyPSF) membrane was characterized by attenuated total refection-Flourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM). It was demonstrated that PGAMA was successfully anchored onto the membrane surface and the grafting yield can be tuned in a wide range up to 5.9 mg/cm(2) by varying the polymerization time. The complexing membrane can adsorb boron rapidly with the equilibrium reached within 2h and has a remarkable high boron adsorption capacity higher than 2.0 mmol/g at optimized conditions. Freundlich, Langmuir, and Dubinin-Radushkevich adsorption isotherms were applied, and the data were best described by Langmuir model. Kinetic data were analyzed, and the data fitted very well to the pseudo-second-order rate expression. The optimal pH for boron uptake is in a wide range of 6-9, and the optimal initial boron concentration is over 300 mg/L. Studies of ionic strength effects indicated the formation of inner-sphere surface complexes. The complexed boron can be leached quantitatively under acid condition. Copyright © 2011 Elsevier Inc. All rights reserved.

  11. Design Process Control for Improved Surface Finish of Metal Additive Manufactured Parts of Complex Build Geometry

    Directory of Open Access Journals (Sweden)

    Mikdam Jamal


    Full Text Available Metal additive manufacturing (AM is increasingly used to create complex 3D components at near net shape. However, the surface finish (SF of the metal AM part is uneven, with surface roughness being variable over the facets of the design. Standard post-processing methods such as grinding and linishing often meet with major challenges in finishing parts of complex shape. This paper reports on research that demonstrated that mass finishing (MF processes are able to deliver high-quality surface finishes (Ra and Sa on AM-generated parts of a relatively complex geometry (both internal features and external facets under select conditions. Four processes were studied in this work: stream finishing, high-energy (HE centrifuge, drag finishing and disc finishing. Optimisation of the drag finishing process was then studied using a structured design of experiments (DOE. The effects of a range of finishing parameters were evaluated and optimal parameters and conditions were determined. The study established that the proposed method can be successfully applied in drag finishing to optimise the surface roughness in an industrial application and that it is an economical way of obtaining the maximum amount of information in a short period of time with a small number of tests. The study has also provided an important step in helping understand the requirements of MF to deliver AM-generated parts to a target quality finish and cycle time.

  12. The PSA-2 glycoprotein complex of Leishmania major is a glycosylphosphatidylinositol-linked promastigote surface antigen. (United States)

    Murray, P J; Spithill, T W; Handman, E


    Polyclonal rabbit antiserum to the Triton X-114 phase material of Leishmania major, which comprises the surface and internal integral membrane proteins of the parasite, was used to screen a lambda gt11 genomic expression library. A recombinant clone producing a Mr 123,000 beta-galactosidase fusion protein was isolated. Antibodies affinity-purified on this fusion protein recognized a complex of three surface-oriented proteins of promastigotes of L. major of Mr 94,000, 90,000, and 80,000 that we have termed the promastigote surface Ag 2 (PSA-2) complex. The DNA sequence of the insert in this clone predicted the 3' end of an open reading frame encoding a hydrophobic C-terminus. The inferred C-terminal sequence was suggestive of a glycosylphosphatidyl-inositol membrane anchoring mechanism. Phosphatidylinositol-specific phospholipase C treatment of the native PSA-2 proteins caused a shift in their electrophoretic mobility with an apparent reduction in the molecular weight of the PSA-2 complex. After phospholipase C treatment these proteins also displayed the cryptic cross-reacting determinant recognized by antibodies to the Trypanosoma brucei variant surface Ag. Moreover, PSA-2, which previously partitioned in the detergent phase after Triton X-114 phase separation, became water-soluble after phospholipase C treatment. Immunoprecipitation of the PSA-2 proteins with sera directed to lectin-binding proteins indicated that these polypeptides may be differentially glycosylated. Finally, these PSA-2 proteins were recognized by sera from some patients with cutaneous leishmaniasis.

  13. Incorporating classic adsorption isotherms into modern surface complexation models: implications for sorption of radionuclides

    International Nuclear Information System (INIS)

    Kulik, D.A.


    Full text of publication follows: Computer-aided surface complexation models (SCM) tend to replace the classic adsorption isotherm (AI) analysis in describing mineral-water interface reactions such as radionuclide sorption onto (hydr) oxides and clays. Any site-binding SCM based on the mole balance of surface sites, in fact, reproduces the (competitive) Langmuir isotherm, optionally amended with electrostatic Coulomb's non-ideal term. In most SCM implementations, it is difficult to incorporate real-surface phenomena (site heterogeneity, lateral interactions, surface condensation) described in classic AI approaches other than Langmuir's. Thermodynamic relations between SCMs and AIs that remained obscure in the past have been recently clarified using new definitions of standard and reference states of surface species [1,2]. On this basis, a method for separating the Langmuir AI into ideal (linear) and non-ideal parts [2] was applied to multi-dentate Langmuir, Frumkin, and BET isotherms. The aim of this work was to obtain the surface activity coefficient terms that make the SCM site mole balance constraints obsolete and, in this way, extend thermodynamic SCMs to cover sorption phenomena described by the respective AIs. The multi-dentate Langmuir term accounts for the site saturation with n-dentate surface species, as illustrated on modeling bi-dentate U VI complexes on goethite or SiO 2 surfaces. The Frumkin term corrects for the lateral interactions of the mono-dentate surface species; in particular, it has the same form as the Coulombic term of the constant-capacitance EDL combined with the Langmuir term. The BET term (three parameters) accounts for more than a monolayer adsorption up to the surface condensation; it can potentially describe the surface precipitation of nickel and other cations on hydroxides and clay minerals. All three non-ideal terms (in GEM SCMs implementation [1,2]) by now are used for non-competing surface species only. Upon 'surface dilution

  14. Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

    Energy Technology Data Exchange (ETDEWEB)

    Veselská, Veronika, E-mail: [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Fajgar, Radek [Department of Analytical and Material Chemistry, Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 135/1, CZ-16502, Prague (Czech Republic); Číhalová, Sylva [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Bolanz, Ralph M. [Institute of Geosciences, Friedrich-Schiller-University Jena, Carl-Zeiss-Promenade 10, DE-07745, Jena (Germany); Göttlicher, Jörg; Steininger, Ralph [ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, DE-76344, Eggenstein-Leopoldshafen (Germany); Siddique, Jamal A.; Komárek, Michael [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic)


    Highlights: • Study of Cr(VI) adsorption on soil minerals over a large range of conditions. • Combined surface complexation modeling and spectroscopic techniques. • Diffuse-layer and triple-layer models used to obtain fits to experimental data. • Speciation of Cr(VI) and Cr(III) was assessed. - Abstract: This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3–10), ionic strengths (0.001–0.1 M KNO{sub 3}), sorbate concentrations (10{sup −4}, 10{sup −5}, and 10{sup −6} M Cr(VI)), and sorbate/sorbent ratios (50–500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

  15. Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

    Directory of Open Access Journals (Sweden)

    Schaller Melinda S


    Full Text Available Abstract 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.

  16. Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite (United States)

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


    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.

  17. Riemann surfaces of complex classical trajectories and tunnelling splitting in one-dimensional systems (United States)

    Harada, Hiromitsu; Mouchet, Amaury; Shudo, Akira


    The topology of complex classical paths is investigated to discuss quantum tunnelling splittings in one-dimensional systems. Here the Hamiltonian is assumed to be given as polynomial functions, so the fundamental group for the Riemann surface provides complete information on the topology of complex paths, which allows us to enumerate all the possible candidates contributing to the semiclassical sum formula for tunnelling splittings. This naturally leads to action relations among classically disjoined regions, revealing entirely non-local nature in the quantization condition. The importance of the proper treatment of Stokes phenomena is also discussed in Hamiltonians in the normal form.

  18. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Directory of Open Access Journals (Sweden)

    Akinori Honda


    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  19. Evaluating polymer degradation with complex mixtures using a simplified surface area method. (United States)

    Steele, Kandace M; Pelham, Todd; Phalen, Robert N


    Chemical-resistant gloves, designed to protect workers from chemical hazards, are made from a variety of polymer materials such as plastic, rubber, and synthetic rubber. One material does not provide protection against all chemicals, thus proper polymer selection is critical. Standardized testing, such as chemical degradation tests, are used to aid in the selection process. The current methods of degradation ratings based on changes in weight or tensile properties can be expensive and data often do not exist for complex chemical mixtures. There are hundreds of thousands of chemical products on the market that do not have chemical resistance data for polymer selection. The method described in this study provides an inexpensive alternative to gravimetric analysis. This method uses surface area change to evaluate degradation of a polymer material. Degradation tests for 5 polymer types against 50 complex mixtures were conducted using both gravimetric and surface area methods. The percent change data were compared between the two methods. The resulting regression line was y = 0.48x + 0.019, in units of percent, and the Pearson correlation coefficient was r = 0.9537 (p ≤ 0.05), which indicated a strong correlation between percent weight change and percent surface area change. On average, the percent change for surface area was about half that of the weight change. Using this information, an equivalent rating system was developed for determining the chemical degradation of polymer gloves using surface area.

  20. Application of the complex cepstrum to the location of acoustic sources near reflective surfaces (United States)

    Fuller, C. R.; Tavakkoli, S.; Elliott, K. B.; Hurst, C. J.; Obrien, W. F.


    The complex cepstrum is used to correct bearing estimations of acoustic sources in the presence of a reflective surface. An automated liftering procedure is used which zeros out a block portion of the cepstrum including the echo information. The problem of the resulting distortion is alleviated by applying a coherence criterion to the recovered direct signals at each microphone. Thus to a large degree the interactive nature of cepstral processing is overcome for this application. For the test signals and geometries considered the cepstrum is shown to accurately correct for bearing errors in acoustic signals contaminated with reflections from nearby surfaces.

  1. Modeling and simulation for fewer-axis grinding of complex surface (United States)

    Li, Zhengjian; Peng, Xiaoqiang; Song, Ci


    As the basis of fewer-axis grinding of complex surface, the grinding mathematical model is of great importance. A mathematical model of the grinding wheel was established, and then coordinate and normal vector of the wheel profile could be calculated. Through normal vector matching at the cutter contact point and the coordinate system transformation, the grinding mathematical model was established to work out the coordinate of the cutter location point. Based on the model, interference analysis was simulated to find out the right position and posture of workpiece for grinding. Then positioning errors of the workpiece including the translation positioning error and the rotation positioning error were analyzed respectively, and the main locating datum was obtained. According to the analysis results, the grinding tool path was planned and generated to grind the complex surface, and good form accuracy was obtained. The grinding mathematical model is simple, feasible and can be widely applied.

  2. Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

    International Nuclear Information System (INIS)

    Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna; Stockmann, Madlen


    In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO 4 by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

  3. Integrating Sound Scattering Measurements in the Design of Complex Architectural Surfaces

    DEFF Research Database (Denmark)

    Peters, Brady


    Digital tools present the opportunity for incorporating performance analysis into the architectural design process. Acoustic performance is an important criterion for architectural design. There is much known about sound absorption but little about sound scattering, even though scattering...... is recognized to be one of the most important factors in predicting the computational prediction of acoustic performance. This paper proposes a workflow for the design of complex architectural surfaces and the prediction of their sound scattering properties. This workflow includes the development...

  4. Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

    Energy Technology Data Exchange (ETDEWEB)

    Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport; Stockmann, Madlen [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes


    In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO{sub 4} by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

  5. A novel Pfs38 protein complex on the surface of Plasmodium falciparum blood-stage merozoites

    DEFF Research Database (Denmark)

    Paul, Gourab; Deshmukh, Arunaditya; Kaur, Inderjeet


    BACKGROUND: The Plasmodium genome encodes for a number of 6-Cys proteins that contain a module of six cysteine residues forming three intramolecular disulphide bonds. These proteins have been well characterized at transmission as well as hepatic stages of the parasite life cycle. In the present...... the development of a multi-sub-unit malaria vaccine based on some of these protein complexes on merozoite surface....

  6. Potential energy surface and rovibrational energy levels of the H2-CS van der Waals complex. (United States)

    Denis-Alpizar, Otoniel; Stoecklin, Thierry; Halvick, Philippe; Dubernet, Marie-Lise; Marinakis, Sarantos


    Owing to its large dipole, astrophysicists use carbon monosulfide (CS) as a tracer of molecular gas in the interstellar medium, often in regions where H(2) is the most abundant collider. Predictions of the rovibrational energy levels of the weakly bound complex CS-H(2) (not yet observed) and also of rate coefficients for rotational transitions of CS in collision with H(2) should help to interpret the observed spectra. This paper deals with the first goal, i.e., the calculation of the rovibrational energy levels. A new four-dimensional intermolecular potential energy surface for the H(2)-CS complex is presented. Ab initio potential energy calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and midbond functions. The potential energy surface was obtained by an analytic fit of the ab initio data. The equilibrium structure of the H(2)-CS complex is found to be linear with the carbon pointing toward H(2) at the intermolecular separation of 8.6 a(o). The corresponding well depth is -173 cm(-1). The potential was used to calculate the rovibrational energy levels of the para-H(2)-CS and ortho-H(2)-CS complexes. The present work provides the first theoretical predictions of these levels. The calculated dissociation energies are found to be 35.9 cm(-1) and 49.9 cm(-1), respectively, for the para and ortho complexes. The second virial coefficient for the H(2)-CS pair has also been calculated for a large range of temperature. These results could be used to assign future experimental spectra and to check the accuracy of the potential energy surface.

  7. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.


    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  8. New strategy for chemically attachment of Schiff base complexes on Multiwalled Carbon Nanotubes surfaces

    Directory of Open Access Journals (Sweden)

    Leila Moradi


    Full Text Available Chemically attachment of Schiff base complexes on multiwalled carbon nanotubes (MWCNTs surfaces through a convenient and simple method was studied. In the first step of this method, we present a new method for preparation of aminated MWCNTs in order to attachment of (new chlorinated salen Schiff bases. Amination of multiwalled carbon nanotubes performed under microwave (MW irradiation through a one pot two step reaction. The chemically attachment of salen Schiff bases on functionalized MWCNTs (salen@MWCNTs performed under a facile simple nucleophilic substitution reaction and complexation of attached salen Schiff bases (salen complex@MWCNTs in last step, have been occurred with reaction of transition metal salts and salen@MWCNTs. The obtained products were characterized in detail, using FTIR, XRD, UV-Vis absorption, SEM and EDX methods.

  9. Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption (United States)

    Padhi, S.; Tokunaga, T.


    Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

  10. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces (United States)

    Bertolino, María Candelaria; Granados, Alejandro Manuel


    In this work we present a detailed study of classic reactions such as ;click reaction; and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV-vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  11. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes (United States)

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


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

  12. A dynamic duo: pairing click chemistry and postpolymerization modification to design complex surfaces. (United States)

    Arnold, Rachelle M; Patton, Derek L; Popik, Vladimir V; Locklin, Jason


    Advances in key 21st century technologies such as biosensors, biomedical implants, and organic light-emitting diodes rely heavily on our ability to imagine, design, and understand spatially complex interfaces. Polymer-based thin films provide many advantages in this regard, but the direct synthesis of polymers with incompatible functional groups is extremely difficult. Using postpolymerization modification in conjunction with click chemistry can circumvent this limitation and result in multicomponent surfaces that are otherwise unattainable. The two methods used to form polymer thin films include physisorption and chemisorption. Physisorbed polymers suffer from instability because of the weak intermolecular forces between the film and the substrate, which can lead to dewetting, delamination, desorption, or displacement. Covalent immobilization of polymers to surfaces through either a "grafting to" or "grafting from" approach provides thin films that are more robust and less prone to degradation. The grafting to technique consists of adsorbing a polymer containing at least one reactive group along the backbone to form a covalent bond with a complementary surface functionality. Grafting from involves polymerization directly from the surface, in which the polymer chains deviate from their native conformation in solution and stretch away from the surface because of the high density of chains. Postpolymerization modification (PPM) is a strategy used by our groups over the past several years to immobilize two or more different chemical functionalities onto substrates that contain covalently grafted polymer films. PPM exploits monomers with reactive pendant groups that are stable under the polymerization conditions but are readily modified via covalent attachment of the desired functionality. "Click-like" reactions are the most common type of reactions used for PPM because they are orthogonal, high-yielding, and rapid. Some of these reactions include thiol-based additions

  13. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system (United States)

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.


    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.

  14. The surface chemistry of divalent metal carbonate minerals; a critical assessment of surface charge and potential data using the charge distribution multi-site ion complexation model

    NARCIS (Netherlands)

    Wolthers, M.; Charlet, L.; Van Cappellen, P.


    The Charge Distribution MUltiSite Ion Complexation or CD–MUSIC modeling approach is used to describe the chemical structure of carbonate mineralaqueous solution interfaces. The new model extends existing surface complexation models of carbonate minerals, by including atomic scale information on

  15. Stability of nano-metric colloidal dispersions of titanium: effect of surface complexation

    International Nuclear Information System (INIS)

    Peyre, Veronique


    This research thesis reports the study of the adsorption of small organic molecules at the surface of nano-particles of mineral oxides (zirconia), and of its effects on the stability of the colloidal dispersion. Adsorption has been quantified by adsorption isotherms and surface titrations. Processes and mechanisms are thus discussed with respect to pH. The influence of various protecting molecules (acetyl acetone, but also acetic acid, citric acid and diethanolamine) has been studied, and notably highlighted the role of the outer face of the complexing agent in the assessment of reactions between particles which govern the compression and re-dispersability properties of protected dispersions. This study is performed by osmotic pressure measurements and by X-ray diffusion at small angles, completed by statistical mechanics calculations [fr

  16. Ultrasonic detection technology based on joint robot on composite component with complex surface

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Juan; Xu, Chunguang; Zhang, Lan [School of Mechanical Engineering, Beijing Institute of Technology, Beijing (China)


    Some components have complex surface, such as the airplane wing and the shell of a pressure vessel etc. The quality of these components determines the reliability and safety of related equipment. Ultrasonic nondestructive detection is one of the main methods used for testing material defects at present. In order to improve the testing precision, the acoustic axis of the ultrasonic transducer should be consistent with the normal direction of the measured points. When we use joint robots, automatic ultrasonic scan along the component surface normal direction can be realized by motion trajectory planning and coordinate transformation etc. In order to express the defects accurately and truly, the robot position and the signal of the ultrasonic transducer should be synchronized.

  17. Formal Killing fields for minimal Lagrangian surfaces in complex space forms (United States)

    Wang, Joe S.


    The differential system for minimal Lagrangian surfaces in a 2C-dimensional, non-flat, complex space form is an elliptic integrable system defined on the Grassmann bundle of oriented Lagrangian 2-planes. This is a 6-symmetric space associated with the Lie group SL(3 , C) , and the minimal Lagrangian surfaces arise as the primitive maps. Utilizing this property, we derive the inductive differential algebraic formulas for a pair of the formal loop algebra sl(3 , C) [ [ λ ] ] -valued canonical formal Killing fields. For applications, (a) we give a complete classification of the (pseudo) Jacobi fields for the minimal Lagrangian system, (b) we obtain an infinite sequence of conservation laws from the components of the canonical formal Killing fields.

  18. Surface Complexation Modeling in Variable Charge Soils: Prediction of Cadmium Adsorption

    Directory of Open Access Journals (Sweden)

    Giuliano Marchi


    Full Text Available ABSTRACT Intrinsic equilibrium constants for 22 representative Brazilian Oxisols were estimated from a cadmium adsorption experiment. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. Intrinsic equilibrium constants were optimized by FITEQL and by hand calculation using Visual MINTEQ in sweep mode, and Excel spreadsheets. Data from both models were incorporated into Visual MINTEQ. Constants estimated by FITEQL and incorporated in Visual MINTEQ software failed to predict observed data accurately. However, FITEQL raw output data rendered good results when predicted values were directly compared with observed values, instead of incorporating the estimated constants into Visual MINTEQ. Intrinsic equilibrium constants optimized by hand calculation and incorporated in Visual MINTEQ reliably predicted Cd adsorption reactions on soil surfaces under changing environmental conditions.

  19. Acid-base surface chemistry and sorption of some lanthanides on K +-saturated Marblehead illite: II. a multisite-surface complexation modeling (United States)

    Kulik, Dmitrii A.; Aja, Stephen U.; Sinitsyn, Vasilii A.; Wood, Scott A.


    The surface reactivity and sorption of Nd and Eu onto K +-saturated Marblehead illite at 25°C, measured in aqueous 0.01, 0.1, and 1.0 M KCl solutions, were interpreted with a multi-site-surface complexation model. Model potentiometric titration and sorption curves (computed using the Gibbs free energy minimization code, Selektor-A) resolve into reactions on variable-charge amphoteric sites on edge surfaces and on permanent-charge siloxane surfaces (φ x). Standard partial molal Gibbs free energy of formation from elements (g 2980) for surface complexes were derived from oxide (SiO 2,am and γ-Al 2O 3) surface deprotonation KA10, KA20 and electrolyte adsorption constants KCl0, KNa0. Because surface complexation reactions on siloxane basal surfaces are negligible in 1 M KCl, models of surface charge and adsorption edges of Nd and Eu presumed that C 1 is equal to 1.6 Fm -2 for amphoteric site types, and a maximum site density of 1.2 ± 0.2 sites nm -2 for the outer-sphere species, (Al>OH 2+Cl -). To obtain values of g 2980 for exchangeable cations and charged X ˜REE complexes, ion exchange sites were assumed to be fully deprotonated in 1.0 M KCl solutions (pH > 2.7). Proton release and REE 3+ uptake on ion exchange sites were then simulated (pH 4.0) from initial values of 20 to 48%. The application of Gibbs free energy minimization to sorption processes is innovative in that simultaneous treatment of surface complexation reactions and minerals stability is feasible in any system without introducing mass-balance constraints particular to surface species.

  20. A Simple and Universal Aerosol Retrieval Algorithm for Landsat Series Images Over Complex Surfaces (United States)

    Wei, Jing; Huang, Bo; Sun, Lin; Zhang, Zhaoyang; Wang, Lunche; Bilal, Muhammad


    Operational aerosol optical depth (AOD) products are available at coarse spatial resolutions from several to tens of kilometers. These resolutions limit the application of these products for monitoring atmospheric pollutants at the city level. Therefore, a simple, universal, and high-resolution (30 m) Landsat aerosol retrieval algorithm over complex urban surfaces is developed. The surface reflectance is estimated from a combination of top of atmosphere reflectance at short-wave infrared (2.22 μm) and Landsat 4-7 surface reflectance climate data records over densely vegetated areas and bright areas. The aerosol type is determined using the historical aerosol optical properties derived from the local urban Aerosol Robotic Network (AERONET) site (Beijing). AERONET ground-based sun photometer AOD measurements from five sites located in urban and rural areas are obtained to validate the AOD retrievals. Terra MODerate resolution Imaging Spectrometer Collection (C) 6 AOD products (MOD04) including the dark target (DT), the deep blue (DB), and the combined DT and DB (DT&DB) retrievals at 10 km spatial resolution are obtained for comparison purposes. Validation results show that the Landsat AOD retrievals at a 30 m resolution are well correlated with the AERONET AOD measurements (R2 = 0.932) and that approximately 77.46% of the retrievals fall within the expected error with a low mean absolute error of 0.090 and a root-mean-square error of 0.126. Comparison results show that Landsat AOD retrievals are overall better and less biased than MOD04 AOD products, indicating that the new algorithm is robust and performs well in AOD retrieval over complex surfaces. The new algorithm can provide continuous and detailed spatial distributions of AOD during both low and high aerosol loadings.

  1. Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization (United States)

    Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.


    We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

  2. Effects of complex terrain on net surface longwave radiation in China (United States)

    Zhu, Xiaochen; Qiu, Xinfa; Zeng, Yan; Ren, Wei; Tao, Bo; Gao, Jiaqi; Liu, Haobo; Tan, Yunjuan


    Net surface longwave radiation (NSLR) is one of key meteorological factors and is strongly influenced by cloud cover, surface temperature, humidity, and local micrometeorological conditions as well as terrain conditions. Realistically estimating NSLR is vitally important for understanding surface radiation balance and investigating micrometeorological factors of air pollution dispersion, especially in regions with complicated terrain. In this study, we proposed a distributed model for estimating NSLR by considering effects of complex local terrain conditions in China. Meteorological data (including mean temperature, relative humidity, and sunshine percentage) and observed NSLR data from 1993 to 2001 together with the digital elevation model data were used to parametrize the model and account for the effects of atmospheric factors and surface terrain factors according to the isotropic principle. The monthly NSLR during 1961-2000 was estimated at a spatial resolution of 1 km. Topographic analysis suggests that the distribution characteristics of NSLR with elevation or slope are consistent with those of field observations. In particular, the estimated NSLR is favorably comparable with site-level observations on the Tibetan Plateau (average relative error < 11%). Our results indicate that this model can describe microscale distribution features in mountainous areas in detail and that this improved approach can be used for NSLR spatial estimation in other regions with complicated terrain.

  3. Investigations of surface-tension effects due to small-scale complex boundaries (United States)

    Feng, Jiansheng

    these two different types of surfaces differed by about 50° ˜ 60°, with the low-adhesion surfaces at about 120° ˜ 130° and the high-adhesion surfaces at about 70° ˜ 80°. Characterizations of both the microscopic structures and macroscopic wetting properties of these product surfaces allowed us to pinpoint the structural features responsible for specific wetting properties. It is found that the advancing contact angle was mainly determined by the primary structures while the receding contact angle is largely affected by the side-wall slope of the secondary features. This study established a platform for further exploration of the structure aspects of surface wettability. In the third and final project (Chapter 4), we demonstrated a new type of microfluidic channel that enable asymmetric wicking of wetting fluids based on structure-induced direction-dependent surface-tension effect. By decorating the side-walls of open microfluidic channels with tilted fins, we were able to experimentally demonstrate preferential wicking behaviors of various IPA-water mixtures with a range of contact angles in these channels. A simplified 2D model was established to explain the wicking asymmetry, and a complete 3D model was developed to provide more accurate quantitative predictions. The design principles developed in this study provide an additional scheme for controlling the spreading of fluids. The research presented in this dissertation spreads out across a wide range of physical phenomena (wicking, wetting, and capillarity), and involves a number of computational and experimental techniques, yet all of these projects are intrinsically united under a common theme: we want to better understand how simple fluids respond to small-scale complex surface structures as manifestations of surface-tension effects. We hope our findings can serve as building blocks for a larger scale endeavor of scientific research and engineering development. After all, the pursue of knowledge is most

  4. Formation mechanism of a silane-PVA/PVAc complex film on a glass fiber surface. (United States)

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


    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

  5. GEOQUIMICO : an interactive tool for comparing sorption conceptual models (surface complexation modeling versus K[D])

    International Nuclear Information System (INIS)

    Hammond, Glenn E.; Cygan, Randall Timothy


    Within reactive geochemical transport, several conceptual models exist for simulating sorption processes in the subsurface. Historically, the K D approach has been the method of choice due to ease of implementation within a reactive transport model and straightforward comparison with experimental data. However, for modeling complex sorption phenomenon (e.g. sorption of radionuclides onto mineral surfaces), this approach does not systematically account for variations in location, time, or chemical conditions, and more sophisticated methods such as a surface complexation model (SCM) must be utilized. It is critical to determine which conceptual model to use; that is, when the material variation becomes important to regulatory decisions. The geochemical transport tool GEOQUIMICO has been developed to assist in this decision-making process. GEOQUIMICO provides a user-friendly framework for comparing the accuracy and performance of sorption conceptual models. The model currently supports the K D and SCM conceptual models. The code is written in the object-oriented Java programming language to facilitate model development and improve code portability. The basic theory underlying geochemical transport and the sorption conceptual models noted above is presented in this report. Explanations are provided of how these physicochemical processes are instrumented in GEOQUIMICO and a brief verification study comparing GEOQUIMICO results to data found in the literature is given

  6. Transmission X-ray scattering as a probe for complex liquid-surface structures

    Energy Technology Data Exchange (ETDEWEB)

    Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; Kuzmenko, Ivan


    The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibility of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.

  7. On the relationship between enamel band complexity and occlusal surface area in Equids (Mammalia, Perissodactyla

    Directory of Open Access Journals (Sweden)

    Nicholas A. Famoso


    Full Text Available Enamel patterns on the occlusal surfaces of equid teeth are asserted to have tribal-level differences. The most notable example compares the Equini and Hipparionini, where Equini have higher crowned teeth with less enamel-band complexity and less total occlusal enamel than Hipparionini. Whereas previous work has successfully quantified differences in enamel band shape by dividing the length of enamel band by the square root of the occlusal surface area (Occlusal Enamel Index, OEI, it was clear that OEI only partially removes the effect of body size. Because enamel band length scales allometrically, body size still has an influence on OEI, with larger individuals having relatively longer enamel bands than smaller individuals. Fractal dimensionality (D can be scaled to any level, so we have used it to quantify occlusal enamel complexity in a way that allows us to get at an accurate representation of the relationship between complexity and body size. To test the hypothesis of tribal-level complexity differences between Equini and Hipparionini, we digitally traced a sample of 98 teeth, one tooth per individual; 31 Hipparionini and 67 Equini. We restricted our sampling to the P3-M2 to reduce the effect of tooth position. After calculating the D of these teeth with the fractal box method which uses the number of boxes of various sizes to calculate the D of a line, we performed a t-test on the individual values of D for each specimen, comparing the means between the two tribes, and a phylogenetically informed generalized least squares regression (PGLS for each tribe with occlusal surface area as the independent variable and D as the dependent variable. The slopes of both PGLS analyses were compared using a t-test to determine if the same linear relationship existed between the two tribes. The t-test between tribes was significant (p < 0.0001, suggesting different D populations for each lineage. The PGLS for Hipparionini was a positive but not

  8. Get a grip on chaos: Tailored measures for complex systems on surfaces (United States)

    Firle, Sascha Oliver

    Complex systems are ubiquitous in physics, biology and mathematics. This thesis is concerned with describing and understanding complex systems. Some new concepts about how large systems can be viewed in a lower dimensional framework are proposed. The systems presented are examples from ecology and chemistry. In both cases we have a large amount of interacting units that can be understood by The predator-prey system investigated consists of ground beetles, Pterostichus cuprens L. (Coleoptera: Carabidae), that feeds on bird-cherry oat aphids. The beetles' movement can consistently be described by a combined model of surface diffusion and biased random walk. This allows conclusions about how fast and in which fashion the beetle covers its habitat. Movement is dependent on aphid densities and predation, in turn modifies aphid distributions locally. The presented generalized functional response theory describes predation rates in the presence of spatial heterogeneity. A single measure for fragmentation captures all essential features of the prey aggregation and allows the estimation of outbreak densities and distributions. The chemical example is the catalytic oxidation of CO on a Pt(110) single crystal surface. Unstable periodic orbits reconstructed from experimental data are used to reveal the topology of the attractor, underlying the time series dynamics. The found braid supports an orbit which implies that the time series is chaotic. The system is simulated numerically by a set of partial differential equations for surface coverage in one space dimension. The bifurcation diagram of the corresponding traveling wave ODE reveals the homoclinic and heteroclinic orbits that organize the phase space and mediate the transition to chaos. Studies in the PDE- framework relate this to the stability and to the interaction of pulse-like solutions.

  9. The interaction of streptococcal enolase with canine plasminogen: the role of surfaces in complex formation.

    Directory of Open Access Journals (Sweden)

    Vinod Balhara

    Full Text Available 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.

  10. Additive surface complexation modeling of uranium(VI) adsorption onto quartz-sand dominated sediments. (United States)

    Dong, Wenming; Wan, Jiamin


    Many aquifers contaminated by U(VI)-containing acidic plumes are composed predominantly of quartz-sand sediments. The F-Area of the Savannah River Site (SRS) in South Carolina (USA) is an example. To predict U(VI) mobility and natural attenuation, we conducted U(VI) adsorption experiments using the F-Area plume sediments and reference quartz, goethite, and kaolinite. The sediments are composed of ∼96% quartz-sand and 3-4% fine fractions of kaolinite and goethite. We developed a new humic acid adsorption method for determining the relative surface area abundances of goethite and kaolinite in the fine fractions. This method is expected to be applicable to many other binary mineral pairs, and allows successful application of the component additivity (CA) approach based surface complexation modeling (SCM) at the SRS F-Area and other similar aquifers. Our experimental results indicate that quartz has stronger U(VI) adsorption ability per unit surface area than goethite and kaolinite at pH ≤ 4.0. Our modeling results indicate that the binary (goethite/kaolinite) CA-SCM under-predicts U(VI) adsorption to the quartz-sand dominated sediments at pH ≤ 4.0. The new ternary (quartz/goethite/kaolinite) CA-SCM provides excellent predictions. The contributions of quartz-sand, kaolinite, and goethite to U(VI) adsorption and the potential influences of dissolved Al, Si, and Fe are also discussed.

  11. Surface complexation modeling of Cd(II) sorption to montmorillonite, bacteria, and their composite (United States)

    Wang, Ning; Du, Huihui; Huang, Qiaoyun; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Chen, Wenli


    Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

  12. Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Powell, B A; Kersting, A; Zavarin, M; Zhao, P


    Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006

  13. Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments (United States)

    Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.


    Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of

  14. Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation. (United States)

    Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio


    A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

  15. Method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation in conjunction with mass spectrometric analysis (United States)

    Laskin, Julia [Richland, WA; Futrell, Jean H [Richland, WA


    The invention relates to a method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation (SID) in conjunction with mass spectrometric analysis. Results demonstrate formation of a wide distribution of structure-specific fragments having wide sequence coverage useful for sequencing and identifying the complex molecules.

  16. Ab initio treatment of the chemical reaction precursor complex Br(2P)-HCN. 1. Adiabatic and diabatic potential surfaces

    NARCIS (Netherlands)

    Fishchuk, A.V.; Merritt, J.M.; Avoird, A. van der


    The three adiabatic potential surfaces of the Br(P-2)-HCN complex that correlate to the P-2 ground state of the Br atom were calculated ab initio. With the aid of a geometry-dependent diabatic mixing angle, also calculated ab initio, these adiabatic potential surfaces were transformed into a set of

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

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


    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

  18. Areal Measurements of Ozone, Water, and Heat Fluxes Over Land With Different Surface Complexity, Using Aircraft

    International Nuclear Information System (INIS)

    Hicks, Bruce B.


    Contemporary models addressing issues of air quality and/or atmospheric deposition continue to exploit air-surface exchange formulations originating from single-tower studies. In reality,these expressions describe situations that are rare in the real world - nearly flat and spatially homogeneous. There have been several theoretical suggestions about how to extend from single-point understanding to areal descriptions, but so far the capability to address the problem experimentally has been limited. In recent years, however, developments in sensing technology have permitted adaptation of eddy-correlation methods to low-flying aircraft in a far more cost-effective manner than previously. A series of field experiments has been conducted, ranging from flat farmland to rolling countryside, employing a recently modified research aircraft operated by the US NationalOceanic and Atmospheric Administration (NOAA). The results demonstrate the complexity of the spatial heterogeneity question,especially for pollutants (ozone in particular). In general, the uncertainty associated with the adoption of any single-point formulation when describing areal averages is likely to be in the range 10% to 40%. In the case of sensible and latent heat fluxes, the overall behavior is controlled by the amount of energy available. For pollutant deposition, there is no constraint equivalent to the net radiation limitation on convective heat exchange. Consequently, dry deposition rates and air-surface exchange of trace gases in general are especially vulnerable to errors in spatial extrapolation. The results indicate that the susceptibility of dry deposition formulations to terrain complexity depends on the deposition velocity itself. For readily transferred pollutants (such as HNO 3 ), a factor of two error could be involved

  19. Surface expression of protein A on magnetosomes and capture of pathogenic bacteria by magnetosome/ antibody complexes

    Directory of Open Access Journals (Sweden)

    Jun eXu


    Full Text Available Magnetosomes are membrane-enclosed magnetite nanocrystals synthesized by magnetotactic bacteria (MTB. They display chemical purity, narrow size ranges, and species-specific crystal morphologies. Specific transmembrane proteins are sorted to the magnetosome membrane (MM. MamC is the most abundant MM protein of Magnetospirillum gryphiswaldense strain MSR-1. MamF is the second most abundant MM protein of MSR-1 and forms stable oligomers. We expressed staphylococcal protein A (SPA, an immunoglobulin-binding protein from the cell wall of Staphylococcus aureus, on MSR-1 magnetosomes by fusion with MamC or MamF. The resulting recombinant magnetosomes were capable of self-assembly with the Fc region of mammalian antibodies (Abs and were therefore useful for functionalization of magnetosomes. Recombinant plasmids pBBR-mamC-spa and pBBR-mamF-spa were constructed by fusing spa (the gene that encodes SPA with mamC and mamF, respectively. Recombinant magnetosomes with surface expression of SPA were generated by introduction of these fusion genes into wild-type MSR-1 or a mamF mutant strain. Studies with a Zeta Potential Analyzer showed that the recombinant magnetosomes had hydrated radii significantly smaller than those of WT magnetosomes and zeta potentials less than -30 mV, indicating that the magnetosome colloids were relatively stable. Observed conjugation efficiencies were as high as 71.24 µg Ab per mg recombinant magnetosomes, and the conjugated Abs retained most of their activity. Numbers of Vibrio parahaemolyticus (a common pathogenic bacterium in seafood captured by recombinant magnetosome/ Ab complexes were measured by real-time fluorescence-based quantitative PCR. One mg of complex was capable of capturing as many as 1.74×107 Vibrio cells. The surface expression system described here will be useful for design of functionalized magnetosomes from MSR-1 and other MTB.

  20. Diazonium salt derivatives of osmium bipyridine complexes: Electrochemical grafting and characterisation of modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, David J. [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Jenkins, Peter [School of Chemistry, National University of Ireland, Galway (Ireland); Polson, Matthew I.J. [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland); Baronian, Keith H.R. [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Downard, Alison J., E-mail: [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand)


    Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N{sub 2}{sup +}){sub 3}](PF{sub 6}){sub 5} (1) and [Os(bpy-ph-N{sub 2}{sup +}){sub 2}Cl{sub 2}](PF{sub 6}){sub 2} (2). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os{sup 2+/3+} couple and electron transfer rate constants of 11.4 s{sup -1} and 35.4 s{sup -1} were measured in ACN and PBS, respectively, for the Os{sup 2+/3+} couple of the film grafted from 1.

  1. Effect of glutamic acid on copper sorption onto kaolinite - Batch experiments and surface complexation modeling. (United States)

    Karimzadeh, Lotfollah; Barthen, Robert; Stockmann, Madlen; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna


    High carbonate content of the European Kupferschiefer ore deposits is a challenge for acid copper leaching (pH ≤ 2). Therefore investigating the mobility behavior of Cu(II) under conditions related to an alternative, neutrophil biohydrometallurgical Cu(II) leaching approach is of interest. As glutamic acid (Glu) might be present as a component in the growth media, we studied its effects on the adsorption of Cu(II) onto kaolinite. The binary and ternary batch sorption measurements of Cu(II) and Glu onto kaolinite were performed in the presence of 10 mM NaClO 4 as background electrolyte and at a pH range from 4 to 9. Sorption experiments were modeled by the charge-distribution multi-site ion complexation (CD-MUSIC) model by using single sorption site (≡SOH) and monodentate surface complexation reactions. Glu sorption on kaolinite is weak (kaolinite mimics the Freundlich model. The proposed CD-MUSIC model provides a close fit to the experimental data and predicts the sorption of Cu(II), Cu(II)-Glu and Glu onto kaolinite as well as the effect of Glu on Cu(II) mobility. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Using Google Earth Surface Metrics to Predict Plant Species Richness in a Complex Landscape

    Directory of Open Access Journals (Sweden)

    Sebastián Block


    Full Text Available Google Earth provides a freely available, global mosaic of high-resolution imagery from different sensors that has become popular in environmental and ecological studies. However, such imagery lacks the near-infrared band often used in studying vegetation, thus its potential for estimating vegetation properties remains unclear. In this study, we assess the potential of Google Earth imagery to describe and predict vegetation attributes. Further, we compare it to the potential of SPOT imagery, which has additional spectral information. We measured basal area, vegetation height, crown cover, density of individuals, and species richness in 60 plots in the oak forests of a complex volcanic landscape in central Mexico. We modelled each vegetation attribute as a function of surface metrics derived from Google Earth and SPOT images, and selected the best-supported linear models from each source. Total species richness was the best-described and predicted variable: the best Google Earth-based model explained nearly as much variation in species richness as its SPOT counterpart (R2 = 0.44 and 0.51, respectively. However, Google Earth metrics emerged as poor predictors of all remaining vegetation attributes, whilst SPOT metrics showed potential for predicting vegetation height. We conclude that Google Earth imagery can be used to estimate species richness in complex landscapes. As it is freely available, Google Earth can broaden the use of remote sensing by researchers and managers in low-income tropical countries where most biodiversity hotspots are found.

  3. Dynamics of Defects and Dopants in Complex Systems: Si and Oxide Surfaces and Interfaces (United States)

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


    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.

  4. B lymphocytes confer immune tolerance via cell surface GARP-TGF-β complex. (United States)

    Wallace, Caroline H; Wu, Bill X; Salem, Mohammad; Ansa-Addo, Ephraim A; Metelli, Alessandra; Sun, Shaoli; Gilkeson, Gary; Shlomchik, Mark J; Liu, Bei; Li, Zihai


    GARP, a cell surface docking receptor for binding and activating latent TGF-β, is highly expressed by platelets and activated Tregs. While GARP is implicated in immune invasion in cancer, the roles of the GARP-TGF-β axis in systemic autoimmune diseases are unknown. Although B cells do not express GARP at baseline, we found that the GARP-TGF-β complex is induced on activated human and mouse B cells by ligands for multiple TLRs, including TLR4, TLR7, and TLR9. GARP overexpression on B cells inhibited their proliferation, induced IgA class-switching, and dampened T cell-independent antibody production. In contrast, B cell-specific deletion of GARP-encoding gene Lrrc32 in mice led to development of systemic autoimmune diseases spontaneously as well as worsening of pristane-induced lupus-like disease. Canonical TGF-β signaling more readily upregulates GARP in Peyer patch B cells than in splenic B cells. Furthermore, we demonstrated that B cells are required for the induction of oral tolerance of T cell-dependent antigens via GARP. Our studies reveal for the first time to our knowledge that cell surface GARP-TGF-β is an important checkpoint for regulating B cell peripheral tolerance, highlighting a mechanism of autoimmune disease pathogenesis.

  5. Petroleum-collecting and dispersing complexes based on oleic acid and nitrogenous compounds as surface-active agents for removing thin petroleum films from water surface. (United States)

    Asadov, Ziyafaddin H; Tantawy, Ahmed H; Zarbaliyeva, Ilhama A; Rahimov, Ravan A


    Petroleum-collecting and dispersing complexes were synthesized on the basis of oleic acid and nitrogen-containing compounds. Surface-active properties (interfacial tension) of the obtained complexes were investigated by stalagmometric method. Petroleum-collecting and dispersing properties of the oleic acid complexes in diluted (5% wt. water or alcoholic solution) and undiluted form have been studied in waters of varying salinity (distilled, fresh and sea waters). Some of physico-chemical indices of the prepared compounds such as solubility, acid and amine numbers as well as electrical conductivity have been determined. The ability of oleic acid complex with ethylenediamine as petro-collecting and dispersing agent towards different types of petroleum has been studied. The influence of thickness and "age" of the petroleum slick on collecting and dispersing capacity of this complex has been clarified. Surface properties studied included critical micelle concentration (CMC), maximum surface excess (Γ(max)), and minimum surface area (A(min)). Free energies of micellization (ΔG°(mic)) and adsorption (ΔG°(ads)) were calculated.

  6. Engineering yeast consortia for surface-display of complex cellulosome structures

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wilfred [University of Delaware


    As our society marches toward a more technologically advanced future, energy and environmental sustainability are some of the most challenging problems we face today. Biomass is one of the most abundant renewable-feedstock for sustainable production of biofuels. However, the main technological obstacle to more widespread uses of this resource is the lack of low-cost technologies to overcome the recalcitrant nature of the cellulosic structure, especially the hydrolysis step on highly ordered celluloses. In this proposal, we successfully engineered several efficient and inexpensive whole-cell biocatalysts in an effort to produce economically compatible and sustainable biofuels, namely cellulosic ethanol. Our approach was to display of a highly efficient cellulolytic enzyme complex, named cellulosome, on the surface of a historical ethanol producer Saccharomyces cerevisiae for the simultaneous and synergistic saccharification and fermentation of cellulose to ethanol. We first demonstrated the feasibility of assembling a mini-cellulosome by incubating E. coli lysates expressing three different cellulases. Resting cells displaying mini-cellulosomes produced 4-fold more ethanol from phosphoric acid-swollen cellulose (PASC) than cultures with only added enzymes. The flexibility to assemble the mini-cellulosome structure was further demonstrated using a synthetic yeast consortium through intracellular complementation. Direct ethanol production from PASC was demonstrated with resting cell cultures. To create a microorganism suitable for a more cost-effective process, called consolidated bioprocessing (CBP), a synthetic consortium capable of displaying mini-cellulosomes on the cell surface via intercellular complementation was created. To further improve the efficiency, a new adaptive strategy of employing anchoring and adaptor scaffoldins to amplify the number of enzymatic subunits was developed, resulting in the creation of an artificial tetravalent cellulosome on the

  7. Mathematical Optimal Sequence Model Development to Process Planes and Other Interconnected Surfaces of Complex Body Parts

    Directory of Open Access Journals (Sweden)

    I. I. Kravchenko


    Full Text Available Experience in application of multi-operational machines CNC (MOM CNC shows that they are efficient only in case of significantly increasing productivity and dramatically reducing time-to-market cycle of new products. Most full technological MOM capabilities are revealed when processing the complex body parts. The more complex is a part design and the more is its number of machined surfaces, the more tools are necessary for its processing and positioning, the more is an efficiency of their application. At the same time, the case history of using these machines in industry shows that MOM CNC are, virtually, used mostly for technological processes of universal equipment, which is absolutely unacceptable. One way to improve the processing performance on MOM CNC is to reduce nonproductive machine time through reducing the mutual idle movements of the working machine. This problem is solved using dynamic programming methods, one of which is the solution of the traveling salesman problem (Bellman's method. With a known plan for treatment of all elementary surfaces of the body part, i.e. the known number of performed transitions, each transition is represented as a vertex of some graph, while technological links between the vertices are its edges. A mathematical model is developed on the Bellman principle, which is adapted to technological tasks to minimize the idle time of mutual idle movements of the working machine to perform all transitions in the optimal sequence. The initial data to fill matrix of time expenditures are time consumed by the hardware after executing the i-th transition, and necessary to complete the j-transition. The programmer fills in matrix cells according to known routing body part taking into account the time for part and table positioning, tool exchange, spindle and table approach to the working zone, and the time of table rotation, etc. The mathematical model was tested when machining the body part with 36 transitions on the

  8. Determination of B-complex vitamins in pharmaceutical formulations by surface-enhanced Raman spectroscopy (United States)

    Junior, Benedito Roberto Alvarenga; Soares, Frederico Luis Felipe; Ardila, Jorge Armando; Durango, Luis Guillermo Cuadrado; Forim, Moacir Rossi; Carneiro, Renato Lajarim


    The aim of this work was to quantify B-complex vitamins in pharmaceutical samples by surface enhanced Raman spectroscopy technique using gold colloid substrate. Synthesis of gold nanoparticles was performed according to an adapted Turkevich method. Initial essays were able to suggest the orientation of molecules on gold nanoparticles surface. Central Composite design was performed to obtain the highest SERS signal for nicotinamide and riboflavin. The evaluated parameters in the experimental design were volume of AuNPs, concentration of vitamins and sodium chloride concentration. The best condition for nicotinamide was NaCl 2.3 × 10- 3 mol L- 1 and 700 μL of AuNPs colloid and this same condition showed to be adequate to quantify thiamine. The experimental design for riboflavin shows the best condition at NaCl 1.15 × 10- 2 mol L- 1 and 2.8 mL of AuNPs colloid. It was possible to quantify thiamine and nicotinamide in presence of others vitamins and excipients in two solid multivitamin formulations using the standard addition procedure. The standard addition curve presented a R2 higher than 0.96 for both nicotinamide and thiamine, at orders of magnitude 10- 7 and 10- 8 mol L- 1, respectively. The nicotinamide content in a cosmetic gel sample was also quantified by direct analysis presenting R2 0.98. The t-student test presented no significant difference regarding HPLC method. Despite the experimental design performed for riboflavin, it was not possible its quantification in the commercial samples.

  9. The Leishmania promastigote surface antigen 2 complex is differentially expressed during the parasite life cycle. (United States)

    Handman, E; Osborn, A H; Symons, F; van Driel, R; Cappai, R


    The promastigote surface antigen 2 (PSA-2) complex comprises a family of antigenically similar polypeptides of M(r) 96,000, 80,000 and 50,000, anchored to the membrane with glycosylphosphatidylinositol. Although PSA-2 was initially detected only in promastigotes, Northern blot analysis indicated that mRNA transcripts are also present in amastigotes. Unlike the situation in promastigotes, where at least four major transcripts (2.6-5.3 kb) were detected, only one major (2.6 kb) and two minor transcripts were present in amastigotes. A cDNA clone encoding a member of the PSA-2 family expressed in amastigotes was isolated using DNA probes. The predicted protein sequence of M(r) 40,000 is distinct from promastigote sequences, but shows significant similarity to previously described members of the family from L major and L amazonensis. Antibodies to the carboxyl terminal sequence conserved in all L major PSA-2 studied to date, as well as antibodies affinity purified on the amastigote cDNA-derived polypeptide recognized a major M(r) 50,000 amastigote polypeptide. Immuno-electron microscopy localized both promastigote and amastigote PSA-2 to the cell surface. The expression of PSA-2 polypeptides during the transformation of amastigotes into promastigotes was ordered in a time-dependent manner, with the promastigote M(r) 80000 polypeptide appearing first, followed by the M(r) 96000 polypeptide. In contrast to the glycosylphosphatidylinositol anchor of promastigote PSA-2, which could be hydrolysed by phosphatidylinositol-specific phospholipase C, the amastigote form was resistant to this enzyme.

  10. Noncontact Surface Roughness Estimation Using 2D Complex Wavelet Enhanced ResNet for Intelligent Evaluation of Milled Metal Surface Quality

    Directory of Open Access Journals (Sweden)

    Weifang Sun


    Full Text Available Machined surfaces are rough from a microscopic perspective no matter how finely they are finished. Surface roughness is an important factor to consider during production quality control. Using modern techniques, surface roughness measurements are beneficial for improving machining quality. With optical imaging of machined surfaces as input, a convolutional neural network (CNN can be utilized as an effective way to characterize hierarchical features without prior knowledge. In this paper, a novel method based on CNN is proposed for making intelligent surface roughness identifications. The technical scheme incorporates there elements: texture skew correction, image filtering, and intelligent neural network learning. Firstly, a texture skew correction algorithm, based on an improved Sobel operator and Hough transform, is applied such that surface texture directions can be adjusted. Secondly, two-dimensional (2D dual tree complex wavelet transform (DTCWT is employed to retrieve surface topology information, which is more effective for feature classifications. In addition, residual network (ResNet is utilized to ensure automatic recognition of the filtered texture features. The proposed method has verified its feasibility as well as its effectiveness in actual surface roughness estimation experiments using the material of spheroidal graphite cast iron 500-7 in an agricultural machinery manufacturing company. Testing results demonstrate the proposed method has achieved high-precision surface roughness estimation.

  11. Evaluation of one-dimensional potential energy surfaces for prediction of spectroscopic properties of hydrogen bonds in linear bonded complexes. (United States)

    Jouypazadeh, Hamidreza; Farrokhpour, Hossein; Solimannejad, Mohammad


    This work evaluated the reliability of the one-dimensional potential energy surface for calculating the spectroscopic properties (rovibrational constants and rotational line energies) of hydrogen bonds in linear bonded complexes by comparing theoretical results with the corresponding experimental results. For this purpose, two hydrogen bonded complexes were selected: the HCN···HCN homodimer and the HCN···HF heterodimer. The one-dimensional potential energy surfaces related to the hydrogen bonds in these complexes were calculated using different computational methods and basis sets. The calculated potential curve of each complex was fitted to an analytical one-dimensional potential function to obtain the potential parameters. The obtained analytical potential function of each complex was used in a two-particle Schrödinger equation to obtain the rovibrational energy levels of the hydrogen bond. Using the calculated rovibrational levels, the rovibrational spectra and constants of each complex were calculated and compared with experimental data available from the literature. Compared with experimental data, the calculated one-dimensional potential energy surface at the QCISD/aug-cc-pVDZ level of theory was found to predict the spectroscopic properties of hydrogen bonds better than the potential curves obtained using other computational methods, especially for the HCN···HCN homodimer complex. Generally, the results obtained for the HCN···HCN homodimer complex were closer to experimental data than those obtained for the HCN···HF heterodimer complex. The investigation performed in this work showed that the one-dimensional potential curve related to the hydrogen bond between two linear molecules can be used to predict the spectroscopic constants of hydrogen bonds. Graphical abstract Potential energy curves of HCN···HCN and HCN···HF complexes calculated at the different computational levels.

  12. Surface complexation modelling: Experiments on the sorption of nickel on quartz

    International Nuclear Information System (INIS)

    Puukko, E.; Hakanen, M.


    Assessing the safety of a final repository for nuclear wastes requires knowledge concerning the way in which the radionuclides released are retarded in the geosphere. The aim of the work is to aquire knowledge of empirical methods repeating the experiments on the sorption of nickel on quartz described in the reports published by the British Geological Survey (BGS). The experimental results were modelled with computer models at the Technical Research Centre of Finland (VTT Chemical Technology). The results showed that the experimental knowledge of the sorption of Ni on quartz have been acheved by repeating the experiments of BGS. Experiments made with the two quartz types, Min-U-Sil 5 (MUS) and Nilsiae, showed the difference in sorption of Ni in the low ionic strength solution (0.001 M NaNO 3 ). The sorption of Ni on MUS was higher than predicted by the Surface Complexation Model (SCM). The phenomenon was also observed by the BGS, and may be due to the different amounts of inpurities in the MUS and in the NLS. In other respects, the results of the sorption experiments fitted quite well with those predicted by the SCM model. (8 refs., 8 figs., 11 tabs.)

  13. Direct protein quantification in complex sample solutions by surface-engineered nanorod probes

    KAUST Repository

    Schrittwieser, Stefan


    Detecting biomarkers from complex sample solutions is the key objective of molecular diagnostics. Being able to do so in a simple approach that does not require laborious sample preparation, sophisticated equipment and trained staff is vital for point-of-care applications. Here, we report on the specific detection of the breast cancer biomarker sHER2 directly from serum and saliva samples by a nanorod-based homogeneous biosensing approach, which is easy to operate as it only requires mixing of the samples with the nanorod probes. By careful nanorod surface engineering and homogeneous assay design, we demonstrate that the formation of a protein corona around the nanoparticles does not limit the applicability of our detection method, but on the contrary enables us to conduct in-situ reference measurements, thus further strengthening the point-of-care applicability of our method. Making use of sandwich assays on top of the nanorods, we obtain a limit of detection of 110 pM and 470 pM in 10-fold diluted spiked saliva and serum samples, respectively. In conclusion, our results open up numerous applications in direct protein biomarker quantification, specifically in point-of-care settings where resources are limited and ease-of-use is of essence.

  14. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity. (United States)

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M


    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  15. Detection of biomolecules in complex media using surface plasmon resonance sensors (United States)

    Malone, Michael R.; Masson, Jean-Francois; Barhnart, Margaret; Beaudoin, Stephen; Booksh, Karl S.


    Detection of multiple biologically relevant molecules was accomplished at sub-ng/mL levels in highly fouling media using fiber- optic based surface plasmon resonance sensors. Myocardial infarction markers, myoglobin and cTnI, were quantified in full serum with limits of detection below 1 ng/mL. Biologically relevant levels are between 15-30 ng/mL and 1-5 ng/mL for myoglobin and cTnI respectively. Cytokines involved in chronic wound healing, Interleukin 1, Interleukin 6, and tumor necrosis factor α, were detected at around 1 ng/mL in cell culture media. Preliminary results in monitoring these cytokines in cell cultures expressing the cytokines were obtained. The protein diagnostic of spinal muscular atrophy, survival motor neuron protein, was quantified from cell lysate. To obtain such results in complex media, the sensor's stability to non-specific protein adsorption had to be optimized. A layer of the N-hydroxysuccinimide ester of 16-mercaptohexadecanoic acid is attached to the sensor. This layer optimizes the antibody attachment to the sensor while minimizing the non-specific signal from serum proteins.

  16. From LIDAR Scanning to 3d FEM Analysis for Complex Surface and Underground Excavations (United States)

    Chun, K.; Kemeny, J.


    Light detection and ranging (LIDAR) has been a prevalent remote-sensing technology applied in the geological fields due to its high precision and ease to use. One of the major applications is to use the detailed geometrical information of underground structures as a basis for the generation of three-dimensional numerical model that can be used in FEM analysis. To date, however, straightforward techniques in reconstructing numerical model from the scanned data of underground structures have not been well established or tested. In this paper, we propose a comprehensive approach integrating from LIDAR scanning to finite element numerical analysis, specifically converting LIDAR 3D point clouds of object containing complex surface geometry into finite element model. This methodology has been applied to the Kartchner Caverns in Arizona for the stability analysis. Numerical simulations were performed using the finite element code ABAQUS. The results indicate that the highlights of our technologies obtained from LIDAR is effective and provide reference for other similar engineering project in practice.

  17. A new ab initio potential energy surface for the NH-He complex (United States)

    Ramachandran, R.; Kłos, J.; Lique, F.


    We present a new three-dimensional potential energy surface (PES) for the NH(X3Σ-)-He van der Waals system, which explicitly takes into account the NH vibrational motion. The NH-He PES was obtained using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations. The augmented correlation-consistent aug-cc-pVXZ (X = Q, 5, 6) basis sets were employed, and the energies obtained were then extrapolated to the complete basis set limit. Using this new PES, we have studied the spectroscopy of the NH-He complex and we have determined a new rotational constant that agrees well with the available experimental data. Collisional excitation of NH(X3Σ-) by He was also studied at the close-coupling level. Calculations of the collisional excitation cross sections of the fine-structure levels of NH by He were performed for energies up to 3500 cm-1, which yield, after thermal average, rate coefficients up to 350 K. The calculated rate coefficients are compared with available experimental measurements at room temperature, and a reasonably good agreement is found between experimental and theoretical data.

  18. Surface-Active Mononuclear and Dinuclear Ru(II) Complexes based on Thio-substituted Terpyridines Bearing Cyclodextrin Recognition Units


    Pikramenou, Zoe; Unwin, Patrick R


    Abstract Ruthenium(II) surface active complexes based on a tpySH ligand have been prepared and characterised, (1) [Ru(tpyada)(tpySH)](PF6)2, (2) [Ru(biptpy)(tpySH)](PF6)2 and (3) [Ru(pm-?-CD(ttp))(tpySH)](PF6)2. The complexes bear a surface active thiol group and a recognition unit which is either a ?-cyclodextrin or a hydrophobic tail (admantyl- or biphenyl) in order to utilise cyclodextrin recognition for the formation of supramolecular wires using bottom up approaches. Monolaye...

  19. GeoComplexity and scale: surface processes and remote sensing of geosystems. GeoComplexity and scale: surface processes and remote sensing of geosystems (United States)

    Muller, Jan-Peter


    Understanding the role of scaling in different planetary surface processes within our Solar System is one of the fundamental goals of planetary and solid earth scientific research. There has been a revolution in planetary surface observations over the past decade for the Earth, Mars and the Moon, especially in 3D imaging of surface shape (from the planetary scale down to resolutions of 75cm). I will examine three areas that I have been active in over the last 25 years giving examples of newly processed global datasets ripe for scaling analysis: topography, BRDF/albedo and imaging. For understanding scaling in terrestrial land surface topography we now have global 30m digital elevation models (DEMs) from different types of sensors (InSAR and stereo-optical) along with laser altimeter data to provide global reference models (to better than 1m in cross-over areas) and airborne laser altimeter data over small areas at resolutions better than 1m and height accuracies better than 10-15cm. We also have an increasing number of sub-surface observations from long wavelength SAR in arid regions, which will allow us to look at the true surface rather than the one buried by sand. We also still have a major limitation of these DEMs in that they represent an unknown observable surface with C-band InSAR DEMs representing being somewhere near the top of the canopy and X-band InSAR and stereo near the top of the canopy but only P-band representing the true understorey surface. I will present some of the recent highlights of topography on Mars including 3D modelling of surface shape from the ESA Mars Express HRSC (High Resolution Stereo Camera), see [1], [2] at 30-100m grid-spacing; and then co-registered to HRSC using a resolution cascade of 20m DTMs from NASA MRO stereo-CTX and 0.75m digital terrain models (as there is no land cover on Mars) DTMs from MRO stereo-HiRISE [3]. Comparable DTMs now exist for the Moon from 100m up to 1m. I will show examples of these DEM/DTM datasets

  20. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study


    Stumpel, Jelle E.; Marco, Saccone; Valentina, Dichiarante; Ossi, Lehtonen; Matti, Virkki; Pierangelo, Metrangolo; Arri, Priimagi


    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, a...

  1. Structure and reactivity of heterogeneous surfaces and study of the geometry of surface complexes. Progress report, January 1, 1984-December 31, 1984

    International Nuclear Information System (INIS)

    Landman, U.


    Since the beginning of this project, our group has been involved in theoretical studies of surface phenomena and processes, aimed toward increasing our understanding of fundamental processes which govern the properties of material surfaces. Our studies cover a wide spectrum of surface phenomena: surface reactivity, surface crystallography, electronic and vibrational structure, dynamical processes, phase transformations and phase change, the properties of interfaces and investigations of material processing and novel materials preparation techniques. In these investigations we develop and employ analytical and novel numerical, simulation, methods for the study of complex surface phenomena. Our recent surface molecular dynamics studies and simulations of laser annealing phenomena opened new avenues for the investigation of the microscopic dynamics and evolution of equilibrium and non-equilibrium processes at surfaces and interfaces. Our current studies of metallic glasses using a new langrangian formulation which includes all components of the total energy (density dependent electron gas, single particle and pair interactions) of the system, represents a novel approach for theoretical studies of this important class of systems

  2. Engineering the cell surface display of cohesins for assembly of cellulosome-inspired enzyme complexes on Lactococcus lactis

    Directory of Open Access Journals (Sweden)

    Wieczorek Andrew S


    Full Text Available Abstract Background The assembly and spatial organization of enzymes in naturally occurring multi-protein complexes is of paramount importance for the efficient degradation of complex polymers and biosynthesis of valuable products. The degradation of cellulose into fermentable sugars by Clostridium thermocellum is achieved by means of a multi-protein "cellulosome" complex. Assembled via dockerin-cohesin interactions, the cellulosome is associated with the cell surface during cellulose hydrolysis, forming ternary cellulose-enzyme-microbe complexes for enhanced activity and synergy. The assembly of recombinant cell surface displayed cellulosome-inspired complexes in surrogate microbes is highly desirable. The model organism Lactococcus lactis is of particular interest as it has been metabolically engineered to produce a variety of commodity chemicals including lactic acid and bioactive compounds, and can efficiently secrete an array of recombinant proteins and enzymes of varying sizes. Results Fragments of the scaffoldin protein CipA were functionally displayed on the cell surface of Lactococcus lactis. Scaffolds were engineered to contain a single cohesin module, two cohesin modules, one cohesin and a cellulose-binding module, or only a cellulose-binding module. Cell toxicity from over-expression of the proteins was circumvented by use of the nisA inducible promoter, and incorporation of the C-terminal anchor motif of the streptococcal M6 protein resulted in the successful surface-display of the scaffolds. The facilitated detection of successfully secreted scaffolds was achieved by fusion with the export-specific reporter staphylococcal nuclease (NucA. Scaffolds retained their ability to associate in vivo with an engineered hybrid reporter enzyme, E. coli β-glucuronidase fused to the type 1 dockerin motif of the cellulosomal enzyme CelS. Surface-anchored complexes exhibited dual enzyme activities (nuclease and β-glucuronidase, and were

  3. Immune evasion proteins of murine cytomegalovirus preferentially affect cell surface display of recently generated peptide presentation complexes. (United States)

    Lemmermann, Niels A W; Gergely, Kerstin; Böhm, Verena; Deegen, Petra; Däubner, Torsten; Reddehase, Matthias J


    For recognition of infected cells by CD8 T cells, antigenic peptides are presented at the cell surface, bound to major histocompatibility complex class I (MHC-I) molecules. Downmodulation of cell surface MHC-I molecules is regarded as a hallmark function of cytomegalovirus-encoded immunoevasins. The molecular mechanisms by which immunoevasins interfere with the MHC-I pathway suggest, however, that this downmodulation may be secondary to an interruption of turnover replenishment and that hindrance of the vesicular transport of recently generated peptide-MHC (pMHC) complexes to the cell surface is the actual function of immunoevasins. Here we have used the model of murine cytomegalovirus (mCMV) infection to provide experimental evidence for this hypothesis. To quantitate pMHC complexes at the cell surface after infection in the presence and absence of immunoevasins, we generated the recombinant viruses mCMV-SIINFEKL and mCMV-Deltam06m152-SIINFEKL, respectively, expressing the K(b)-presented peptide SIINFEKL with early-phase kinetics in place of an immunodominant peptide of the viral carrier protein gp36.5/m164. The data revealed approximately 10,000 K(b) molecules presenting SIINFEKL in the absence of immunoevasins, which is an occupancy of approximately 10% of all cell surface K(b) molecules, whereas immunoevasins reduced this number to almost the detection limit. To selectively evaluate their effect on preexisting pMHC complexes, cells were exogenously loaded with SIINFEKL peptide shortly after infection with mCMV-SIINFEKA, in which endogenous presentation is prevented by an L174A mutation of the C-terminal MHC-I anchor residue. The data suggest that pMHC complexes present at the cell surface in advance of immunoevasin gene expression are downmodulated due to constitutive turnover in the absence of resupply.

  4. Application of a surface complexation model to the interactions of Pu and Am with Esk Estuary sediments

    International Nuclear Information System (INIS)

    Turner, D.R.; Knox, S.; Titley, J.G.; Hamilton-Taylor, J.; Kelly, M.; Williams, G.


    Previous work has shown that Pu is remobilised from Esk sediments at low salinities of overlying water. A constant capacitance surface complexation model has been developed in order to understand and model the chemical processes occurring. The model is based on detailed chemical characterisation of sediment samples from the estuary. The following measurements were carried out to provide input parameters for the model: specific surface area; total surface sites (tritium exchange); proton and major ion exchange (potentiometric titration); and actinide (Pu and Am) partition coefficient as a function of pH and salinity at sediment and actinide concentrations typical of the Esk. (author)

  5. Analytical modeling provides new insight into complex mutual coupling between surface loops at ultrahigh fields. (United States)

    Avdievich, N I; Pfrommer, A; Giapitzakis, I A; Henning, A


    Ultrahigh-field (UHF) (≥7 T) transmit (Tx) human head surface loop phased arrays improve both the Tx efficiency (B 1 + /√P) and homogeneity in comparison with single-channel quadrature Tx volume coils. For multi-channel arrays, decoupling becomes one of the major problems during the design process. Further insight into the coupling between array elements and its dependence on various factors can facilitate array development. The evaluation of the entire impedance matrix Z for an array loaded with a realistic voxel model or phantom is a time-consuming procedure when performed using electromagnetic (EM) solvers. This motivates the development of an analytical model, which could provide a quick assessment of the Z-matrix. In this work, an analytical model based on dyadic Green's functions was developed and validated using an EM solver and bench measurements. The model evaluates the complex coupling, including both the electric (mutual resistance) and magnetic (mutual inductance) coupling. Validation demonstrated that the model does well to describe the coupling at lower fields (≤3 T). At UHFs, the model also performs well for a practical case of low magnetic coupling. Based on the modeling, the geometry of a 400-MHz, two-loop transceiver array was optimized, such that, by simply overlapping the loops, both the mutual inductance and the mutual resistance were compensated at the same time. As a result, excellent decoupling (below -40 dB) was obtained without any additional decoupling circuits. An overlapped array prototype was compared (signal-to-noise ratio, Tx efficiency) favorably to a gapped array, a geometry which has been utilized previously in designs of UHF Tx arrays. Copyright © 2017 John Wiley & Sons, Ltd.

  6. Titanium biomaterials with complex surfaces induced aberrant peripheral circadian rhythms in bone marrow mesenchymal stromal cells. (United States)

    Hassan, Nathaniel; McCarville, Kirstin; Morinaga, Kenzo; Mengatto, Cristiane M; Langfelder, Peter; Hokugo, Akishige; Tahara, Yu; Colwell, Christopher S; Nishimura, Ichiro


    Circadian rhythms maintain a high level of homeostasis through internal feed-forward and -backward regulation by core molecules. In this study, we report the highly unusual peripheral circadian rhythm of bone marrow mesenchymal stromal cells (BMSCs) induced by titanium-based biomaterials with complex surface modifications (Ti biomaterial) commonly used for dental and orthopedic implants. When cultured on Ti biomaterials, human BMSCs suppressed circadian PER1 expression patterns, while NPAS2 was uniquely upregulated. The Ti biomaterials, which reduced Per1 expression and upregulated Npas2, were further examined with BMSCs harvested from Per1::luc transgenic rats. Next, we addressed the regulatory relationship between Per1 and Npas2 using BMSCs from Npas2 knockout mice. The Npas2 knockout mutation did not rescue the Ti biomaterial-induced Per1 suppression and did not affect Per2, Per3, Bmal1 and Clock expression, suggesting that the Ti biomaterial-induced Npas2 overexpression was likely an independent phenomenon. Previously, vitamin D deficiency was reported to interfere with Ti biomaterial osseointegration. The present study demonstrated that vitamin D supplementation significantly increased Per1::luc expression in BMSCs, though the presence of Ti biomaterials only moderately affected the suppressed Per1::luc expression. Available in vivo microarray data from femurs exposed to Ti biomaterials in vitamin D-deficient rats were evaluated by weighted gene co-expression network analysis. A large co-expression network containing Npas2, Bmal1, and Vdr was observed to form with the Ti biomaterials, which was disintegrated by vitamin D deficiency. Thus, the aberrant BMSC peripheral circadian rhythm may be essential for the integration of Ti biomaterials into bone.

  7. Assessment of land surface complexity in relation to information capacity and NDVI in different landform regions using landsat data (United States)

    Wang, Xuhong; Zhang, Zhe; Cao, Mingming; Qin, Huijie; Cao, Yakun


    Information capacity is a grayscale digital image quality evaluation model based on multi-dimensional histogram. As local region characteristics of pixels are taken into account in the calculation, it can objectively and effectively characterize the structural feature information of these ground objects. Information capacity is related to image gray levels, while gray levels of remote sensing imagery reflect the complexity of surface landscape. Information capacity is firstly used in geo-science research in this paper, and spatial variation of information capacity in different landform areas is discussed. The results show that spatial the variation of information capacity is closely related to complexity of regional surface structure in different landform types. Generally, information capacity of mountain is the largest, information capacity of hills and plain is followed in order. Moreover, information capacity is sensitive to the change rate of vegetation coverage of different land covers. There are strong correlation between information capacity and NDVI standard deviation, and the correlation coefficient respectively is 0.8347 or 0.8648 in different experimental areas. This study shows that information capacity can effectively characterize the complexity of the regional surface structure and have great significance for quantitative research of surface feature complexity.

  8. Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

    Energy Technology Data Exchange (ETDEWEB)

    Kostyrko, T., E-mail:; Ślusarski, T. [Faculty of Physics, A. Mickiewicz University, ul. Umultowska 85, 61-614 Poznań (Poland)


    A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

  9. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    Energy Technology Data Exchange (ETDEWEB)

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J., E-mail: [INQUIMAE-CONICET, Departamento de Química Inorgánica, Analítica y Química-Física, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA (Argentina)


    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  10. Estimation of surface energy fluxes under complex terrain of Mt. Qomolangma over the Tibetan Plateau

    NARCIS (Netherlands)

    Chen, Xuelong; Su, Zhongbo; Ma, Y.; Yang, K.; Wang, B.


    Surface solar radiation is an important parameter in surface energy balance models and in estimation of evapotranspiration. This study developed a DEM based radiation model to estimate instantaneous clear sky solar radiation for surface energy balance system to obtain accurate energy absorbed by the

  11. Crystal structure, Hirshfeld surfaces and DNA cleavage investigation of two copper(II) complexes containing polypyridine and salicylide ligands. (United States)

    Luo, Yang-Hui; Sun, Bai-Wang


    Two copper complexes 1 [Cu2(phen)2(salicylaldehyde)2(ClO4)2] and 2 [Cu2 (2,2'-dipyridyl)2(salicylaldehyde)2(ClO4)2] have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. These two complexes were display binuclear structure with Cu(II) ions in distorted octahedral environment but antipodal orientation of the binuclear units between them. Molecular Hirshfeld surfaces revealed that the crystal structures of 1 and 2 were supported mainly by H-H, C-H⋯π, π⋯π (C-C), and C-H⋯O intermolecular interactions. DNA cleavage experiments of complexes 1 and 2 revealed that these complexes can intercalation with DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Planification de trajectoires pour placement automatise de fibres sur surfaces de geometries complexes (United States)

    Hely, Clement

    During the past 50 years, the use of composite materials drastically increase, mainly thanks to the interest of aeronautical industries for these strong and lightweight materials. To improve the productivity of composite materials manufacturing some of the largest aeronautics companies began to develop automated processes such as Automated Fibre Placement (AFP). The AFP workcells currently used by the industry were mainly developed for production of large, nearly flat, plates with low curvatures such as aircraft fuselages. However, the fields of aeronautics and sport goods production begin nowadays to show an interest for manufacturing of smaller and more complex parts. The aim of the project in which this research takes place is to design a new AFP workcell and to develop new techniques allowing production of parts with small size and complex geometry. The work presented in this thesis focuses on the path planning on multi-axial revolution surfaces, e.g. Y-shaped tubes of constant circular cross section. Several path planning algorithms will be presented aiming at the exhaustive coverage of a mandrel with pre-impregnated (prepreg) composite tape. The methodology used in two of these algorithms is to individually cover each branch of the Y-shaped part with paths deriving from a helix. In the first one, the helix will be cut at the boundary between a branch and the junction region (algorithm HD) while in the second (algorithm HA) the pseudo-helix path can be adjusted to follow this boundary. These two methods were shown to have some drawbacks compromising their practical use and possibly leading to parts with diminished mechanical properties. To avoid these drawbacks, two others algorithms were developed with a new methodology. With them, the aim is to cover two branches of the Y-shape with a continuous course (i.e. without cut). The first one uses a well known strategy which defines plies with a constant fibre orientation. Parallel paths are then computed to

  13. One-level modeling for diagnosing surface winds over complex terrain. II - Applicability to short-range forecasting (United States)

    Alpert, P.; Getenio, B.; Zak-Rosenthal, R.


    The Alpert and Getenio (1988) modification of the Mass and Dempsey (1985) one-level sigma-surface model was used to study four synoptic events that included two winter cases (a Cyprus low and a Siberian high) and two summer cases. Results of statistical verification showed that the model is not only capable of diagnosing many details of surface mesoscale flow, but might also be useful for various applications which require operative short-range prediction of the diurnal changes of high-resolution surface flow over complex terrain, for example, in locating wildland fires, determining the dispersion of air pollutants, and predicting changes in wind energy or of surface wind for low-level air flights.

  14. Investigate the complex process in particle-fluid based surface generation technology using reactive molecular dynamics method (United States)

    Han, Xuesong; Li, Haiyan; Zhao, Fu


    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.

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

    Directory of Open Access Journals (Sweden)

    Xuesong Han


    Full Text Available 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.


    Directory of Open Access Journals (Sweden)

    A. V. Gorevoy


    Full Text Available The problem of non-contact surface defect area measurement at complex-shape objects under videoendoscopic control is considered. Major factors contributing to the measurement uncertainty are analyzed for the first time. The proposed method of accuracy analysis is based on the evaluation of 3D coordinates of surface points from 2D projections under assumption of projective camera model and Mahalanobis distance minimization in the image plane. Expressions for area measurement error caused by sum-of-triangles approximation are obtained analytically for practically important cases of cylindrical and spherical surfaces. It is shown that the magnitude of this error component for a single triangle does not exceed 1% for the real values of parameters of the endoscopic imaging system. Expressions are derived for area measurement uncertainty evaluation on arbitrary shape surfaces, caused by measurement errors of 3D coordinates of individual points with and without a priori information about surface shape. Verification of the obtained expressions with real experiment data showed that area measurement error for a complex figure, given by a set of points, is mainly caused by ignoring the fact that these points belong to the surface. It is proved that the use of a priori information about investigated surface shape, which is often available from the design documentation, in many cases would radically improve the accuracy of surface defects area measurement. The presented results are valid for stereoscopic, shadow and phase methods of video endoscopic measurements and can be effectively used in development of new non-contact measuring endoscopic systems and modernization of existing ones.

  17. Chemodynamics of Soft Nanoparticulate Metal Complexes: From the Local Particle/Medium Interface to a Macroscopic Sensor Surface. (United States)

    Town, Raewyn M; Pinheiro, José Paulo; van Leeuwen, Herman P


    The lability of a complex species between a metal ion M and a binding site S, MS, is conventionally defined with respect to an ongoing process at a reactive interface, for example, the conversion or accumulation of the free metal ion M by a sensor. In the case of soft charged multisite nanoparticulate complexes, the chemodynamic features that are operative within the micro environment of the particle body generally differ substantially from those for dissolved similar single-site complexes in the same medium. Here we develop a conceptual framework for the chemodynamics and the ensuing lability of soft (3D) nanoparticulate metal complexes. The approach considers the dynamic features of MS at the intraparticulate level and their impact on the overall reactivity of free metal ions at the surface of a macroscopic sensing interface. Chemodynamics at the intraparticulate level is shown to involve a local reaction layer at the particle/medium interface, while at the macroscopic sensor level an operational reaction layer is invoked. Under a certain window of conditions, volume exclusion of the nanoparticle body near the medium/sensor interface is substantial and affects the properties of the reaction layer and the overall lability of the nanoparticulate MS complex toward the reactive surface.

  18. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

    Directory of Open Access Journals (Sweden)

    Jelle E. Stumpel


    Full Text Available In recent years, supramolecular complexes comprising a poly(4-vinylpyridine backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs. The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer–azobenzene complexes.

  19. Surface-Relief Gratings in Halogen-Bonded Polymer-Azobenzene Complexes: A Concentration-Dependence Study. (United States)

    Stumpel, Jelle E; Saccone, Marco; Dichiarante, Valentina; Lehtonen, Ossi; Virkki, Matti; Metrangolo, Pierangelo; Priimagi, Arri


    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer-azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer-azobenzene complexes.

  20. Comparison of surface extraction techniques performance in computed tomography for 3D complex micro-geometry dimensional measurements

    DEFF Research Database (Denmark)

    Torralba, Marta; Jiménez, Roberto; Yagüe-Fabra, José A.


    micro-geometries as well (i.e., in the sub-mm dimensional range). However, there are different factors that may influence the CT process performance, being one of them the surface extraction technique used. In this paper, two different extraction techniques are applied to measure a complex miniaturized...... Canny algorithm. This algorithm has proven to provide accurate results in parts with simple geometries, but its suitability for 3D complex geometries has not been proven so far. To verify the measurement results and compare both techniques, reference measurements are performed on an optical coordinate...

  1. Surface-Enhanced Raman Scattering of the Complexes of Silver with Adenine and dAMP

    NARCIS (Netherlands)

    Otto, Cornelis; Hoeben, F.P.; Hoeben, F.P.; Greve, Jan


    The behaviour of adenine and 2'-deoxyadenosine-5'-monophosphate (dAMP) at positive surface potentials of a silver working electrode was investigated using surface-enhanced Raman scattering (SERS). The use of positive potentials in the presence of adenine or dAMP leads to a rapid accumulation of an

  2. Effective surface passivation of multi-shelled InP quantum dots through a simple complexing with titanium species (United States)

    Jo, Jung-Ho; Kim, Min-Seok; Han, Chang-Yeol; Jang, Eun-Pyo; Do, Young Rag; Yang, Heesun


    Fluorescent efficiency of various visible quantum dots (QDs) has been incessantly improved to meet industrially high standard mainly through the advance in core/shell heterostructural design, however, their stability against degradable environments appears still lacking. The most viable strategy to cope with this issue was to exploit chemically inert oxide phases to passivate QD surface in the form of either individual overcoating or matrix embedding. Herein, we report a simple but effective means to passivate QD surface by complexing its organic ligands with a metal alkoxide of titanium isopropoxide (Ti(i-PrO)4). For this, highly efficient red-emitting InP QDs with a multi-shell structure of ZnSeS intermediate plus ZnS outer shell are first synthesized and then the surface of resulting InP/ZnSeS/ZnS QDs is in-situ decorated with Ti(i-PrO)4. The presence of Tisbnd O species from Ti(i-PrO)4 on QD surface is verified by x-ray photoelectron and Fourier transform infrared spectroscopic analyses. Two comparative dispersions of pristine versus Ti(i-PrO)4-complexed QDs are exposed for certain periods of time to UV photon and heat and their temporal changes in photoluminescence are monitored, resulting in a huge improvement in QD stability from the latter ones through Ti(i-PrO)4-mediated better surface passivation.

  3. Direct Imaging of DNA/Lipid Complexes Interacting with Liposome Surfaces and Fibroblasts (United States)

    Lin, Alison J.; Idziak, Stefan H. J.; Rädler, Joachim; George, Cyril X.; Safinya, Cyrus R.; Samuel, Charles E.


    Video-enhanced light microscopy techniques (phase contrast, differential interference contrast, and fluorescence) were used for direct imaging of the structure and dynamics of nucleic acid-cationic liposome complexes both on liposomes (a model cell) and within the cytoplasm of Mouse L929 Fibroblasts. The experiments are designed to enable us to correlate the complex's structure to the transfection efficiencies (i.e. the uptake and expression of nucleic acid) in animal cells. The ultimate goal of the project is to design an optimal non-viral vector (carrier of nucleic acids). Fluorescence labeling of both the lipid and nucleic acid components is used for visualization experiments at the level of single complexes interacting with a single cell (e.g. a giant liposome or an isolated mammalian cell). This allows us to follow the temporal path of a complex. Direct motion versus random Brownian diffusion are readily distinguished. Micropipettes were used for placement of cells and microinjection into cells.

  4. Composition and structure of Si-doped NiTi with a complex surface profile (United States)

    Slabodchikov, Vladimir A.; Ovchinnikov, Stanislav V.; Kuznetsov, Vladimir M.


    The paper presents Auger spectroscopy and electron microscopy data on the elemental composition and structure of NiTi specimens with blind holes doped with Si through plasma immersion ion implantation. The data demonstrate how silicon is distributed through the depth of NiTi from its front surface and along the side of its hole. The upper layer formed upon treatment is shown to be amorphous, and its thickness measuring several tens of nanometers is about two times larger on the side surface of the hole than on the front surface.

  5. Final Report: Optimal Model Complexity in Geological Carbon Sequestration: A Response Surface Uncertainty Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ye [Univ. of Wyoming, Laramie, WY (United States)


    The critical component of a risk assessment study in evaluating GCS is an analysis of uncertainty in CO2 modeling. In such analyses, direct numerical simulation of CO2 flow and leakage requires many time-consuming model runs. Alternatively, analytical methods have been developed which allow fast and efficient estimation of CO2 storage and leakage, although restrictive assumptions on formation rock and fluid properties are employed. In this study, an intermediate approach is proposed based on the Design of Experiment and Response Surface methodology, which consists of using a limited number of numerical simulations to estimate a prediction outcome as a combination of the most influential uncertain site properties. The methodology can be implemented within a Monte Carlo framework to efficiently assess parameter and prediction uncertainty while honoring the accuracy of numerical simulations. The choice of the uncertain properties is flexible and can include geologic parameters that influence reservoir heterogeneity, engineering parameters that influence gas trapping and migration, and reactive parameters that influence the extent of fluid/rock reactions. The method was tested and verified on modeling long-term CO2 flow, non-isothermal heat transport, and CO2 dissolution storage by coupling two-phase flow with explicit miscibility calculation using an accurate equation of state that gives rise to convective mixing of formation brine variably saturated with CO2. All simulations were performed using three-dimensional high-resolution models including a target deep saline aquifer, overlying caprock, and a shallow aquifer. To evaluate the uncertainty in representing reservoir permeability, sediment hierarchy of a heterogeneous digital stratigraphy was mapped to create multiple irregularly shape stratigraphic models of decreasing geologic resolutions: heterogeneous (reference), lithofacies, depositional environment, and a (homogeneous) geologic formation. To ensure model

  6. Curvature Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Curvature was calculated from the bathymetry surface for each raster cell using the ArcGIS 3D Analyst "Curvature" Tool. Curvature describes the rate of change of...

  7. Rugosity Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Rugosity was calculated from the bathymetry surface for each cell using the "Rugosity" function in the Benthic Terrain Modeler toolbox (Jenness 2002, 2004; Wright et...

  8. An initial research on solute migration model coupled with adsorption of surface complexation in groundwater

    International Nuclear Information System (INIS)

    Qian Tianwei; Chen Fanrong


    The influence of solution chemical action in groundwater on solute migration has attracted increasing public attention, especially adsorption action occurring on surface of solid phase and liquid phase, which has play a great role in solute migration. There are various interpretations on adsorption mechanism, in which surface complexion is one of successful hypothesis. This paper first establishes a geochemical model based on surface complexion and then coupled it with traditional advection-dispersion model to constitute a solute migration model, which can deal with surface complexion action. The simulated results fit very well with those obtained by the precursors, as compared with a published famous example, which indicates that the model set up by this paper is successful. (authors)

  9. Profile Curvature Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Profile curvature was calculated from the bathymetry surface for each raster cell using the ArcGIS 3D Analyst "Curvature" Tool. Profile curvature describes the rate...

  10. Slope Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Slope was calculated from the bathymetry surface for each raster cell using ArcGIS's Spatial Analyst 'Slope' Tool. Slope describes the maximum steepness of a terrain...

  11. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa


    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  12. Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

    Energy Technology Data Exchange (ETDEWEB)

    Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)


    Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

  13. Modeling the Excess Cell Surface Stored in a Complex Morphology of Bleb-Like Protrusions.

    Directory of Open Access Journals (Sweden)

    Maryna Kapustina


    Full Text Available Cells transition from spread to rounded morphologies in diverse physiological contexts including mitosis and mesenchymal-to-amoeboid transitions. When these drastic shape changes occur rapidly, cell volume and surface area are approximately conserved. Consequently, the rounded cells are suddenly presented with a several-fold excess of cell surface whose area far exceeds that of a smooth sphere enclosing the cell volume. This excess is stored in a population of bleb-like protrusions (BLiPs, whose size distribution is shown by electron micrographs to be skewed. We introduce three complementary models of rounded cell morphologies with a prescribed excess surface area. A 2D Hamiltonian model provides a mechanistic description of how discrete attachment points between the cell surface and cortex together with surface bending energy can generate a morphology that satisfies a prescribed excess area and BLiP number density. A 3D random seed-and-growth model simulates efficient packing of BLiPs over a primary rounded shape, demonstrating a pathway for skewed BLiP size distributions that recapitulate 3D morphologies. Finally, a phase field model (2D and 3D posits energy-based constitutive laws for the cell membrane, nematic F-actin cortex, interior cytosol, and external aqueous medium. The cell surface is equipped with a spontaneous curvature function, a proxy for the cell surface-cortex couple, that is a priori unknown, which the model "learns" from the thin section transmission electron micrograph image (2D or the "seed and growth" model image (3D. Converged phase field simulations predict self-consistent amplitudes and spatial localization of pressure and stress throughout the cell for any posited stationary morphology target and cell compartment constitutive properties. The models form a general framework for future studies of cell morphological dynamics in a variety of biological contexts.

  14. A preliminary investigation of the applicability of surface complexation modeling to the understanding of transportation cask weeping

    International Nuclear Information System (INIS)

    Granstaff, V.E.; Chambers, W.B.; Doughty, D.H.


    A new application for surface complexation modeling is described. These models, which describe chemical equilibria among aqueous and adsorbed species, have typically been used for predicting groundwater transport of contaminants by modeling the natural adsorbents as various metal oxides. Our experiments suggest that this type of modeling can also explain stainless steel surface contamination and decontamination mechanisms. Stainless steel transportation casks, when submerged in a spent fuel storage pool at nuclear power stations, can become contaminated with radionuclides such as 137 Cs, 134 Cs, and 60 Co. Subsequent release or desorption of these contaminants under varying environmental conditions occasionally results in the phenomenon known as open-quotes cask weeping.close quotes We have postulated that contaminants in the storage pool adsorb onto the hydrous metal oxide surface of the passivated stainless steel and are subsequently released (by conversion from a fixed to a removable form) during transportation, due to varying environmental factors, such as humidity, road salt, dirt, and acid rain. It is well known that 304 stainless steel has a chromium enriched passive surface layer; thus its adsorption behavior should be similar to that of a mixed chromium/iron oxide. To help us interpret our studies of reversible binding of dissolved metals on stainless steel surfaces, we have studied the adsorption of Co +2 on Cr 2 O 3 . The data are interpreted using electrostatic surface complexation models. The FITEQL computer program was used to obtain the model binding constants and site densities from the experimental data. The MINTEQA2 computer speciation model was used, with the fitted constants, in an attempt to validate this approach

  15. Directed assembly of functional light harvesting antenna complexes onto chemically patterned surfaces

    International Nuclear Information System (INIS)

    Escalante, Maryana; Maury, Pascale; Bruinink, Christiaan M; Werf, Kees van der; Olsen, John D; Timney, John A; Huskens, Jurriaan; Hunter, C Neil; Subramaniam, Vinod; Otto, Cees


    We report the directed assembly of the photosynthetic membrane proteins LH1 and LH2 isolated from the purple bacterium Rhodobacter sphaeroides onto chemically patterned substrates. Nanoimprint lithography was used to pattern discrete regions of amino- and fluoro-terminated or poly(ethylene glycol) self-assembled monolayers onto a glass substrate. Densely packed layers of assembled protein complexes were observed with atomic force microscopy. The protein complexes attached selectively to the amino-terminated regions by electrostatic interactions. Spectral images generated with a hybrid scanning probe and fluorescence microscope confirmed that the patterned proteins retained their native optical signatures

  16. Wear of carbide inserts with complex surface treatment when milling nickel alloy (United States)

    Fedorov, Sergey; Swe, Min Htet; Kapitanov, Alexey; Egorov, Sergey


    One of the effective ways of strengthening hard alloys is the creating structure layers on their surface with the gradient distribution of physical and mechanical properties between the wear-resistant coating and the base material. The article discusses the influence of the near-surface layer which is modified by low-energy high-current electron-beam alloying and the upper anti-friction layer in a multi-component coating on the wear mechanism of the replaceable multifaceted plates in the dry milling of the difficult to machine nickel alloys.

  17. Validation of solar radiation surfaces from MODIS and reanalysis data over topographically complex terrain (United States)

    Todd A. Schroeder; Robbie Hember; Nicholas C. Coops; Shunlin Liang


    The magnitude and distribution of incoming shortwave solar radiation (SW) has significant influence on the productive capacity of forest vegetation. Models that estimate forest productivity require accurate and spatially explicit radiation surfaces that resolve both long- and short-term temporal climatic patterns and that account for topographic variability of the land...

  18. The complex dispersion relation of surface plasmon polaritons at gold/para-hexaphenylene interfaces

    DEFF Research Database (Denmark)

    Lemke, Christoph; Leißner, Till; Klick, Alwin


    Two-photon photoemission electron microscopy (2P-PEEM) is used to measure the real and imaginary part of the dispersion relation of surface plasmon polaritons at different interface systems. A comparison of calculated and measured dispersion data for a gold/vacuum interface demonstrates...

  19. Carborane–β-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

    NARCIS (Netherlands)

    Neirynck, Pauline; Neirynck, P.; Schimer, J.; Jonkheijm, Pascal; Milroy, L.G.; Cigler, P.; Brunsveld, Luc


    Supramolecular chemistry provides an attractive entry to generate dynamic and well-controlled bioactive surfaces. Novel host–guest systems are urgently needed to provide a broader affinity and applicability portfolio. A synthetic strategy to carborane–peptide bioconjugates was therefore developed to

  20. On the source inversion of fugitive surface layer releases. Part II. Complex sources (United States)

    Sanfélix, V.; Escrig, A.; López-Lilao, A.; Celades, I.; Monfort, E.


    The experimental measurement of fugitive emissions of particulate matter entails inherent complexity because they are usually discontinuous, of short duration, may be mobile, and are affected by weather conditions. Owing to this complexity, instead of experimental measurements, emission factors are used to inventory such emissions. Unfortunately, emission factor datasets are still very limited at present and are insufficient to identify problematic operations and appropriately select control measures. To extend these datasets, a source inversion methodology (described in Part I of this work) was applied to field campaigns in which operation-specific fugitive particulate matter emission factors were determined for several complex fugitive sources, some of which were mobile. Mobile sources were treated as a superposition of instantaneous sources. The experimental campaigns were conducted at ports (bulk solids terminals), aggregate quarries, and cement factories, encompassing powder handling operations and vehicle circulation on paved and unpaved roads. Emission factors were derived for the operations and materials involved in these scenarios and compared with those available in the emission factor compilations. Significant differences were observed between the emission factors obtained in the studied handling operations. These differences call into question the use of generic emission factors and highlight the need for more detailed studies in this field.

  1. Carborane-beta-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

    Czech Academy of Sciences Publication Activity Database

    Neirynck, P.; Schimer, Jiří; Jonkheijm, P.; Milroy, L. G.; Cígler, Petr; Brunsveld, L.


    Roč. 3, č. 4 (2015), s. 539-545 ISSN 2050-750X R&D Projects: GA MŠk(CZ) LH11027 Institutional support: RVO:61388963 Keywords : beta-cyclodextrine/carborane host-guest system * supramolecular chemistry * bioactive surfaces Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.872, year: 2015

  2. Complex surface deformation of Akutan volcano, Alaska revealed from InSAR time series (United States)

    Wang, Teng; DeGrandpre, Kimberly; Lu, Zhong; Freymueller, Jeffrey T.


    Akutan volcano is one of the most active volcanoes in the Aleutian arc. An intense swarm of volcano-tectonic earthquakes occurred across the island in 1996. Surface deformation after the 1996 earthquake sequence has been studied using Interferometric Synthetic Aperture Radar (InSAR), yet it is hard to determine the detailed temporal behavior and spatial extent of the deformation due to decorrelation and the sparse temporal sampling of SAR data. Atmospheric delay anomalies over Akutan volcano are also strong, bringing additional technical challenges. Here we present a time series InSAR analysis from 2003 to 2016 to reveal the surface deformation in more detail. Four tracks of Envisat data acquired from 2003 to 2010 and one track of TerraSAR-X data acquired from 2010 to 2016 are processed to produce high-resolution surface deformation, with a focus on studying two transient episodes of inflation in 2008 and 2014. For the TerraSAR-X data, the atmospheric delay is estimated and removed using the common-master stacking method. These derived deformation maps show a consistently uplifting area on the northeastern flank of the volcano. From the TerraSAR-X data, we quantify the velocity of the subsidence inside the caldera to be as high as 10 mm/year, and identify another subsidence area near the ground cracks created during the 1996 swarm.

  3. Downscaling Land Surface Temperature in Complex Regions by Using Multiple Scale Factors with Adaptive Thresholds. (United States)

    Yang, Yingbao; Li, Xiaolong; Pan, Xin; Zhang, Yong; Cao, Chen


    Many downscaling algorithms have been proposed to address the issue of coarse-resolution land surface temperature (LST) derived from available satellite-borne sensors. However, few studies have focused on improving LST downscaling in urban areas with several mixed surface types. In this study, LST was downscaled by a multiple linear regression model between LST and multiple scale factors in mixed areas with three or four surface types. The correlation coefficients (CCs) between LST and the scale factors were used to assess the importance of the scale factors within a moving window. CC thresholds determined which factors participated in the fitting of the regression equation. The proposed downscaling approach, which involves an adaptive selection of the scale factors, was evaluated using the LST derived from four Landsat 8 thermal imageries of Nanjing City in different seasons. Results of the visual and quantitative analyses show that the proposed approach achieves relatively satisfactory downscaling results on 11 August, with coefficient of determination and root-mean-square error of 0.87 and 1.13 °C, respectively. Relative to other approaches, our approach shows the similar accuracy and the availability in all seasons. The best (worst) availability occurred in the region of vegetation (water). Thus, the approach is an efficient and reliable LST downscaling method. Future tasks include reliable LST downscaling in challenging regions and the application of our model in middle and low spatial resolutions.

  4. Analysis of progression of fatigue conditions in biceps brachii muscles using surface electromyography signals and complexity based features. (United States)

    Karthick, P A; Makaram, Navaneethakrishna; Ramakrishnan, S


    Muscle fatigue is a neuromuscular condition where muscle performance decreases due to sustained or intense contraction. It is experienced by both normal and abnormal subjects. In this work, an attempt has been made to analyze the progression of muscle fatigue in biceps brachii muscles using surface electromyography (sEMG) signals. The sEMG signals are recorded from fifty healthy volunteers during dynamic contractions under well defined protocol. The acquired signals are preprocessed and segmented in to six equal parts for further analysis. The features, such as activity, mobility, complexity, sample entropy and spectral entropy are extracted from all six zones. The results are found showing that the extracted features except complexity feature have significant variations in differentiating non-fatigue and fatigue zone respectively. Thus, it appears that, these features are useful in automated analysis of various neuromuscular activities in normal and pathological conditions.

  5. The NO-carbon reaction: the influence of potassium and CO on reactivity and populations of oxygen surface complexes

    Energy Technology Data Exchange (ETDEWEB)

    Diana Lopez; Joseph Calo [Brown University, Providence, RI (United States). Division of Engineering


    Results on the effects of a metal catalyst and the role of CO as a reducing agent are reported for a resin char and a Wyodak coal char, as well as demineralized samples of the latter. The effect of an active metal catalyst, such as potassium in the current work, is to significantly increase the reactivity both by increasing the number of reaction sites via the catalyst dispersion and reducing the activation energy and by increasing CO{sub 2} production. The latter is a beneficial result because it means that less carbon is consumed per molecule of NO reduced. Additional CO in the gas phase 'catalyzes' NO reduction via the creation of more labile surface complexes and facilitation of desorption of other oxygen complexes. This effect decreases with an increasing temperature and disappears by about 1123 K. The activation energy of this reaction is comparable to that induced by the metal catalyst. 21 refs., 9 figs., 2 tabs.

  6. A coupled remote sensing and the Surface Energy Balance with Topography Algorithm (SEBTA) to estimate actual evapotranspiration under complex terrain (United States)

    Gao, Z. Q.; Liu, C. S.; Gao, W.; Chang, N. B.


    Evapotranspiration (ET) may be used as an ecological indicator to address the ecosystem complexity. The accurate measurement of ET is of great significance for studying environmental sustainability, global climate changes, and biodiversity. Remote sensing technologies are capable of monitoring both energy and water fluxes on the surface of the Earth. With this advancement, existing models, such as SEBAL, S_SEBI and SEBS, enable us to estimate the regional ET with limited temporal and spatial scales. This paper extends the existing modeling efforts with the inclusion of new components for ET estimation at varying temporal and spatial scales under complex terrain. Following a coupled remote sensing and surface energy balance approach, this study emphasizes the structure and function of the Surface Energy Balance with Topography Algorithm (SEBTA). With the aid of the elevation and landscape information, such as slope and aspect parameters derived from the digital elevation model (DEM), and the vegetation cover derived from satellite images, the SEBTA can fully account for the dynamic impacts of complex terrain and changing land cover in concert with some varying kinetic parameters (i.e., roughness and zero-plane displacement) over time. Besides, the dry and wet pixels can be recognized automatically and dynamically in image processing thereby making the SEBTA more sensitive to derive the sensible heat flux for ET estimation. To prove the application potential, the SEBTA was carried out to present the robust estimates of 24 h solar radiation over time, which leads to the smooth simulation of the ET over seasons in northern China where the regional climate and vegetation cover in different seasons compound the ET calculations. The SEBTA was validated by the measured data at the ground level. During validation, it shows that the consistency index reached 0.92 and the correlation coefficient was 0.87.

  7. Phosphorescence quenching of fac-tris(2-phenylpyridyl)iridium(iii) complexes in thin films on dielectric surfaces. (United States)

    Ribierre, J C; Ruseckas, A; Staton, S V; Knights, K; Cumpstey, N; Burn, P L; Samuel, I D W


    We study the influence of the film thickness on the time-resolved phosphorescence and the luminescence quantum yield of fac-tris(2-phenylpyridyl)iridium(iii) [Ir(ppy)3]-cored dendrimers deposited on dielectric substrates. A correlation is observed between the surface quenching velocity and the quenching rate by intermolecular interactions in the bulk film, which suggests that both processes are controlled by dipole-dipole interactions between Ir(ppy)3 complexes at the core of the dendrimers. It is also found that the surface quenching velocity decreases as the refractive index of the substrate is increased. This can be explained by partial screening of dipole-dipole interactions by the dielectric environment.

  8. The monothiocyanate complexes of chromium ion(III) on the silver electrode by the surface enhanced Raman scattering (United States)

    Wang, Huanru; Wu, Guozhen


    Two adsorbate forms of the monothiocyanate complex of chromium ion on the silver electrode are identified in the surface enhanced Raman scattering. The spectroscopic, especially the electronic, properties of these two forms under different applied voltages on the electrode and under both 632.8 and 514.5 nm excitations are studied by the bond force constants (bond orders) and the bond polarizability derivatives which are retrieved from the Raman intensities by an algorithm developed by Wu and co-workers [B. Tian, G. Wu, G. Liu, J. Chem. Phys. 87 (1987) 7300]. The work shows the potential of this approach to the surface enhanced Raman scattering and other fields like resonance Raman that involve vibronic coupling.

  9. Surface complexation modeling of U(VI) sorption on GMZ bentonite in the presence of fulvic acid

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jie [Lanzhou Univ. (China). Radiochemistry Laboratory; Ministry of Industry and Information Technology, Guangzhou (China). The 5th Electronics Research Inst.; Luo, Daojun [Ministry of Industry and Information Technology, Guangzhou (China). The 5th Electronics Research Inst.; Qiao, Yahua; Wang, Liang; Zhang, Chunming [Ministry of Environmental Protection, Beijing (China). Nuclear and Radiation Safety Center; Wu, Wangsuo [Lanzhou Univ. (China). Radiochemistry Laboratory; Ye, Yuanlv [Ministry of Environmental Protection, Beijing (China). Nuclear and Radiation Safety Center; Lanzhou Univ. (China). Radiochemistry Laboratory


    In this work, experiments and modeling for the interactions between uranyl ion and GMZ bentonite in the presence of fulvic acid are presented. The results demonstrated that FA is strongly bound to GMZ bentonite, and these molecules have a very large effect on the U(VI) sorption. The results also demonstrated that U(VI) sorption to GMZ bentonite in the presence and absence of sorbed FA can be well predicted by combining SHM and DLM. According to the model calculations, the nature of the interactions between FA with U(VI) at GMZ bentonite surface is mainly surface complex. The first attempt to simulate clay interaction with humus by the SHM model.

  10. A simple method for the preparation of difficult 99mTc complexes using surface adsorbed stannous ions

    International Nuclear Information System (INIS)

    Maddalena, D.J.; Snowdon, G.M.; Pojer, P.M.


    A simple new technique where stannous tin is adsorbed on the inner surface of plastic tubing and used to reduce ( 99m Tc) pertechnetate prior to labelling radiopharmaceuticals, has been evaluated, using some lipophillic and metal containing ligands. Complexes formed using the technique had good labelling efficiency and behaved the same in rat biodistribution studies as those prepared using conventional labelling methods. The labelling efficiency of the ligands was not related to their lipophillicity suggesting that this technique may be useful for labelling lipophillic and other difficult ligands such as those containing metals, which are incompatible with free stannous ions in solution. (M.E.L.) [es

  11. Discrete complexes immobilized onto click-SBA-15 silica: controllable loadings and the impact of surface coverage on catalysis. (United States)

    Nakazawa, Jun; Smith, Brian J; Stack, T Daniel P


    Azidopropyl functionalized mesoporous silica SBA-15 were prepared with variable azide loadings of 0.03-0.7 mmol g(-1) (~2-50% of maximal surface coverage) through a direct synthesis, co-condensation approach. These materials are functionalized selectively with ethynylated organic moieties through a copper-catalyzed azide alkyne cycloaddition (CuAAC) or "click" reaction. Specific loading within a material can be regulated by either the azide loading or limiting the alkyne reagent relative to the azide loading. The immobilization of ferrocene, pyrene, tris(pyridylmethyl)amine (TPA), and iron porphyrin (FeTPP) demonstrates the robust nature and reproducibility of this two-step synthetic attachment strategy. Loading-sensitive pyrene fluorescence correlates with a theoretically random surface distribution, rather than a uniform one; site-isolation of tethered moieties ~15 Å in length occurs at loadings less than 0.02 mmol g(-1). The effect of surface loading on reactivity is observed in the oxygenation of SBA-15-[Cu(I)(TPA)]. SBA-15-[Mn(II)(TPA)]-catalyzed epoxidation exhibits a systematic dependence on surface loading. A comparison of homogeneous, site-isolated and site-dense complexes provides insight into catalyst speciation and ligand activity.

  12. Excitation of multipolar surface plasmon resonance in plasmonic nanoparticles by complex accelerating beams

    International Nuclear Information System (INIS)

    Yang, Yang; Li, Jiafang; Li, Zhi-Yuan; Chen, Yue-Gang


    In this paper, through a vector-spherical harmonics approach, we investigate the optical spectra of plasmonic Au nanoparticles excited by two special accelerating beams: a non-paraxial Airy beam and a Bessel beam. We systematically analyze the impacts of the beam profile, phase, and helical wave front of the electromagnetic fields on the optical spectrum and the excitation of the surface plasmon resonance (SPR). We find that the high-order phase in the Airy beam would result in strong plasmonic oscillations in the optical spectra, while the cone angle and orbital angular momentum carried by the Bessel beam could be employed to engineer the plasmon modes excited in Au nanoparticles. Furthermore, the optical spectrum excited by a combined Airy–Bessel–Gauss beam is discussed. The study could help to deeply explore new ways to manipulate SPR in metal nanoparticles via the wave front engineering of optical beams for enhancing light–matter interaction and optical sensing performance. (paper)

  13. Chirality of weakly bound complexes: The potential energy surfaces for the hydrogen-peroxide−noble-gas interactions

    Energy Technology Data Exchange (ETDEWEB)

    Roncaratti, L. F., E-mail:; Leal, L. A.; Silva, G. M. de [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Pirani, F. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, V. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Instituto de Física, Universidade Federal da Bahia, 40210 Salvador (Brazil); Gargano, R. [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Departments of Chemistry and Physics, University of Florida, Quantum Theory Project, Gainesville, Florida 32611 (United States)


    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 of 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.

  14. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure

    International Nuclear Information System (INIS)

    Biswas, S.; Singh, G.P.; Ram, S.; Fecht, H.-J.


    Stable anisotropic nanorods of surface modified CrO 2 (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr 4+ ions by Ag atoms on the CrO 2 surface (topotactic surface layer) via an etching reaction of a CrO 2 -polymer complex with Ag + ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO 2 such that it no longer converts to Cr 2 O 3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO 2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d 5/2 and 3d 3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO 2 powders or composites. Such a large MR-value in the Coulomb blockade regime ( 2 nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO 2 . • Tailoring useful GMR property in CrO 2 nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO 2 nanorods

  15. The complex dynamics of the seasonal component of USA's surface temperature

    Directory of Open Access Journals (Sweden)

    A. Vecchio


    Full Text Available The dynamics of the climate system has been investigated by analyzing the complex seasonal oscillation of monthly averaged temperatures recorded at 1167 stations covering the whole USA. We found the presence of an orbit-climate relationship on time scales remarkably shorter than the Milankovitch period {related to the nutational forcing}. The relationship manifests itself through occasional destabilization of the phase of the seasonal component due to the local changing of balance between direct insolation and the net energy received by the Earth. Quite surprisingly, we found that the local intermittent dynamics is modulated by a periodic component of about 18.6 yr due to the nutation of the Earth, which represents the main modulation of the Earth's precession. The global effect in the last century results in a cumulative phase-shift of about 1.74 days towards earlier seasons, in agreement with the phase shift expected from the Earth's precession. The climate dynamics of the seasonal cycle can be described through a nonlinear circle-map, indicating that the destabilization process can be associated to intermittent transitions from quasi-periodicity to chaos.

  16. Formation, surface characterization, and electrocatalytic application of self-assembled monolayer films of tetra-substituted manganese, iron, and cobalt benzylthio phthalocyanine complexes

    CSIR Research Space (South Africa)

    Akinbulu, IA


    Full Text Available Molecular thin films of manganese (SAM-2), iron (SAM-3), and cobalt (SAM-4) phthalocyanine complexes, non-peripherally tetra-substituted with benzylmercapto, were formed on polycrystalline gold disc electrode by selfassembly technique. Surface...

  17. Surface complexation modeling of groundwater arsenic mobility: Results of a forced gradient experiment in a Red River flood plain aquifer, Vietnam

    DEFF Research Database (Denmark)

    Jessen, Søren; Postma, Dieke; Larsen, Flemming


    Three surface complexation models (SCMs) developed for, respectively, ferrihydrite, goethite and sorption data for a Pleistocene oxidized aquifer sediment from Bangladesh were used to explore the effect of multicomponent adsorption processes on As mobility in a reduced Holocene floodplain aquifer...

  18. Adaptive Robust Online Constructive Fuzzy Control of a Complex Surface Vehicle System. (United States)

    Wang, Ning; Er, Meng Joo; Sun, Jing-Chao; Liu, Yan-Cheng


    In this paper, a novel adaptive robust online constructive fuzzy control (AR-OCFC) scheme, employing an online constructive fuzzy approximator (OCFA), to deal with tracking surface vehicles with uncertainties and unknown disturbances is proposed. Significant contributions of this paper are as follows: 1) unlike previous self-organizing fuzzy neural networks, the OCFA employs decoupled distance measure to dynamically allocate discriminable and sparse fuzzy sets in each dimension and is able to parsimoniously self-construct high interpretable T-S fuzzy rules; 2) an OCFA-based dominant adaptive controller (DAC) is designed by employing the improved projection-based adaptive laws derived from the Lyapunov synthesis which can guarantee reasonable fuzzy partitions; 3) closed-loop system stability and robustness are ensured by stable cancelation and decoupled adaptive compensation, respectively, thereby contributing to an auxiliary robust controller (ARC); and 4) global asymptotic closed-loop system can be guaranteed by AR-OCFC consisting of DAC and ARC and all signals are bounded. Simulation studies and comprehensive comparisons with state-of-the-arts fixed- and dynamic-structure adaptive control schemes demonstrate superior performance of the AR-OCFC in terms of tracking and approximation accuracy.

  19. Conformational Explosion: Understanding the Complexity of the Para-Dialkylbenzene Potential Energy Surfaces (United States)

    Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.


    This talk focuses on the single-conformation spectroscopy of small-chain para-dialkylbenzenes. This work builds on previous studies from our group on long-chain n-alkylbenzenes that identified the first folded structure in octylbenzene. The dialkylbenzenes are representative of a class of molecules that are common components of coal and aviation fuel and are known to be present in vehicle exhaust. We bring the molecules para-diethylbenzene, para-dipropylbenzene and para-dibutylbenzene into the gas phase and cool the molecules in a supersonic expansion. The jet-cooled molecules are then interrogated using laser-induced fluorescence excitation, fluorescence dip IR spectroscopy (FDIRS) and dispersed fluorescence. The LIF spectra in the S_{0}-S_{1} origin region show dramatic increases in the number of resolved transitions with increasing length of alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an 'egg carton' shape to the potential energy surface. We use a combination of electronic frequency shift and alkyl CH stretch infrared spectra to generate a consistent set of conformational assignments.

  20. Efficient near-real-time monitoring of 3D surface displacements in complex landslide scenarios (United States)

    Allasia, Paolo; Manconi, Andrea; Giordan, Daniele; Baldo, Marco; Lollino, Giorgio


    Ground deformation measurements play a key role in monitoring activities of landslides. A wide spectrum of instruments and methods is nowadays available, going from in-situ to remote sensing approaches. In emergency scenarios, monitoring is often based on automated instruments capable to achieve accurate measurements, possibly with a very high temporal resolution, in order to achieve the best information about the evolution of the landslide in near-real-time, aiming at early warning purposes. However, the available tools for a rapid and efficient exploitation, understanding and interpretation of the retrieved measurements is still a challenge. This issue is particularly relevant in contexts where monitoring is fundamental to support early warning systems aimed at ensuring safety to people and/or infrastructures. Furthermore, in many cases the results obtained might be of difficult reading and divulgation, especially when people of different backgrounds are involved (e.g. scientists, authorities, civil protection operators, decision makers, etc.). In this work, we extend the concept of automatic and near real time from the acquisition of measurements to the data processing and divulgation, in order to achieve an efficient monitoring of surface displacements in landslide scenarios. We developed an algorithm that allows to go automatically and in near-real-time from the acquisition of 3D displacements on a landslide area to the efficient divulgation of the monitoring results via WEB. This set of straightforward procedures is called ADVICE (ADVanced dIsplaCement monitoring system for Early warning), and has been already successfully applied in several emergency scenarios. The algorithm includes: (i) data acquisition and transfer protocols; (ii) data collection, filtering, and validation; (iii) data analysis and restitution through a set of dedicated software, such as ©3DA [1]; (iv) recognition of displacement/velocity threshold and early warning (v) short term

  1. Complex Indigenous Organic Matter Embedded in Apollo 17 Volcanic Black Glass Surface Deposits (United States)

    Thomas-Keprta, Kathie L.; Clemett, S. J.; Ross, D. K.; Le, L.; Rahman, Z.; Gonzalez, C.; McKay, D. S.; Gibson, E. K.


    Papers presented at the first Lunar Science Conference [1] and those published in the subsequent Science Moon Issue [2] reported the C content of Apollo II soils, breccias, and igneous rocks as rang-ing from approx.50 to 250 parts per million (ppm). Later Fegley & Swindle [3] summarized the C content of bulk soils from all the Apollo missions as ranging from 2.5 (Apollo 15) to 280 ppm (Apollo 16) with an overall average of 124+/- 45 ppm. These values are unexpectedly low given that multiple processes should have contributed (and in some cases continue to contribute) to the lunar C inventory. These include exogenous accretion of cometary and asteroidal dust, solar wind implantation, and synthesis of C-bearing species during early lunar volcanism. We estimate the contribution of C from exogenous sources alone is approx.500 ppm, which is approx.4x greater than the reported average. While the assessm ent of indigenous organic matter (OM) in returned lunar samples was one of the primary scientific goals of the Apollo program, extensive analysis of Apollo samples yielded no evidence of any significant indigenous organic species. Furthermore, with such low concentrations of OM reported, the importance of discriminating indigenous OM from terrestrial contamination (e.g., lunar module exhaust, sample processing and handling) became a formidable task. After more than 40 years, with the exception of CH4 [5-7], the presence of indigenous lunar organics still remains a subject of considerable debate. We report for the first time the identification of arguably indigenous OM present within surface deposits of black glass grains collected on the rim of Shorty crater during the Apollo 17 mission by astronauts Eugene Cernan and Harrison Schmitt.

  2. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure (United States)

    Biswas, S.; Singh, G. P.; Ram, S.; Fecht, H.-J.


    Stable anisotropic nanorods of surface modified CrO2 (˜18 nm diameter) with a correlated diamagnetic layer (2-3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr4+ ions by Ag atoms on the CrO2 surface (topotactic surface layer) via an etching reaction of a CrO2-polymer complex with Ag+ ions in hot water followed by heating the dried sample at 300-400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO2 such that it no longer converts to Cr2O3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d5/2 and 3d3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (-) 7.6% at 77 K, than reported values in compacted CrO2 powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO2 nanorods.

  3. Accurate prediction of complex free surface flow around a high speed craft using a single-phase level set method (United States)

    Broglia, Riccardo; Durante, Danilo


    This paper focuses on the analysis of a challenging free surface flow problem involving a surface vessel moving at high speeds, or planing. The investigation is performed using a general purpose high Reynolds free surface solver developed at CNR-INSEAN. The methodology is based on a second order finite volume discretization of the unsteady Reynolds-averaged Navier-Stokes equations (Di Mascio et al. in A second order Godunov—type scheme for naval hydrodynamics, Kluwer Academic/Plenum Publishers, Dordrecht, pp 253-261, 2001; Proceedings of 16th international offshore and polar engineering conference, San Francisco, CA, USA, 2006; J Mar Sci Technol 14:19-29, 2009); air/water interface dynamics is accurately modeled by a non standard level set approach (Di Mascio et al. in Comput Fluids 36(5):868-886, 2007a), known as the single-phase level set method. In this algorithm the governing equations are solved only in the water phase, whereas the numerical domain in the air phase is used for a suitable extension of the fluid dynamic variables. The level set function is used to track the free surface evolution; dynamic boundary conditions are enforced directly on the interface. This approach allows to accurately predict the evolution of the free surface even in the presence of violent breaking waves phenomena, maintaining the interface sharp, without any need to smear out the fluid properties across the two phases. This paper is aimed at the prediction of the complex free-surface flow field generated by a deep-V planing boat at medium and high Froude numbers (from 0.6 up to 1.2). In the present work, the planing hull is treated as a two-degree-of-freedom rigid object. Flow field is characterized by the presence of thin water sheets, several energetic breaking waves and plungings. The computational results include convergence of the trim angle, sinkage and resistance under grid refinement; high-quality experimental data are used for the purposes of validation, allowing to

  4. Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    NARCIS (Netherlands)

    Ridley, M.K.; Hiemstra, T.; Riemsdijk, van W.H.; Machesky, M.L.


    Acid–base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in

  5. Complex trend of magnetic order in Fe clusters on 4d transition-metal surfaces. I. Experimental evidence and Monte Carlo simulations

    Czech Academy of Sciences Publication Activity Database

    Sessi, V.; Otte, F.; Krotzky, S.; Tieg, C.; Wasniowska, M.; Ferriani, P.; Heinze, S.; Honolka, Jan; Kern, K.


    Roč. 89, č. 20 (2014), "205425-1"-"205425-6" ISSN 1098-0121 Institutional support: RVO:68378271 Keywords : iron atoms on 4d metal surfaces * surface magnetism * complex spin order * indirect exchange interactions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.736, year: 2014

  6. Surface-enhanced Raman scattering and density functional theory study of 1,4-benzenedithiol and its silver complexes. (United States)

    Shao, Yangfan; Li, Chongyang; Feng, Yuanming; Lin, Wang


    This paper experimentally and theoretically investigated Raman and surface-enhanced Raman scattering (SERS) of 1,4-benzenedithiol (1,4-BDT). Density functional theory methods were used to study Raman scattering spectra of isolated 1,4-BDT and 1,4-BDT-Agn (n=2,4,6) complexes with B3LYP/6-311+g(d)(C,H,S)/Lanl2dz(Ag) basis set. A full assignment of the Raman spectrum of 1,4-BDT has been made based on the DFT analysis. The calculated data showed good agreement with experimental observations. The adsorption sites, metal cluster size, and HOMO-LUMO energies are discussed to give insight in the SERS mechanisms for 1,4-BDT molecules. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Assessing the contributions of surface waves and complex rays to far-field Mie scattering by use of the Debye series (United States)

    Hovenac, Edward A.; Lock, James A.


    The contributions of complex rays and the secondary radiation shed by surface waves to scattering by a dielectric sphere are calculated in the context of the Debye series expansion of the Mie scattering amplitudes. Also, the contributions of geometrical rays are reviewed and compared with the Debye series. Interference effects between surface waves, complex waves, and geometrical waves are calculated, and the possibility of observing these interference effects is discussed. Experimental data supporting the observation of a surface wave-geometrical pattern is presented.

  8. Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments (United States)

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


    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.

  9. Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex

    Energy Technology Data Exchange (ETDEWEB)

    Nasri, Sameh; Ajili, Yosra [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Jaidane, Nejm-Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Kalugina, Yulia N. [Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Halvick, Philippe; Stoecklin, Thierry [Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex (France); Hochlaf, Majdi, E-mail: [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)


    Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

  10. Phthalocyaninato complexes with peripheral alkylthio chains: disk-like adsorbate species for the vertical anchoring of ligands on gold surfaces. (United States)

    Siemeling, Ulrich; Schirrmacher, Christian; Glebe, Ulrich; Bruhn, Clemens; Baio, Joe E; Arnadóttir, Líney; Castner, David G; Weidner, Tobias


    Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, β-positioned, alkylthio substituents SR (1a: R = n-C(8)H(17), 1b: R = n-C(12)H(25)), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to Mn(II).

  11. Synthesis, structural characterization, Hirshfeld surface analysis and spectroscopic studies of cadmium (II) chloride complex with 4-hydroxy-1-methylpiperidine

    Energy Technology Data Exchange (ETDEWEB)

    Soudani, S. [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia); Ferretti, V. [Department of Chemical and Pharmaceutical Sciences and Center for Structural Diffractometry, via Fossato di Mortara 17, I-44121 Ferrara (Italy); Jelsch, C. [CRM2, CNRS, Institut Jean Barriol, Université de Lorraine, Vandoeuvre les Nancy CEDEX (France); Lefebvre, F. [Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie Physique Electronique, 69626 Villeurbanne Cedex (France); Nasr, C. Ben, E-mail: [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia)


    The chemical preparation, crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the novel cadmium (II) 4-hydroxy-1-methylpiperidine complex, Cd{sub 4}Cl{sub 10}(C{sub 6}H{sub 14}NO){sub 2}·2H{sub 2}O, have been reported. The atomic arrangement can be described as built up by an anionic framework, formed by edge sharing CdCl{sub 6} and CdCl{sub 5}O octahedral linear chains spreading along the a-axis. These chains are interconnected by water molecules via O–H⋯Cl and O–H⋯O hydrogen bonds to form layers parallel to (011) plane. The organic cations are inserted between layers through C–H⋯Cl hydrogen bonds. Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the H{sub C}⋯Cl and H{sub C}⋯H{sub C} intermolecular interactions are the most abundant contacts of the organic cation in the crystal packing. The statistical analysis of crystal contacts reveals the driving forces in the packing formation. The {sup 13}C and {sup 15}N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and of the IR bands.

  12. Low-coverage surface diffusion in complex periodic energy landscapes. II. Analytical solution for systems with asymmetric hops (United States)

    Gosálvez, Miguel A.; Otrokov, Mikhail M.; Ferrando, Nestor; Ryabishchenkova, Anastasia G.; Ayuela, Andres; Echenique, Pedro M.; Chulkov, Evgueni V.


    This is part II in a series of two papers that introduce a general expression for the tracer diffusivity in complex, periodic energy landscapes with M distinct hop rates in one-, two-, and three-dimensional diluted systems (low coverage, single-tracer limit). While Part I [Gosálvez et al., Phys. Rev. B 93, 075429 (2016), 10.1103/PhysRevB.93.075429] focuses on the analysis of diffusion in systems where the end sites of the hops are located symmetrically with respect to the hop origins (symmetric hops), as encountered in many ideal surfaces and bulk materials, this report (Part II) presents a more general approach to determining the tracer diffusivity in systems where the end sites can be located asymmetrically with respect to the hop origins (asymmetric hops), as observed in reconstructed and/or chemically modified surfaces and/or bulk materials. The obtained diffusivity formulas for numerous systems are validated against kinetic Monte Carlo simulations and previously reported analytical expressions based on the continuous-time random walk (CTRW) method. The proposed method corrects some of the CTRW formulas and provides new expressions for difficult cases that have not been solved earlier. This demonstrates the ability of the proposed formalism to describe tracer diffusion.

  13. Surface stabilized GMR nanorods of silver coated CrO{sub 2} synthesized via a polymer complex at ambient pressure

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, S., E-mail: [The LNM Institute of Information Technology, Jaipur-302031 (India); Singh, G.P. [Centre for Nanotechnology, Central University of Jharkhand, Ranchi-835205 (India); Ram, S. [Materials Science Centre, Indian Institute of Technology, Kharagpur-721302 (India); Fecht, H.-J. [Insitut für Micro-und Nanomaterialien, Universität Ulm, Albert Einstein Allee-47, Ulm, D-89081, and Forschungszentrum Karlsruhe, Institute of Nanotechnology, Karlsruhe, D-76021 (Germany)


    Stable anisotropic nanorods of surface modified CrO{sub 2} (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr{sup 4+} ions by Ag atoms on the CrO{sub 2} surface (topotactic surface layer) via an etching reaction of a CrO{sub 2}-polymer complex with Ag{sup +} ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO{sub 2} such that it no longer converts to Cr{sub 2}O{sub 3} in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO{sub 2} structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d{sub 5/2} and 3d{sub 3/2} X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO{sub 2} powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO{sub 2} nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO{sub 2}. • Tailoring useful GMR property in CrO{sub 2} nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO{sub 2} nanorods.

  14. Non-invasive identification of metal-oxalate complexes on polychrome artwork surfaces by reflection mid-infrared spectroscopy. (United States)

    Monico, Letizia; Rosi, Francesca; Miliani, Costanza; Daveri, Alessia; Brunetti, Brunetto G


    In this work a reflection mid-infrared spectroscopy study of twelve metal-oxalate complexes, of interest in art conservation science as alteration compounds, was performed. Spectra of the reference materials highlighted the presence of derivative-like and/or inverted features for the fundamental vibrational modes as result of the main contribution from the surface component of the reflected light. In order to provide insights in the interpretation of theses spectral distortions, reflection spectra were compared with conventional transmission ones. The Kramers-Kronig (KK) algorithm, employed to correct for the surface reflection distortions, worked properly only for the derivative-like bands. Therefore, to pay attention to the use of this algorithm when interpreting the reflection spectra is recommended. The outcome of this investigation was exploited to discriminate among different oxalates on thirteen polychrome artworks analyzed in situ by reflection mid-infrared spectroscopy. The visualization of the νs(CO) modes (1400-1200 cm(-1)) and low wavenumber bands (below 900 cm(-1)) in the raw reflection profiles allowed Ca, Cu and Zn oxalates to be identified. Further information about the speciation of different hydration forms of calcium oxalates were obtained by using the KK transform. The work proves reflection mid-infrared spectroscopy to be a reliable and sensitive spectro-analytical method for identifying and mapping different metal-oxalate alteration compounds on the surface of artworks, thus providing conservation scientists with a non-invasive tool to obtain information on the state of conservation and causes of alteration of artworks. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model

    International Nuclear Information System (INIS)

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Rod, Kenton A.


    Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent-sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO U O 2 HCO 3 and SO U O 2 OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions

  16. Effect of pullulan nanoparticle surface charges on HSA complexation and drug release behavior of HSA-bound nanoparticles.

    Directory of Open Access Journals (Sweden)

    Xiaojun Tao

    Full Text Available Nanoparticle (NP compositions such as hydrophobicity and surface charge are vital to determine the presence and amount of human serum albumin (HSA binding. The HSA binding influences drug release, biocompatibility, biodistribution, and intercellular trafficking of nanoparticles (NPs. Here, we prepared 2 kinds of nanomaterials to investigate HSA binding and evaluated drug release of HSA-bound NPs. Polysaccharides (pullulan carboxyethylated to provide ionic derivatives were then conjugated to cholesterol groups to obtain cholesterol-modified carboxyethyl pullulan (CHCP. Cholesterol-modified pullulan (CHP conjugate was synthesized with a similar degree of substitution of cholesterol moiety to CHCP. CHCP formed self-aggregated NPs in aqueous solution with a spherical structure and zeta potential of -19.9 ± 0.23 mV, in contrast to -1.21 ± 0.12 mV of CHP NPs. NPs could quench albumin fluorescence intensity with maximum emission intensity gradually decreasing up to a plateau at 9 to 12 h. Binding constants were 1.12 × 10(5 M(-1 and 0.70 × 10(5 M(-1 to CHP and CHCP, respectively, as determined by Stern-Volmer analysis. The complexation between HSA and NPs was a gradual process driven by hydrophobic force and inhibited by NP surface charge and shell-core structure. HSA conformation was altered by NPs with reduction of α-helical content, depending on interaction time and particle surface charges. These NPs could represent a sustained release carrier for mitoxantrone in vitro, and the bound HSA assisted in enhancing sustained drug release.

  17. Implementation and Testing of Advanced Surface Boundary Conditions Over Complex Terrain in A Semi-idealized Model (United States)

    Li, Y.; Epifanio, C.


    In numerical prediction models, the interaction between the Earth's surface and the atmosphere is typically accounted for in terms of surface layer parameterizations, whose main job is to specify turbulent fluxes of heat, moisture and momentum across the lower boundary of the model domain. In the case of a domain with complex geometry, implementing the flux conditions (particularly the tensor stress condition) at the boundary can be somewhat subtle, and there has been a notable history of confusion in the CFD community over how to formulate and impose such conditions generally. In the atmospheric case, modelers have largely been able to avoid these complications, at least until recently, by assuming that the terrain resolved at typical model resolutions is fairly gentle, in the sense of having relatively shallow slopes. This in turn allows the flux conditions to be imposed as if the lower boundary were essentially flat. Unfortunately, while this flat-boundary assumption is acceptable for coarse resolutions, as grids become more refined and the geometry of the resolved terrain becomes more complex, the appproach is less justified. With this in mind, the goal of our present study is to explore the implementation and usage of the full, unapproximated version of the turbulent flux/stress conditions in atmospheric models, thus taking full account of the complex geometry of the resolved terrain. We propose to implement the conditions using a semi-idealized model developed by Epifanio (2007), in which the discretized boundary conditions are reduced to a large, sparse-matrix problem. The emphasis will be on fluxes of momentum, as the tensor nature of this flux makes the associated stress condition more difficult to impose, although the flux conditions for heat and moisture will be considered as well. With the resulotion of 90 meters, some of the results show that the typical differences between flat-boundary cases and full/stress cases are on the order of 10%, with extreme

  18. Study of solid/liquid and solid/gas interfaces in Cu–isoleucine complex by surface X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Ferrer, Pilar, E-mail: [SpLine Spanish CRG Beamline at the ESRF, 38000 Grenoble (France); Instituto de Ciencia de Materiales de Madrid, 28049 Madrid (Spain); Rubio-Zuazo, Juan; Castro, German R. [SpLine Spanish CRG Beamline at the ESRF, 38000 Grenoble (France); Instituto de Ciencia de Materiales de Madrid, 28049 Madrid (Spain)


    The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal–amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu–isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal–amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu–isoleucine complex under different ambient conditions. Cu(Ile){sub 2} crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu–isoleucine crystal was measured under a protective dry N{sub 2} gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

  19. Effect of surface conditioning modalities on the repair bond strength of resin composite to the zirconia core / veneering ceramic complex. (United States)

    Ozcan, Mutlu; Valandro, Luiz Felipe; Pereira, Sarina Maciel; Amaral, Regina; Bottino, Marco Antonio; Pekkan, Gurel


    This study evaluated the effect of different surface conditioning protocols on the repair strength of resin composite to the zirconia core / veneering ceramic complex, simulating the clinical chipping phenomenon. Forty disk-shaped zirconia core (Lava Zirconia, 3M ESPE) (diameter: 3 mm) specimens were veneered circumferentially with a feldspathic veneering ceramic (VM7, Vita Zahnfabrik) (thickness: 2 mm) using a split metal mold. They were then embedded in autopolymerizing acrylic with the bonding surfaces exposed. Specimens were randomly assigned to one of the following surface conditioning protocols (n = 10 per group): group 1, veneer: 4% hydrofluoric acid (HF) (Porcelain Etch) + core: aluminum trioxide (50-µm Al2O3) + core + veneer: silane (ESPE-Sil); group 2: core: Al2O3 (50 µm) + veneer: HF + core + veneer: silane; group 3: veneer: HF + core: 30 µm aluminum trioxide particles coated with silica (30 µm SiO2) + core + veneer: silane; group 4: core: 30 µm SiO2 + veneer: HF + core + veneer: silane. Core and veneer ceramic were conditioned individually but no attempt was made to avoid cross contamination of conditioning, simulating the clinical intraoral repair situation. Adhesive resin (VisioBond) was applied to both the core and the veneer ceramic, and resin composite (Quadrant Posterior) was bonded onto both substrates using polyethylene molds and photopolymerized. After thermocycling (6000 cycles, 5°C-55°C), the specimens were subjected to shear bond testing using a universal testing machine (1 mm/min). Failure modes were identified using an optical microscope, and scanning electron microscope images were obtained. Bond strength data (MPa) were analyzed statistically using the non-parametric Kruskal-Wallis test followed by the Wilcoxon rank-sum test and the Bonferroni Holm correction (α = 0.05). Group 3 demonstrated significantly higher values (MPa) (8.6 ± 2.7) than those of the other groups (3.2 ± 3.1, 3.2 ± 3, and 3.1 ± 3.5 for groups 1, 2, and 4

  20. Chemical functionalization of crystalline silicon surface with complexes of type (M3 (Dpa) 4X2) for the development of electronic devices

    International Nuclear Information System (INIS)

    Sanchez Zamora, Maria Alejandra


    New surfaces on crystalline silicon (100) diamines have been developed. The diamines 4-aminopyridine, 4-aminomethylpyridine and 1,12-dodecildiame, and self-assembled surfaces Si-diamine-metallic complexes, with cooper (II) acetate and trimetal Cu 3 (dpa) 4 CI 2 were studied. These surfaces are characterized with X-ray photoelectron spectroscopy (XPS), chemical force microscopy (CFM), by contact angle and cyclic voltammetry (CV). The XPS has suggested the formation of diamines monolayers with covalent binding to crystalline silicon, and modification of these surfaces, with metal complexes by coordination chemistry. The CFM has confirmed that surfaces are modified with diamines and cooper (II) acetate, and that were determined different chemical forces according to the change. The contact angle has been suggested that the functionalized surface with 4-aminomethylpyridine has had similar basicity to 1,12-dodecildiame, and more than 4-aminopyridine. This implies that the coordination with metallics complexes is benefited with 4-aminopyridine, which in turn is reflected with electrochemical data. Cyclic voltammetry analysis have showed that silicon surfaces with 4-aminomethylpyridine and 4-aminopyridine with cooper (II) acetate and trimetal have been electrochemically active. Thus, the surfaces could to have interesting applications in molecular electronics. (author) [es

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

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


    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

  2. Crustal seismicity associated to rpid surface uplift at Laguna del Maule Volcanic Complex, Southern Volcanic Zone of the Andes (United States)

    Cardona, Carlos; Tassara, Andrés; Gil-Cruz, Fernando; Lara, Luis; Morales, Sergio; Kohler, Paulina; Franco, Luis


    Laguna del Maule Volcanic Complex (LMVC, Southern Andes of Chile) has been experiencing large rates (ca. 30 cm/yr) of surface uplift as detected since 2008 by satellite geodetic measurements. Previous works have modeled the source of this deformation as an inflating rectangular sub-horizontal sill underlying LMVC at 5 km depth, which is supposedly related to an active process of magmatic replenishment of a shallow silicic reservoir. However little is known about the tectonic context on which this activity is taking place, particularly its relation with crustal seismicity that could help understanding and monitoring the current deformation process. Here we present the first detailed characterization of the seismic activity taking place at LMVC and integrate it with structural data acquired in the field in order to illuminate the possible connection between the ongoing process of surface uplift and the activation of crustal faults. Our main finding is the recognition of repetitive volcano-tectonic (VT) seismic swarms that occur periodically between 2011 and 2014 near the SW corner of the sill modeled by InSAR studies. A cross-correlation analysis of the waveforms recorded for these VT events allows identifying three different seismic families. Families F1 and F3 share some common features in the stacked waveform and its locations, which markedly differ from those of family F2. Swarms belonging to this later family are more energetic and its energy was increasing since 2011 to a peak in January 2013, which coincide with maximum vertical velocities detected by local GPS stations. This points to a common process relating both phenomena. The location of VT seismic swarms roughly coincides with the intersection of a NE-SW lineament with a WNW-ESE lineament. The former shows clear field evidences of dextral strike-slip that are fully consistent with one nodal plane of focal mechanism for well-recorded F2 events. The conjugate nodal plane of these focal mechanisms could

  3. Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

    KAUST Repository

    Aly, Shawkat Mohammede


    Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4-N,N,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs. © 2014 American Chemical Society.

  4. Applying a modified Donnan model to describe the surface complexation of chromate to iron oxyhydroxide agglomerates with heteromorphous pores. (United States)

    Wei, Zongsu; Semiat, Raphael


    In this study, a modified Donnan model (mDM) is incorporated into surface complexation model (SCM) to better understand the physicochemical processes for adsorption of hexavalent chromium, Cr(VI), on porous iron oxyhydroxide agglomerates (IOAs). The mDM includes a chemical potential term μ att to account for ionic transport and electrostatic interaction in micropores (d mi 2nm) demonstrating high Cr(VI) adsorption in a broad range of ionic strengths. The batch data was then fitted with Donnan model in PHREEQC to obtain Stern (ψ S ) and Donnan (ψ D ) potentials used for μ att calculation. The decreasing μ att values with ionic strength indicated obstructing effect of electrolyte ions on Cr(VI) uptake in micropores. Finally, the ionic activity coefficients and reaction constants were corrected using Pitzer model due to the high level electrolytes accumulated in the Donnan layer through osmotic and electrostatic attraction. Results of this study have captured the effects of inner structure of IOAs on Cr(VI) uptake and quantitatively discerned the contribution of micropores and macropores for adsorption reactions at different ionic strengths. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Exploring inclusion complexes of ionic liquids with α- and β- cyclodextrin by NMR, IR, mass, density, viscosity, surface tension and conductance study (United States)

    Barman, Biraj Kumar; Rajbanshi, Biplab; Yasmin, Ananya; Roy, Mahendra Nath


    The formation of the host-guest inclusion complexes of ionic liquids namely [BMIm]Cl and [HMIm]Cl with α-CD and β-CD were studied by means of physicochemical and spectroscopic methods. Conductivity and surface tension study were in good agreement with the 1H NMR and FT-IR studies which confirm the formation of the inclusion complexes. The Density and viscosity study also supported the formation of the ICs. Further the stoichiometry was determined 1:1 for each case and the association constants and thermodynamic parameters derived supported the most feasible formation of the [BMIm]Cl- β-CD inclusion complex.

  6. Refined ab initio intermolecular ground-state potential energy surface for the He-C2H2 van der Waals complex

    DEFF Research Database (Denmark)

    Fernández, Berta; Henriksen, Christian; Farrelly, David


    A refined CCSD(T) intermolecular potential energy surface is developed for the He-C2H2 van der Waals complex. For this, 206 points on the intermolecular potential energy surface, evaluated using the CCSD(T) method and the aug-cc-pVQZ basis set extended with a set of 3s3p2d1f1g midbond functions...... previously by Munteanu and Fernández (J. Chem. Phys., 123, 014309, 2005) but differs notably at short range. The improved potential energy surface should, therefore, be particularly useful for computations of collision line broadening. Dynamical calculations of a number of rovibrational bound state energies...

  7. Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Fatima Abu Saleemh


    Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

  8. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    Energy Technology Data Exchange (ETDEWEB)

    Ridley, Mora K. [Texas Tech University, Lubbock; Hiemstra, T [Oak Ridge National Laboratory (ORNL); Van Riemsdijk, Willem H. [Wageningen University and Research Centre, The Netherlands; Machesky, Michael L. [Illinois State Water Survey, Champaign, IL


    Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic

  9. Using skin surface temperature to differentiate between complex regional pain syndrome type 1 patients after a fracture and control patients with various complaints after a fracture

    NARCIS (Netherlands)

    S.P. Niehof (Sjoerd); A. Beerthuizen (Annemerle); F.J.P.M. Huygen (Frank); F.J. Zijlstra (Freek)


    textabstractOBJECTIVE: In this study, we assessed the validity of skin surface temperature recordings, based on various calculation methods applied to the thermographic data, to diagnose acute complex regional pain syndrome type 1 (CRPS1) fracture patients. METHODS: Thermographic recordings of the

  10. Studies of surface complexation of H+, NpO2+, Co2+, Th4+ onto TiO2 and H+, UO22+ onto alumina

    International Nuclear Information System (INIS)

    Jakobsson, Anna-Maria; Albinsson, Yngve


    This report describes the determination of surface complexation reactions of some radionuclides on mineral oxides from sorption experiments and potentiometric titrations. The surface acidity constants of the mineral oxide have been determined using potentiometric titrations. A description and discussion of the extrapolation method used is included as well as the calibration method which is of uttermost importance for calculating the constants. In this report it is shown that the data close to pH pzc can not be used to calculate the apparent equilibrium constants since the assumption that either the positive or negative sites dominate gives rise to a pK app that approach infinity. Furthermore it is shown that it is a fair estimation to assume a linear relationship between the inner surface charge and the potential since pure titanium dioxide gives a pK app that has a linear dependence on the inner surface charge. Besides the surface acidity constants, the capacitance of the inner layer has been calculated from this linear dependence. The values of these agree well with other proposed in the literature. The sorption of cobalt, thorium and neptunyl ions onto titanium dioxide and uranyl ions onto alumina from aqueous solution was studied as a function of pH and ionic strength in a C0 2 free environment at moderate radionuclide concentrations. Two different experimental methods were employed; an on-line method in which samples withdrawn at a specific pH are separated and measured, and a batch method. There is no significant difference between the average results from the two methods, however the on-line method provides less scatter. Also, using this method we were able to study the desorption easily and thus the reversibility of the reactions. There is no difference in sorption between the different ionic strengths for Np, Th, Co and U ions. This indicates the formation of inner sphere complexes with the surface. Neptunyl ion forms a neutral complex with the titanium


    Directory of Open Access Journals (Sweden)

    I. Salvador


    Full Text Available This work is part of a research on the use of terrestrial laser scanner, integrated with total station and GPS, for the documentation and comprehension of complex architectures in up-land sites. The research is performed in the framework of the project "Ambiente e Paesaggi dei siti di Altura Trentini" – APSAT (Environment and landscape of hill-top sites in Trentino, a multidisciplinary project focused on the evolution of hill-top anthropic system in the Trentino region, Italy. The study area is located in the Gresta Valley and this work concerns on the Nagià Grom site, fortified by the Austria-Hungarian Army during the World War I. The site has been interested by a significant restore operation of a large series of entrenches paths and fortifications in the last decade. The survey herein described has involved an area once interested by military barracks with Officers' Mess, water provision and by one of the biggest field kitchens discovered in the Trentino region. A second survey involved the tunnel connecting the ammunition depot to the artillery stations. The nature of such complex architectures, characterized by an irregular and composite 3D span leads, in general, to necessary simple surveys and representations and somehow to simplified studies too. The 3D point cloud, once filtered by the massive presence of dense vegetation, eventually constitutes a rich data set for further analyses on the spatial, geological, architectural and historical properties of the site. The analysis has been carried out on two different scales. At the architectural-scale, the comparison to historic photos has allowed to understand how the original structure of the barracks was made and to find building characters that now are lost. The on-site observation of the underground stratigraphic splices and their analysis in the 3D point cloud, e.g., spatial extension and slope, have permitted the understanding of the special excavation process guided by the

  12. Effect of partial or complete elimination of light-harvesting complexes on the surface electric properties and the functions of cyanobacterial photosynthetic membranes. (United States)

    Dobrikova, Anelia G; Domonkos, Ildikó; Sözer, Özge; Laczkó-Dobos, Hajnalka; Kis, Mihály; Párducz, Árpád; Gombos, Zoltán; Apostolova, Emilia L


    Influence of the modification of the cyanobacterial light-harvesting complex [i.e. phycobilisomes (PBS)] on the surface electric properties and the functions of photosynthetic membranes was investigated. We used four PBS mutant strains of Synechocystis sp. PCC6803 as follows: PAL (PBS-less), CK (phycocyanin-less), BE (PSII-PBS-less) and PSI-less/apcE(-) (PSI-less with detached PBS). Modifications of the PBS content lead to changes in the cell morphology and surface electric properties of the thylakoid membranes as well as in their functions, such as photosynthetic oxygen-evolving activity, P700 kinetics and energy transfer between the pigment-protein complexes. Data reveal that the complete elimination of PBS in the PAL mutant causes a slight decrease in the electric dipole moments of the thylakoid membranes, whereas significant perturbations of the surface charges were registered in the membranes without assembled PBS-PSII macrocomplex (BE mutant) or PSI complex (PSI-less mutant). These observations correlate with the detected alterations in the membrane structural organization. Using a polarographic oxygen rate electrode, we showed that the ratio of the fast to the slow oxygen-evolving PSII centers depends on the partial or complete elimination of light-harvesting complexes, as the slow operating PSII centers dominate in the PBS-less mutant and in the mutant with detached PBS. Copyright © Physiologia Plantarum 2012.

  13. Use of Alternatives to Air-Fluidized Support Surfaces in the Care of Complex Wounds in Postflap and Postgraft Patients


    Fleck, Cynthia A.; Rappl, Laurie M.; Simman, Richard; Titterington, Virginia; Conwill, Jill; Koerner, Cathy; Locke, Pam; Bechtold, Dawn; Papantonio, Cathie; Gray, Deborah P.; Lawrence, Kathleen


    Air-fluidized support surface therapy has many drawbacks, such as dehydration, in an already difficult recovery for those wound patients who have undergone flap and graft surgery. In addition, patient care and handling are also problematic. Patients complain of discomfort, and the instability of the surface interferes with patient stability in side lying and semi-Fowler's positions. Alternative support surfaces can be considered for postflap or postgraft patients. Such technologies as alterna...

  14. Surface modification of coronary artery stent by Ti-O/Ti-N complex film coating prepared with plasma immersion ion implantation and deposition

    International Nuclear Information System (INIS)

    Huang, N.; Leng, Y.X.; Yang, P.


    This paper reported the work of surface coating of Ti-O/Ti-N complex films on coronary stents by means of the plasma immersion ion implantation/deposition process. The deformation behavior of the Ti-O/Ti-N coated stainless steel stents was investigated. In vivo investigation of the anticoagulation behavior of Ti-O coated coronary stents was also performed. The results of mechanical characterization of the Ti-O/Ti-N coated stents show that the film has strong binding strength, and to some extent the ability to withstand plastic deformation. The biological response behavior of the coated stent surface was significantly different from the uncoated. The results of implantation of stents into rabbit ventral aorta show no thrombus formation on the surfaces of the Ti-O coated stents, although serious coagulation had occurred on the surfaces of unmodified stents over a period of 4 weeks under conditions with no anticoagulant

  15. [Optimization on preparation of hawthorn fruit total flavonoids-phospholipid complex using Plackett-Burman design, central composite design and response surface methodology]. (United States)

    Shi, Ya-Jun; Wu, Pin-Jiang; Wei, Ping


    To choose the optimal conditions for the formation of the complex with total flavonoids in hawthorn fruit and phospholipid. Solvent evaporation process was used to prepare hawthorn total flavonoids phospholipid complex. The evaluation criterion was the complex ratio. The experiment inspected the significance of influential factor of preparation technology by Plackett-Burman design and optimized significance of factor and level with the central composite design. The binomial and linear equations were fitted to the data of overall desirabilities, and the resulting equation was used to produce 3-D response surface graphs, through which the optimal formulation was predicted. The ratio of total flavonoids to phospholipid, flavonoids concentration and reaction temperature had significant influence on the craft. It was showed that the correlation coefficient of second-order quadratic model was high. The correlation coefficient reached 0.9886. The optimum conditions for the preparation of the complex were as follows: phospholipids/total flavonoids was 3 : 1, the temperature was 40 degrees C and the concentration of principal agent was 10 mg/mL The deviation between the result of the best craft verification test and the binomial fitting equation forecast value was less than 2.0%. Response surface methodology is successfully used to optimize the preparation of total flavonoids in hawthorn phospholipid complex. The optimized process is reliable, stable and available for the industrial production.

  16. Covalent co-immobilization of heparin/laminin complex that with different concentration ratio on titanium surface for selectively direction of platelets and vascular cells behavior

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jian; Chen, Yuan; Liu, Tao; Wang, Xue; Liu, Yang; Wang, Yuan; Chen, Junying, E-mail:; Huang, Nan


    Highlights: • Extracellular matrix inspired surface modification with fibronectin, heparin and VEGF to construct a favorable microenvironment for selectively anticoagulant and promote endothelialization. • Take the advantage of specific intermolecular interaction, the bioactivity of above biomolecules was more efficiently maintained in compared with the common used covalent immobilization method. • Poly-l-lysine was used as a novel interlayer for surface amination, and in comparison, PLL coating was more feasible and the degradation product had no harm to human body. - Abstract: Surface biofunctional modification of coronary artery stent to improve the hemocompatibility and selectively accelerate endothelium regeneration but prevent restenosis have been become a new hotspot. For this, a novel method was developed in this work by co-immobilization of Ln and heparin complex on poly-L-lysine modified Ti surface. Take the advantage of the specific interaction between Ln and heparin, Ln and heparin complexes with different concentration ratios were set up for creating different exposure density of these two types of biomolecules. According to biocompatibility evaluation results, the Hep/Ln complexes modified surface displayed less platelet adhesion and activation. Especially, on L(150)H and L(200)H surface, the AT III binding quantity, APTT value and anti-coagulation property of modified surface were significantly promoted. Furthermore, the adherent density and proliferation activity of ECs and EPCs were positively correlated with Ln concentration. Notably, the proliferation of both ECs and EPCs on L(100)H, L(150)H and L(200)H surface were greatly promoted. Another hand, the proliferation activity of SMCs was significantly inhibited on Hep/Ln modified surfaces, which was considered mainly due to the inhibitory effect of heparin to SMCs. According to the existing results, this study demonstrated that in a certain range of heparin and laminin concentration ratio

  17. Assessment of Land Surface Complexity In Relation To Information Capacity and the Fractal Dimension in Different Landform Regions Using Landsat Data (United States)

    Hong, Wang Xu; Huijie, Qin; Zhe, Zhang; Fei, Li


    Remote sensing images are highly structured, and contiguous pixels of space domain have strong correlations that contain abundant information on land surface structure features and land surface electromagnetic radiation features. The information capacity model, which is a quality evaluation model based on a multi-dimensional histogram, includes local correlations within different pixels. Thus, the information capacity can illustrate land surface structural information more objectively and effectively than other single-pixel calculation models. Our results reveal that the information capacity value correlates well with the meaningful grey level of remote sensing imagery. This high correlation is related to the complexity of terrestrial surface landscapes. Therefore, information capacity, as applied to geoscience, is introduced in this study to demonstrate the spatial differentiation of information capacity of different landform regions. Generally, the information capacity of a mountain is large and is followed in decreasing order by those of the hills and the plains. Moreover, the correlation between information capacity and the fractal dimension is analysed. Based on the results of this study, it can be concluded that the level of correlation for information capacity and the fractal dimension is high, and the correlation coefficient for the basic landform areas and the loess landform areas is 0.874 and 0.825, respectively. Finally, this paper proposes that information capacity be used as a new reference index for geoscientific analysis in quantitative research on the characteristics of land surface complexity.

  18. Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids (United States)

    Frasconi, Marco; Mazzei, Franco


    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.

  19. Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces. (United States)

    Wilmsmeyer, Amanda R; Gordon, Wesley O; Davis, Erin Durke; Mantooth, Brent A; Lalain, Teri A; Morris, John R


    A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

  20. 12-Crown-4-based amphipathic lipid and corresponding metal cation complexes for gene therapy applications: FT-IR characterization and surface charge determination (United States)

    Bruni, P.; Fino, V.; Pisani, M.; Tosi, G.; Stipa, P.; Ferraris, P.; Francescangeli, O.


    The new lipid 1,2- O-dioleyl-3- O-{2-[(12-crown-4)-methoxy]-ethyl}- sn-glycerol, 12C4L, has been synthesized. This molecule can coordinate different cations that should make the corresponding liposome a good candidate as vector of genetic material for possible applications in gene therapy. An important feature of the molecule is the possibility to modulate the net surface charge of their complexes with metal cations, which is important to provide efficient DNA transfections. The molecule and its complexes with some metal cations (Mg 2+, Ca 2+, Mn 2+) have been characterized by FT-IR spectroscopy and band attributions confirmed by Density Functional Theory calculations. The net surface charge has been determined by Z potential determinations.

  1. A surface complexation model of YREE sorption on Ulva lactuca in 0.05-5.0 M NaCl solutions (United States)

    Zoll, Alison M.; Schijf, Johan


    We present distribution coefficients, log iKS, for the sorption of yttrium and the rare earth elements (YREEs) on BCR-279, a dehydrated tissue homogenate of a marine macroalga, Ulva lactuca, resembling materials featured in chemical engineering studies aimed at designing renewable biosorbents. Sorption experiments were conducted in NaCl solutions of different ionic strength (0.05, 0.5, and 5.0 M) at T = 25 °C over the pH range 2.7-8.5. Distribution coefficients based on separation of the dissolved and particulate phase by conventional filtration (3 kDa) using an existing pH-dependent model. Colloid-corrected values were renormalized to free-cation concentrations by accounting for YREE hydrolysis and chloride complexation. At each ionic strength, the pH dependence of the renormalized values is accurately described with a non-electrostatic surface complexation model (SCM) that incorporates YREE binding to three monoprotic functional groups, previously characterized by alkalimetric titration, as well as binding of YREE-hydroxide complexes (MOH2+) to the least acidic one (pKa ∼ 9.5). In non-linear regressions of the distribution coefficients as a function of pH, each pKa was fixed at its reported value, while stability constants of the four YREE surface complexes were used as adjustable parameters. Data for a single fresh U. lactuca specimen in 0.5 M NaCl show generally the same pH-dependent behavior but a lower degree of sorption and were excluded from the regressions. Good linear free-energy relations (LFERs) between stability constants of the YREE-acetate and YREE-hydroxide solution complex and surface complexes with the first and third functional group, respectively, support their prior tentative identifications as carboxyl and phenol. A similar confirmation for the second group is precluded by insufficient knowledge of the stability of YREE-phosphate complexes and a perceived lack of YREE binding in 0.05 M NaCl; this issue awaits further study. The results

  2. Slope of the Slope Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Slope of slope was calculated from the bathymetry surface for each raster cell by applying the ArcGIS Spatial Analyst 'Slope' Tool to a previously created slope...

  3. Emergence of complex behavior in pili-based motility in early stages of P. aeruginosa surface adaptation (United States)

    Brill-Karniely, Yifat; Jin, Fan; Wong, Gerard C. L.; Frenkel, Daan; Dobnikar, Jure


    Pseudomonas aeruginosa move across surfaces by using multiple Type IV Pili (TFP), motorized appendages capable of force generation via linear extension/retraction cycles, to generate surface motions collectively known as twitching motility. Pseudomonas cells arrive at a surface with low levels of piliation and TFP activity, which both progressively increase as the cells sense the presence of a surface. At present, it is not clear how twitching motility emerges from these initial minimal conditions. Here, we build a simple model for TFP-driven surface motility without complications from viscous and solid friction on surfaces. We discover the unanticipated structural requirement that TFP motors need to have a minimal amount of effective angular rigidity in order for cells to perform the various classes of experimentally-observed motions. Moreover, a surprisingly small number of TFP are needed to recapitulate movement signatures associated with twitching: Two TFP can already produce movements reminiscent of recently observed slingshot type motion. Interestingly, jerky slingshot motions characteristic of twitching motility comprise the transition region between different types of observed crawling behavior in the dynamical phase diagram, such as self-trapped localized motion, 2-D diffusive exploration, and super-diffusive persistent motion.

  4. Uniform superhydrophobic surfaces using micro/nano complex structures formed spontaneously by a simple and cost-effective nonlithographic process based on anodic aluminum oxide technology

    International Nuclear Information System (INIS)

    Kim, Dae-Ho; Cho, Chae-Ryong; Kim, Jong-Man; Kim, Yongsung; Kim, Byung Min; Ko, Jong Soo


    This paper presents a uniform micro/nano double-roughened superhydrophobic surface with a high static contact angle (CA) and low contact angle hysteresis (CAH). The proposed micro/nano complex structured surfaces were self-fabricated simply and efficiently using a very simple and low-cost nonlithographic sequential process, which consists of aluminum (Al) sputtering, anodization of the Al layer and pore widening, without specific equipment and additional subsequent processes. The wetting properties of the fabricated surfaces were characterized by measuring the static CAs and the CAHs after plasma polymerized fluorocarbon coating with a low surface energy. The measured static CA and CAH were 154 ± 2.3° and 5.7 ± 0.8°, respectively, showing that the fabricated double-roughened surfaces exhibit superhydrophobic behaviors clearly. In addition, the proposed double-scaled surfaces at a wafer-level exhibited uniform superhydrophobic behaviors across the wafer with an apparent CA and CAH of 153.9 ± 0.8° and 4.9 ± 1.3°, respectively.

  5. A novel cationic cobalt(III) Schiff base complex: Preparation, crystal structure, Hirshfeld surface analysis, antimicrobial activities and molecular docking. (United States)

    Yousef Ebrahimipour, S; Machura, Barbara; Mohamadi, Maryam; Khaleghi, Moj


    A novel Co(III) complex, [Co(L)(Imi) 3 ]Cl incorporating 2-((3-methoxy-2-oxidobenzylidene)amino)-4-methylphenolate (L 2- ), as a dibasic deprotonated Schiff base ligand and imidazole (Imi) was synthesized and fully characterized using physicochemical and spectroscopic techniques including elemental analysis, conductance measurement, FT-IR, UV-Vis and X-ray single crystal diffraction. As the conductivity data showed, the synthesized complex had a 1:1 ionic nature. The structure of the complex was found to be distorted octahedral in which, O/N donor atoms of the Schiff base ligand and N atoms of three imidazole groups were involved. Antimicrobial activity of the Co(III) complex as well as the its parent Schiff base ligand against two Gram-positive bacteria (S. Aureus and M. luteus), two Gram-negative bacteria (E. coli and P. aeruginosa) and a fungus (C. Albicans) was studied. Moreover, the antimicrobial activity of [Co(L)(Imi) 3 ]Cl was investigated using molecular docking of the complex with GlcN-6-P synthase. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Acid-base properties and surface complexation modeling of phosphate anion adsorption by wasted low grade iron ore with high phosphorus. (United States)

    Yuan, Xiaoli; Bai, Chenguang; Xia, Wentang; An, Juan


    The adsorption phenomena and specific reaction processes of phosphate onto wasted low grade iron ore with high phosphorus (WLGIOWHP) were studied in this work. Zeta potential and Fourier transform infrared spectroscopy (FTIR) analyses were used to elucidate the interaction mechanism between WLGIOWHP and aqueous solution. The results implied that the main adsorption mechanism was the replacement of surface hydroxyl groups by phosphate via the formation of inner-sphere complex. The adsorption process was characterized by chemical adsorption onto WLGIOWHP. The non-electrostatic model (NEM) was used to simulate the surface adsorption of phosphate onto WLGIOWHP. The total surface site density and protonation constants for NEM (N(T)=1.6×10(-4) mol/g, K(a1)=2.2×10(-4), K(a2)=6.82×10(-9)) were obtained by non-linear data fitting of acid-base titrations. In addition, the NEM was used to establish the surface adsorption complexation modeling of phosphate onto WLGIOWHP. The model successfully predicted the adsorption of phosphate onto WLGIOWHP from municipal wastewater. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Preliminary study of the effect of the turbulent flow field around complex surfaces on their acoustic characteristics (United States)

    Olsen, W. A.; Boldman, D.


    Fairly extensive measurements have been conducted of the turbulent flow around various surfaces as a basis for a study of the acoustic characteristics involved. In the experiments the flow from a nozzle was directed upon various two-dimensional surface configurations such as the three-flap model. A turbulent flow field description is given and an estimate of the acoustic characteristics is provided. The developed equations are based upon fundamental theories for simple configurations having simple flows. Qualitative estimates are obtained regarding the radiation pattern and the velocity power law. The effect of geometry and turbulent flow distribution on the acoustic emission from simple configurations are discussed.

  8. Theoretical study of the He-HF+ complex. II. Rovibronic states from coupled diabatic potential energy surfaces

    NARCIS (Netherlands)

    Dhont, G.S.F.; Zeimen, W.B.; Groenenboom, G.C.; Avoird, A. van der


    The bound rovibronic levels of the He-HF+ complex were calculated for total angular momentum J=1/2, 3/2, 5/2, 7/2, and 9/2 with the use of ab initio diabatic intermolecular potentials presented in Paper I and the inclusion of spin-orbit coupling. The character of the rovibronic states was

  9. Iridium and ruthenium complexes covalently bonded to carbon surfaces by means of electrochemical oxidation of aromatic amines

    Czech Academy of Sciences Publication Activity Database

    Sandroni, M.; Volpi, G.; Fiedler, Jan; Buscaino, R.; Viscardi, G.; Milone, L.; Gobetto, R.; Nervi, C.


    Roč. 158, 1-2 (2010), s. 22-28 ISSN 0920-5861 R&D Projects: GA ČR GA203/09/0705 Institutional research plan: CEZ:AV0Z40400503 Keywords : functionalization * glassy carbon electrode * metallorganic complexes * cyclic voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.993, year: 2010

  10. New five coordinated supramolecular structured cadmium complex as precursor for CdO nanoparticles: Synthesis, crystal structure, theoretical and 3D Hirshfeld surface analyses (United States)

    Ghanbari Niyaky, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.


    In this paper, a combined experimental and theoretical study on a new CdLBr2 complex (L = N1-(2-bromobenzylidene)-N2-(2-((E)-(2-bromobenzylidene) amino)ethyl) ethane-1,2-diamine) synthesized via template method, is described. The crystal structure analysis of the complex indicates that, the Cd(II) ion is centered in a distorted square pyramidal space constructed by three iminic nitrogens of the ligand as well as two bromide anions. More analysis of crystal packing proposed a supramolecular structure stabilized by some non-covalent interactions such as Br⋯Br and Xsbnd H⋯Br (X = N and C) in solid state. Furthermore, 3D Hirshfeld surface analyses and DFT studies were applied for theoretical investigation of the complexes. Theoretical achievements were found in a good agreement with respect to the experimental data. To evaluate the nature of bonding and the strength of the intra and inter-molecular interactions a natural bond orbital (NBO) analysis on the complex structure was performed. Time dependent density functional theory (TD-DFT) was also applied to predict the electronic spectral data of the complex as compared with the experimental ones. CdLBr2 complex as nano-structure compound was also prepared under ultrasonic conditions and characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). Finally, it was found that the cadmium complex can be used as a suitable precursor for preparation of CdO nanoparticles via calcination process at 600 °C under air atmosphere.

  11. Calcium-microRNA Complexes Functionalized Nanotubular Implant Surface for Highly Efficient Transfection and Enhanced Osteogenesis of Mesenchymal Stem Cells

    DEFF Research Database (Denmark)

    Song, Wen; Yang, Chuanxu; Svend Le, Dang Quang


    effective delivery method of small RNA therapeutics into hMSCs from an implant surface by calcium ions. First, we demonstrated that simple Ca/siGFP nanocomplexes were able to efficiently silence GFP in GFP-expressing hMSCs with adequate Ca2+ concentration (>5 mM). In addition, a single transfection could...

  12. On Monin–Obukhov Scaling in and Above the Atmospheric Surface Layer: The Complexities of Elevated Scintillometer Measurements

    NARCIS (Netherlands)

    Braam, M.; Bosveld, F.C.; Moene, A.F.


    In scintillometry Monin–Obukhov similarity theory (MOST) is used to calculate the surface sensible heat flux from the structure parameter of temperature (CT2)(CT2) . In order to prevent saturation a scintillometer can be installed at an elevated level. However, in that case the observation level

  13. Architectures and Mechanical Properties of Drugs and Complexes of Surface-active Compounds at Air-water and Oil-water Interfaces. (United States)

    Sarker, Dipak K


    Drugs can represents a multitude of compounds from proteins and peptides, such as growth hormones and insulin and on to simple organic molecules such as flurbiprofen, ibuprofen and lidocaine. Given the chemical nature of these compounds two features are always present. A portion or portions of the molecule that has little affinity for apolar surfaces and media and the opposite a series of part or one large part that has considerable affinity for hydrophilic, polar or charged media and surfaces. A series of techniques are routinely used to probe the molecular interactions that can arise between components, such as the drug, a range of surface-active excipients and flavor compounds, for example terpenoids and the solvent or dispersion medium. Fifty-eight papers were included in the review, a large number (16) being of a theoretical nature and an equally large number (14) directly pertaining to medicine and pharmacy; alongside experimental data and phenomenological modelling. The review therefore simultaneously represents an amalgam of review article and research paper, with routinely used or established (10) and well-reported methodologies (also included in the citations within the review). Experimental data included from various sources as diverse as foam micro-conductivity, interferometric measurements of surface adsorbates and laser fluorescence spectroscopy (FRAP) are used to indicate the complexity and utility of foams and surface soft matter structures for a range of purposes but specifically, here for encapsulation and incorporation of therapeutics actives (pharmaceutical molecules, vaccines and excipients used in medicaments). Techniques such as interfacial tensiometry, interfacial rheology (viscosity, elasticity and visco-elasticity) and nanoparticle particle size (hydrodynamic diameter) and charge measurements (zeta potential), in addition to atomic force and scanning electron microscopy have proven to be very useful in understanding how such elemental

  14. Potentiometric surfaces of the Arnold Engineering Development Complex Area, Arnold Air Force Base, Tennessee, May and September 2011 (United States)

    Haugh, Connor J.; Robinson, John A.


    Arnold Air Force Base occupies about 40,000 acres in Coffee and Franklin Counties, Tennessee. The primary mission of Arnold Air Force Base is to provide risk-reduction information in the development of aerospace products through test and evaluation. This mission is achieved in part through test facilities at Arnold Engineering Development Complex (AEDC), which occupies about 4,000 acres in the center of Arnold Air Force Base. Arnold Air Force Base is underlain by gravel and limestone aquifers, the most productive of which is the Manchester aquifer. Several volatile organic compounds, primarily chlorinated solvents, have been identified in the groundwater at Arnold Air Force Base. In 2011, the U.S. Geological Survey, in cooperation with the U.S. Air Force, Arnold Air Force Base, completed a study of groundwater flow focused on the Arnold Engineering Development Complex area. The Arnold Engineering Development Complex area is of particular concern because within this area (1) chlorinated solvents have been identified in the groundwater, (2) the aquifers are dewatered around below-grade test facilities, and (3) there is a regional groundwater divide.

  15. The role of surface electrostatics on the stability, function and regulation of human cystathionine β-synthase, a complex multidomain and oligomeric protein. (United States)

    Pey, Angel L; Majtan, Tomas; Kraus, Jan P


    Human cystathionine β-synthase (hCBS) is a key enzyme of sulfur amino acid metabolism, controlling the commitment of homocysteine to the transsulfuration pathway and antioxidant defense. Mutations in hCBS cause inherited homocystinuria (HCU), a rare inborn error of metabolism characterized by accumulation of toxic homocysteine in blood and urine. hCBS is a complex multidomain and oligomeric protein whose activity and stability are independently regulated by the binding of S-adenosyl-methionine (SAM) to two different types of sites at its C-terminal regulatory domain. Here we study the role of surface electrostatics on the complex regulation and stability of hCBS using biophysical and biochemical procedures. We show that the kinetic stability of the catalytic and regulatory domains is significantly affected by the modulation of surface electrostatics through noticeable structural and energetic changes along their denaturation pathways. We also show that surface electrostatics strongly affect SAM binding properties to those sites responsible for either enzyme activation or kinetic stabilization. Our results provide new insight into the regulation of hCBS activity and stability in vivo with implications for understanding HCU as a conformational disease. We also lend experimental support to the role of electrostatic interactions in the recently proposed binding modes of SAM leading to hCBS activation and kinetic stabilization. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Groundwater and surface-water interaction and effects of pumping in a complex glacial-sediment aquifer, phase 2, east-central Massachusetts (United States)

    Eggleston, Jack R.; Zarriello, Phillip J.; Carlson, Carl S.


    The U.S. Geological Survey, in cooperation with the Town of Framingham, Massachusetts, has investigated the potential of proposed groundwater withdrawals at the Birch Road well site to affect nearby surface water bodies and wetlands, including Lake Cochituate, the Sudbury River, and the Great Meadows National Wildlife Refuge in east-central Massachusetts. In 2012, the U.S. Geological Survey developed a Phase 1 numerical groundwater model of a complex glacial-sediment aquifer to synthesize hydrogeologic information and simulate potential future pumping scenarios. The model was developed with MODFLOW-NWT, an updated version of a standard USGS numerical groundwater flow modeling program that improves solution of unconfined groundwater flow problems. The groundwater model and investigations of the aquifer improved understanding of groundwater–surface-water interaction and the effects of groundwater withdrawals on surface-water bodies and wetlands in the study area. The initial work also revealed a need for additional information and model refinements to better understand this complex aquifer system.

  17. Host-guest chemistry of dendrimer-drug complexes. 2. Effects of molecular properties of guests and surface functionalities of dendrimers. (United States)

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


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

  18. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas


    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  19. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst. (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Bouhoute, Yassine; Szeto, Kai C; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja K; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Basset, Jean-Marie


    The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH 2 t Bu) 3 was selectively prepared by grafting of MoO(CH 2 t Bu) 3 Cl onto partially dehydroxylated silica (silica 700 ) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO 3 /SiO 2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  20. Application of surface complexation modelling: Nickel sorption on quartz, manganese oxide, kaolinite and goethite, and thorium on silica

    International Nuclear Information System (INIS)

    Olin, M.; Lehikoinen, J.


    The study is a follow-up to a previous modelling task on mechanistic sorption. The experimental work has been carried out at the Laboratory of Radiochemistry, University of Helsinki (HYRL), and the sorption modelling was performed using the HYDRAQL code. Parameters taken from the open literature were employed in the modelling phase. The thermodynamic data for aqueous solutions were extracted from the EQ3/6 database and subsequently modified for HYDRAQL where necessary. The experimental data were obtained from five different experiments, four of which concerned the adsorption of nickel. The first experimental system was a mixture of Nilsiae quartz and manganese dioxide. In the second experiment, quartz was equilibrated with a fresh and saline groundwater simulant instead of an electrolyte solution. The third and fourth experiments dealt with nickel adsorption from an electrolyte solution onto goethite and kaolinite surfaces respectively. In the fifth experiment, adsorption of thorium onto a quartz surface was investigated

  1. Nitrogen and phosphorus retention in surface waters: an inter-comparison of predictions by catchment models of different complexity

    Czech Academy of Sciences Publication Activity Database

    Hejzlar, Josef; Anthony, S.; Arheimer, B.; Behrendt, H.; Bouraoui, F.; Grizzetti, B.; Groenendijk, P.; Jeuken, M.H.J.L.; Johnsson, H.; Lo Porto, A.; Kronvang, B.; Panagopoulos, Y.; Siderius, C.; Silgram, M.; Venohr, M.; Žaloudík, Jiří


    Roč. 11, č. 3 (2009), s. 584-593 ISSN 1464-0325 R&D Projects: GA AV ČR(CZ) 1QS600170504 Grant - others:EC(XE) EVK1-2001-00062 Institutional research plan: CEZ:AV0Z60170517 Keywords : catchment modelling * phosphorus and nitrogen retention in surface waters * diffuse sources * source apportionment * MONERIS * EveNFlow * TRK * SWAT * NL-CAT Subject RIV: DJ - Water Pollution ; Quality Impact factor: 2.225, year: 2009

  2. Multifunctional Ultra-High Vacuum Apparatus for Studies of the Interactions of Chemical Warfare Agents on Complex Surfaces (United States)


    45 Briefly, a vacuum manifold with known volume is backfilled to a de- sired pressure with the gas, as measured by a capacitance manometer (MKS...accompany the research of these toxic, often very low vapor pressure , compounds. While results of vacuum-based surface science techniques may not...developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure , compounds

  3. Intracellular trafficking of bio-nanocapsule-liposome complex: Identification of fusogenic activity in the pre-S1 region of hepatitis B virus surface antigen L protein. (United States)

    Somiya, Masaharu; Sasaki, Yasuo; Matsuzaki, Takashi; Liu, Qiushi; Iijima, Masumi; Yoshimoto, Nobuo; Niimi, Tomoaki; Maturana, Andrés Daniel; Kuroda, Shun'ichi


    Bio-nanocapsules (BNCs) are a hollow nanoparticle consisting of about 100-nm liposome (LP) embedding about 110 molecules of hepatitis B virus (HBV) surface antigen (HBsAg) L protein as a transmembrane protein. Owing to the human hepatocyte-recognizing domains on the N-terminal region (pre-S1 region), BNCs have recently been shown to attach and enter into human hepatic cells using the early infection mechanism of HBV. Since BNCs could form a complex with an LP containing various drugs and genes, BNC-LP complexes have been used as a human hepatic cell-specific drug and gene-delivery system in vitro and in vivo. However, the role of BNCs in cell entry and intracellular trafficking of payloads in BNC-LP complexes has not been fully elucidated. In this study, we demonstrate that low pH-dependent fusogenic activity resides in the N-terminal part of pre-S1 region (NPLGFFPDHQLDPAFG), of which the first FF residues are essential for the activity, and which facilitates membrane fusion between LPs in vitro. Moreover, BNC-LP complexes can bind human hepatic cells specifically, enter into the cells via clathrin-mediated endocytosis, and release their payloads mostly into the cytoplasm. Taken together, the BNC portion of BNC-LP complexes can induce membrane fusion between LPs and endosomal membranes under low pH conditions, and thereby facilitate the endosomal escape of payloads. Furthermore, the fusogenic domain of the pre-S1 region of HBsAg L protein may play a pivotal role in the intracellular trafficking of not only BNC-LP complexes but also of HBV. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Template synthesis of two new supramolecular zinc(II) complexes containing pentadentate N3O2 semicarbazone ligand: Nanostructure synthesis, Hirshfeld surface analysis, and DFT studies (United States)

    Tyula, Yunes Abbasi; Zabardasti, Abedien; Goudarziafshar, Hamid; Roudsari, Majid Sadeghi; Dusek, Michal; Eigner, Vaclav


    Two new zinc(II) complexes, [Zn(H2dapsc) (CH3OH)2][ZnBr2Cl2] (1) and [Zn(H2dapsc) (CH3OH)Br]Br.(CH3OH) (2), where H2dapsc is 2,6-diacetylpyridine bis(semicarbazone), were synthesized using a template method in which the pentadentate N3O2 semicarbazone ligand derived from [1 + 2] condensation of 2,6-diacetylpyridine and semicarbazide in the presence of zinc(II) ion as template agent. These compounds were characterized by IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Their single crystal X-ray structures showed that in both complex cations, the metal center has a distorted pentagonal-bipyramidal geometry in which the semicarbazone (H2dapsc) ligand occupies the equatorial plane, while the axial positions occupy by two methanol ligands in (1) and two bromo and methanol ligands in (2). Furthermore, the impact of the close intermolecular contacts on the crystal packing of (1) and (2) have been further studied using Hirshfeld surface analysis. Density Functional Theory (DFT) method was applied for the calculation of HOMO-LUMO energy gap, atomic charges and vibrational frequencies of title complexes. Moreover, the nanostructure of zinc complex was synthesized by a sonochemical method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy, and elemental analysis.

  5. The topological matter of holonomy displacement on the principal U(n) -bundle over Dn,m , related to complex surfaces (United States)

    Byun, Taechang


    Consider U(n) → U(n , m) / U(m) → π Dn,m , where Dn,m = U(n , m) /(U(n) × U(m)) . Given a nontrivial X ∈Mm×n(C) and g ∈ U(n , m) , consider a complete oriented surface S = S(X , g) with a complex structure in Dn,m and a "new" area form ω (X , g) on the surface S . Let c : [ 0 , 1 ] → S be a smooth, simple, closed, orientation-preserving curve and c ˆ : [ 0 , 1 ] → U(n , m) / U(m) its horizontal lift. Then the holonomy displacement is given by the right action of eΨ for some Ψ ∈SpanR i(X∗ X)k k = 1 p ⊂ u(n) , p =the number of distinct positiveeigenvalues ofX∗ X

  6. A silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes

    KAUST Repository

    Espinas, Jeff


    A well-defined silica-based material with a homogeneous nanolayer presenting identical pairs of vicinal silanols has been prepared by reaction of the surface organometallic species [≡SiOZr(CH 2CMe 3) 3], obtained on a silica dehydroxylated at 900 °C, with the double-decker-shaped silsesquioxane (OH) 2DD(OH) 2. The surface structure has been established using extensive NMR characterization ( 1H, 13C, 29Si, HETCOR, double-quantum, triple-quantum). Treatment with Zr(CH 2CMe 3) 4 leads to the first well-defined single-site bipodal grafted bis-neopentyl zirconium complex. © 2012 American Chemical Society.

  7. Type IX secretion: the generation of bacterial cell surface coatings involved in virulence, gliding motility and the degradation of complex biopolymers. (United States)

    Veith, Paul D; Glew, Michelle D; Gorasia, Dhana G; Reynolds, Eric C


    The Type IX secretion system (T9SS) is present in over 1000 sequenced species/strains of the Fibrobacteres-Chlorobi-Bacteroidetes superphylum. Proteins secreted by the T9SS have an N-terminal signal peptide for translocation across the inner membrane via the SEC translocon and a C-terminal signal for secretion across the outer membrane via the T9SS. Nineteen protein components of the T9SS have been identified including three, SigP, PorX and PorY that are involved in regulation. The inner membrane proteins PorL and PorM and the outer membrane proteins PorK and PorN interact and a complex comprising PorK and PorN forms a large ring structure of 50 nm in diameter. PorU, PorV, PorQ and PorZ form an attachment complex on the cell surface of the oral pathogen, Porphyromonas gingivalis. P. gingivalis T9SS substrates bind to PorV suggesting that after translocation PorV functions as a shuttle protein to deliver T9SS substrates to the attachment complex. The PorU component of the attachment complex is a novel Gram negative sortase which catalyses the cleavage of the C-terminal signal and conjugation of the protein substrates to lipopolysaccharide, anchoring them to the cell surface. This review presents an overview of the T9SS focusing on the function of T9SS substrates and machinery components. © 2017 John Wiley & Sons Ltd.

  8. Edmonston Measles Virus Prevents Increased Cell Surface Expression of Peptide-Loaded Major Histocompatibility Complex Class II Proteins in Human Peripheral Monocytes


    Yilla, Mamadi; Hickman, Carole; McGrew, Marcia; Meade, Elizabeth; Bellini, William J.


    Gamma interferon (IFN-γ) induces expression of the gene products of the major histocompatibility complex (MHC), whereas IFN-α/β can interfere with or suppress class II protein expression. In separate studies, measles virus (MV) was reported to induce IFN-α/β and to up-regulate MHC class II proteins. In an attempt to resolve this paradox, we examined the surface expression of MHC class I and class II proteins in MV-infected peripheral monocytes in the presence and absence of IFN-α/β. Infection...

  9. The creation of the analytical information system to serve the process of complex decommissioning of nuclear submarines (NSM) and surface ships (SS) with nuclear power installations (NPI)

    International Nuclear Information System (INIS)

    Terentiev, V.G.; Yakovlev, N.E.; Tyurin, A.V.


    Management of the decommissioning of nuclear vessels includes information collection, accumulation, systematisation and analysis on the complex utilization of nuclear submarines and surface ships with nuclear power installations and on treatment of spent nuclear fuel and radioactive wastes. The relevant data on radiation and ecology, science and technology, law and economy, administration and management should be properly processed. The general objective of the analytical information system (AIS) development, described in the present paper, is the efficiency upgrading for nuclear submarine utilization management and decision making. The report considers information provision and functioning principles as well as software/hardware solutions associated with the AIS creation. (author)

  10. Surface-based molecular self-assembly: Langmuir-Blodgett films of amphiphilic Ln(III) complexes. (United States)

    Wales, Dominic J; Kitchen, Jonathan A


    The unique photophysical properties of the Ln(III) series has led to significant research efforts being directed towards their application in sensors. However, for "real-life" applications, these sensors should ideally be immobilised onto surfaces without loss of function. The Langmuir-Blodgett (LB) technique offers a promising method in which to achieve such immobilisation. This mini-review focuses on synthetic strategies for film formation, the effect that film formation has on the physical properties of the Ln(III) amphiphile, and concludes with examples of Ln(III) LB films being used as sensors.

  11. Zn(II)-concentration dependent Raman spectra in the dithizone complex on gold nanoparticle surfaces in environmental water samples (United States)

    Ly, Nguyen Hoang; Joo, Sang-Woo


    After the formation of dithizone with metal ion complexes, a selective Raman detection method for the Zn2+ ions in aqueous solutions was developed by observing the intensity change of the ring mode peaks at ∼1585 cm-1 on gold nanoparticles (AuNPs). At high concentrations of Zn2+ ions, the conformation of the dithizone complex may have different orientations on AuNPs to yield the spectral changes at ca. ∼510 and ∼1585 cm-1. The concentration dependent spectra changes indicated that a detection limit would be in the submicromolar region of Zn2+ ions. The other ions of Mg2+, K+, Fe3+, Hg2+, Co2+, Fe2+, Pb2+, Cu2+, Ni2+, Cr3+, NH4+, Cd2+, Na+, Ca2+, and Mn2+ at micromolar concentrations of 1 μM did not produce such spectral changes. The detection limit based on the Raman band intensities was estimated to be as low as 500 nM of Zn2+ ion in aqueous solutions. The three real samples of tap, river, and seawater were tested under the interference of the commonly existing interfering ions. Despite the presence of highly concentrated Na, Ca, Mg, and K, our interfacial spectroscopic methodology of Zn2+ determination could be applied in the environmental water samples.

  12. Histochemical evidence for the differential surface labeling, uptake, and intracellular transport of a colloidal gold-labeled insulin complex by normal human blood cells

    International Nuclear Information System (INIS)

    Ackerman, G.A.; Wolken, K.W.


    A colloidal gold-labeled insulin-bovine serum albumin (GIA) reagent has been developed for the ultrastructural visualization of insulin binding sites on the cell surface and for tracing the pathway of intracellular insulin translocation. When applied to normal human blood cells, it was demonstrated by both visual inspection and quantitative analysis that the extent of surface labeling, as well as the rate and degree of internalization of the insulin complex, was directly related to cell type. Further, the pathway of insulin (GIA) transport via round vesicles and by tubulo-vesicles and saccules and its subsequent fate in the hemic cells was also related to cell variety. Monocytes followed by neutrophils bound the greatest amount of labeled insulin. The majority of lymphocytes bound and internalized little GIA, however, between 5-10% of the lymphocytes were found to bind considerable quantities of GIA. Erythrocytes rarely bound the labeled insulin complex, while platelets were noted to sequester large quantities of the GIA within their extracellular canalicular system. GIA uptake by the various types of leukocytic cells appeared to occur primarily by micropinocytosis and by the direct opening of cytoplasmic tubulo-vesicles and saccules onto the cell surface in regions directly underlying surface-bound GIA. Control procedures, viz., competitive inhibition of GIA labeling using an excess of unlabeled insulin in the incubation medium, preincubation of the GIA reagent with an antibody directed toward porcine insulin, and the incorporation of 125I-insulin into the GIA reagent, indicated the specificity and selectivity of the GIA histochemical procedure for the localization of insulin binding sites

  13. When lithography meets self-assembly: a review of recent advances in the directed assembly of complex metal nanostructures on planar and textured surfaces (United States)

    Hughes, Robert A.; Menumerov, Eredzhep; Neretina, Svetlana


    One of the foremost challenges in nanofabrication is the establishment of a processing science that integrates wafer-based materials, techniques, and devices with the extraordinary physicochemical properties accessible when materials are reduced to nanoscale dimensions. Such a merger would allow for exacting controls on nanostructure positioning, promote cooperative phenomenon between adjacent nanostructures and/or substrate materials, and allow for electrical contact to individual or groups of nanostructures. With neither self-assembly nor top-down lithographic processes being able to adequately meet this challenge, advancements have often relied on a hybrid strategy that utilizes lithographically-defined features to direct the assembly of nanostructures into organized patterns. While these so-called directed assembly techniques have proven viable, much of this effort has focused on the assembly of periodic arrays of spherical or near-spherical nanostructures comprised of a single element. Work directed toward the fabrication of more complex nanostructures, while still at a nascent stage, has nevertheless demonstrated the possibility of forming arrays of nanocubes, nanorods, nanoprisms, nanoshells, nanocages, nanoframes, core-shell structures, Janus structures, and various alloys on the substrate surface. In this topical review, we describe the progress made in the directed assembly of periodic arrays of these complex metal nanostructures on planar and textured substrates. The review is divided into three broad strategies reliant on: (i) the deterministic positioning of colloidal structures, (ii) the reorganization of deposited metal films at elevated temperatures, and (iii) liquid-phase chemistry practiced directly on the substrate surface. These strategies collectively utilize a broad range of techniques including capillary assembly, microcontact printing, chemical surface modulation, templated dewetting, nanoimprint lithography, and dip-pen nanolithography and

  14. Study of the surface modification with oleic acid of nanosized HfO{sub 2} synthesized by the polymerized complex derived sol-gel method

    Energy Technology Data Exchange (ETDEWEB)

    Ramos-Gonzalez, R., E-mail: [Centro de Investigacion en Quimica Aplicada, Blvd. Enrique Reyna Hermosillo No. 140, Saltillo, Coahuila 25250 (Mexico); Garcia-Cerda, L.A. [Centro de Investigacion en Quimica Aplicada, Blvd. Enrique Reyna Hermosillo No. 140, Saltillo, Coahuila 25250 (Mexico); Quevedo-Lopez, M.A. [University of Texas at Dallas, 800 West Campbell Road, Richardson, TX 75080-3021 (United States)


    The synthesis of nanosized hafnium oxide by the polymerized complex derived sol-gel method is reported. The structural and morphological characterization of the HfO{sub 2} was carried out by X-ray diffraction and scanning electron microscopy. The surface of hafnium oxide nanoparticles was modified by capping with oleic acid. The nanoparticle surface area was measured by the gas adsorption technique in order to determine the minimal amount of oleic acid needed to obtain a uniform coverage of the hafnium oxide. The existence of organic layer can be confirmed by Fourier transform spectroscopy, solid state nuclear magnetic resonance spectroscopy, thermal gravimetric analysis and transmission electron microscopy. The FTIR and solid state NMR results reveal that oleic acid is chemisorbed as a carboxylate onto the HfO{sub 2} nanoparticle surface and confirm the formation of a monomolecular layer of oleic acid surrounding the HfO{sub 2}. The cover density of oleic acid on the HfO{sub 2} increases with the amount of oleic acid used to modify the nanoparticles and the surface properties of HfO{sub 2} nanoparticles modified with oleic acid change from hydrophilic to hydrophobic.

  15. In various protein complexes, disordered protomers have large per-residue surface areas and area of protein-, DNA- and RNA-binding interfaces. (United States)

    Wu, Zhonghua; Hu, Gang; Yang, Jianyi; Peng, Zhenling; Uversky, Vladimir N; Kurgan, Lukasz


    We provide first large scale analysis of the peculiarities of surface areas of 5658 dissimilar (below 50% sequence similarity) proteins with known 3D-structures that bind to proteins, DNA or RNAs. We show here that area of the protein surface is highly correlated with the protein length. The size of the interface surface is only modestly correlated with the protein size, except for RNA-binding proteins where larger proteins are characterized by larger interfaces. Disordered proteins with disordered interfaces are characterized by significantly larger per-residue areas of their surfaces and interfaces when compared to the structured proteins. These result are applicable for proteins involved in interaction with DNA, RNA, and proteins and suggest that disordered proteins and binding regions are less compact and more likely to assume extended shape. We demonstrate that disordered protein binding residues in the interfaces of disordered proteins drive the increase in the per residue area of these interfaces. Our results can be used to predict in silico whether a given protomer from the DNA, RNA or protein complex is likely to be disordered in its unbound form. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  16. A Hirshfeld surface analysis, crystal structure and spectroscopic properties of new Zn(II) complex with N-aminoethylpiperazine ligand (United States)

    El Glaoui, Maroua; El Glaoui, Maher; Jelsch, Christian; Aubert, Emmanuel; Lefebvre, Frédéric; Ben Nasr, Chérif


    A new organic-inorganic hybrid material, 1-amonioethylpiperazine-1, 4-diium tetrachloridozincate(II) chloride, (C6H18N3)[ZnCl4]Cl, has been synthesized and characterized by various physicochemical techniques including UV-visible absorption, Infra-Red (IR), Raman and NMR spectroscopies. The compound crystallizes in the monoclinic system and P21 space group with Z = 2 and the following unit cell dimensions: a = 7.1728 (6), b = 12.4160 (11), c = 8.0278 (7) Å, β = 97.513 (1)°, V = 708.80 (11) Å3. In this structure, the Zn2+ ion, surrounded by four chlorides, adopts a distorted tetrahedral coordination geometry. The structure of this compound consists of monomeric 1-amonioethylpiperazine-1, 4-diium trications and monomeric [ZnCl4]2- and Cl- anions. These entities are interconnected by means of hydrogen bonding contacts [Nsbnd H⋯Cl, Csbnd H⋯Cl], forming a three-dimensional network. Intermolecular interactions were investigated by Hirshfeld surfaces. More than three quarters of the interaction surface in the crystal packing is constituted by attractive and favored H⋯Cl hydrogen bonds. The 13C and 15N CP-MAS NMR spectra are discussed and the vibrational absorption bands were identified by infrared and Raman spectroscopy.

  17. Mycobacterium icosiumassiliensis sp. nov., a New Member in the Mycobacterium terrae Complex Isolated from Surface Water in Algeria. (United States)

    Djouadi, Lydia N; Levasseur, Anthony; Khalil, Jacques Bou; Blanc-Taileur, Caroline; Asmar, Shady; Ghiloubi, Wassila; Natèche, Farida; Drancourt, Michel


    An acid-fast, rapidly growing, rod-shaped microorganism designated 8WA6 was isolated from a lake in Algiers, Algeria. The lake water was characterized by a temperature of 18 °C, a pH of 7.82, a copper concentration of 8.6 µg/L, and a cadmium concentration of 0.6 µg/L. First-line molecular identification confirmed the 8WA6 isolate to be a member of the Mycobacterium terrae complex, sharing 99.4 % 16S rRNA gene sequence similarity with M. arupense AR-30097, 98.2 % partial hsp65 gene sequence similarity with M. terrae 28K766, and 97.1 % partial rpoB gene sequence similarity with Mycobacterium sp. FI-05396. Its 4.89-Mb genome exhibits a 66.8 GC % and an average nucleotide identity of 64.5 % with M. tuberculosis, 70.5 % with M. arupense, and 75 % with M. asiaticum. In the M. terrae complex, Mycobacterium 8WA6 was unique in exhibiting growth at 42 °C, negative reaction for nitrate reduction, urease activity and Tween 80 hydrolysis, and a positive reaction for α-glucosidase and β-glucosidase. Its protein profile determined by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed a unique spectrum similar to M. arupense and M. terrae, exhibiting eleven specific peaks at 3787.791, 4578.019, 6349.630, 6855.638, 7202.310, 8149.608, 8775.257, 10,224.588, 10,484.116, 12,226.379, and 12,636.871 m/z. Minimal inhibitory concentrations (MIC) for antibiotics, determined by microdilution, indicated a broad spectrum resistance, except for rifabutin (MIC, 0.5 g/L) and cefoxitin (MIC, 16 g/L). We concluded that the 8WA6 isolate is a representative isolate of a previously undescribed species in the M. terrae complex, which was named M. icosiumassiliensis sp. nov. with strain 8WA6 (Collection de Souches de l'Unité des Rickettsies, CSUR P1561, Deutsche Sammlung von Mikroorganismen und Zellkulturen, DSM 100711) as the type strain.

  18. FRET structure with non-radiative acceptor provided by dye-linker-glass surface complex and single-molecule photodynamics by TIRFM-polarized imaging

    International Nuclear Information System (INIS)

    Tani, Toshiro; Mashimo, Kei; Suzuki, Tetsu; Horiuchi, Hiromi; Oda, Masaru


    We present our recent study of microscopic single-molecule imaging on the artificial complex of tetramethylrhodamine linked with a propyl chain onto silica glass surface, i.e. an asymmetric fluorescence resonance energy transfer (FRET) structure with non-radiative acceptor. In the synthesis of the complex, we used a mixture of two kinds of isomers to introduce rather small photodynamic difference among them. This isomeric structure change will provide more or less a distinctive photophysical change in e.g. non-radiative relaxation rate. Our recent observation at room temperatures, so far, shows that such contributions can be discriminated in the histograms of the fluorescent spot intensities; broad but distinctive multi-components appear. To identify the isomeric difference as a cause of structures, some configurational assumptions are necessary. One such basic prerequisite is that the transition dipoles of the chromophores should be oriented almost parallel to the glass surface. In order to make clear the modeling, we also provide preliminary experiments on the polarization dependence of the imaging under rotating polarization in epi-illumination

  19. Structure of a Glomulin-RBX1-CUL1 Complex: Inhibition of a RING E3 Ligase through Masking of Its E2-Binding Surface

    Energy Technology Data Exchange (ETDEWEB)

    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. (BWH); (LBNL); (SJCH); (DFCI)


    The approximately 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 SCF{sup FBW7} 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.

  20. Structure of a Glomulin-RBX1-CUL1 complex: inhibition of a RING E3 ligase through masking of its E2-binding surface (United States)

    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.


    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

  1. A method and example of seismically imaging near‐surface fault zones in geologically complex areas using Vp, Vs, and their ratios (United States)

    Catchings, Rufus D.; Rymer, Michael J.; Goldman, Mark R.; Sickler, Robert R.; Criley, Coyn J.


    The determination of near‐surface (vadose zone and slightly below) fault locations and geometries is important because assessment of ground rupture, strong shaking, geologic slip rates, and rupture histories occurs at shallow depths. However, seismic imaging of fault zones at shallow depths can be difficult due to near‐surface complexities, such as weathering, groundwater saturation, massive (nonlayered) rocks, and vertically layered strata. Combined P‐ and S‐wave seismic‐refraction tomography data can overcome many of the near‐surface, fault‐zone seismic‐imaging problems because of differences in the responses of elastic (bulk and shear) moduli of P and S waves to shallow‐depth, fault‐zone properties. We show that high‐resolution refraction tomography images of P‐ to S‐wave velocity ratios (VP/VS) can reliably identify near‐surface faults. We demonstrate this method using tomography images of the San Andreas fault (SAF) surface‐rupture zone associated with the 18 April 1906 ∼M 7.9 San Francisco earthquake on the San Francisco peninsula in California. There, the SAF cuts through Franciscan mélange, which consists of an incoherent assemblage of greywacke, chert, greenstone, and serpentinite. A near‐vertical zone (∼75° northeast dip) of high P‐wave velocities (up to 3000  m/s), low S‐wave velocities (∼150–600  m/s), high VP/VS ratios (4–8.8), and high Poisson’s ratios (0.44–0.49) characterizes the main surface‐rupture zone to a depth of about 20 m and is consistent with nearby trench observations. We suggest that the combined VP/VSimaging approach can reliably identify most near‐surface fault zones in locations where many other seismic methods cannot be applied.

  2. Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA (United States)

    Sharif, M.S.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.


    The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6. m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6. m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory. ?? 2011 Elsevier Ltd.

  3. Electron Transfer Mediator Effects in Water Oxidation Catalysis by Solution and Surface-Bound Ruthenium Bpy-Dicarboxylate Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Sheridan, Matthew V.; Sherman, Benjamin D.; Marquard, Seth L.; Fang, Zhen; Ashford, Dennis L.; Wee, Kyung-Ryang; Gold, Alexander S.; Alibabaei, Leila; Rudd, Jennifer A.; Coggins, Michael K.; Meyer, Thomas J.


    Electrocatalytic water oxidation by the catalyst, ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) bis-isoquinoline (isoq), [Ru(bda)(isoq)2], 1, was investigated at metal oxide electrodes surface-derivatized with electron transfer (ET) mediators. At indium-doped tin oxide (ITO) in pH 7.2 in H2PO4–/HPO42– buffers in 0.5 M NaClO4 with added acetonitrile (MeCN), the catalytic activity of 1 is enhanced by the surface-bound redox mediators [Ru (4,4'-PO3H2-bpy)(4,4'-R-bpy)2]2+ (RuPbpyR22+, R = Br, H, Me, or OMe, bpy = 2,2'-bipyridine). Rate-limiting ET between the Ru3+ form of the mediator and the RuIV(O) form in the [RuV/IV(O)]+/0 couple of 1 is observed at relatively high concentrations of HPO42– buffer base under conditions where O···O bond formation is facilitated by atom-proton transfer (APT). For the solution [Ru(bpy)3]3+/2+ mediator couple and 1 as the catalyst, catalytic currents vary systematically with the concentration of mediator and the HPO42– buffer base concentration. Electron transfer mediation of water oxidation catalysis was also investigated on nanoparticle TiO2 electrodes co-loaded with catalyst [Ru(bda)(py-4-O(CH2)3-PO3H2)2], 2, (py = pyridine) and RuPbpyR22+ (R = H, Me, or OMe) with an interplay between rate-limiting catalyst oxidation and rate-limiting O···O bond formation by APT. Lastly, the co-loaded assembly RuPbpyR22+ + 2 has been investigated in a dye-sensitized photoelectrosynthesis cell for water splitting.

  4. Resisting the seduction of "ethics creep": using Foucault to surface complexity and contradiction in research ethics review. (United States)

    Guta, Adrian; Nixon, Stephanie A; Wilson, Michael G


    In this paper we examine "ethics creep", a concept developed by Haggerty (2004) to account for the increasing bureaucratization of research ethics boards and institutional review boards (REB/IRBs) and the expanding reach of ethics review. We start with an overview of the recent surge of academic interest in ethics creep and similar arguments about the prohibitive effect of ethics review. We then introduce elements of Michel Foucault's theoretical framework which are used to inform our analysis of empirical data drawn from a multi-phase study exploring the accessibility of community-engaged research within existing ethics review structures in Canada. First, we present how ethics creep emerged both explicitly and implicitly in our data. We then present data that demonstrate how REB/IRBs are experiencing their own form of regulation. Finally, we present data that situate ethics review alongside other trends affecting the academy. Our results show that ethics review is growing in some ways while simultaneously being constrained in others. Drawing on Foucauldian theory we reframe ethics creep as a repressive hypothesis which belies the complexity of the phenomenon it purports to explain. Our discussion complicates ethics creep by proposing an understanding of REB/IRBs that locates them at the intersection of various neoliberal discourses about the role of science, ethics, and knowledge production. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Microfilament association of ASGP-2, the concanavalin A-binding glycoprotein of the cell-surface sialomucin complex of 13762 rat mammary ascites tumor cells

    Energy Technology Data Exchange (ETDEWEB)

    Vanderpuye, L.A.; Carraway, C.A.C.; Carraway, K.L. (Univ. of Miami School of Medicine, FL (USA))


    Microfilament-associated proteins and membrane-microfilament interactions are being investigated in microvilli isolated from 13762 rat mammary ascites tumor cells. Phalloidin shift analyses on velocity sedimentation gradients of Triton X-100 extracts of ({sup 3}H)-glucosamine-labeled microvilli identified a 120-kDa cell-surface glycoprotein associated with the microvillar microfilament core. The identification was verified by concanavalin A (Con A) blots of one- and two-dimensional (2D) electrophoresis gels of sedimented microfilament cores. By 2D-electrophoresis and lectin analyses the 120-kDa protein appeared to be a fraction of ASGP-2, the major Con A-binding glycoprotein of the sialomucin complex of the 13762 cells. This identity was confirmed by immunoblot analyses using immunoblot-purified anti-ASGP-2 from anti-membrane serum prepared against microvillar membranes. Proteolysis of the microvilli with subtilisin or trypsin resulted in an increase in the amount of ASGP-2 associated with the microfilament cores. Proteolysis of isolated microvillar membranes, which contain actin but not microfilaments, also increased the association of ASGP-2 with a Triton-insoluble, actin-containing membrane fraction. Since the Triton-insoluble membrane residue is enriched in actin-containing transmembrane complex, which contains a different glycoprotein, the authors suggest that the ASGP-2 is binding indirectly via this complex to the microfilament core in the intact microvilli.

  6. Surface charge-transfer complex formation of catechol on titanium(IV) oxide and the application to bio-sensing. (United States)

    Murata, Yusuke; Hori, Hiroshige; Taga, Atsushi; Tada, Hiroaki


    Adsorption properties of 2-hydroxyphenol (catechol) on TiO2 particles has been studied at 298K. The adsorption proceeds from the aqueous solution with the Langmuir type behavior. Diffuse reflectance infrared spectra of the catechol-adsorbed TiO2 suggested that catechol is adsorbed on TiO2 solution via the chelation to the surface Ti ions. The adsorption induces a strong absorption in the whole visible region, of which intensity increases with an increase in the adsorption amount. Photoelectrochemical experiments and molecular orbital calculations indicate that the absorption stems from the charge-transfer (CT) transition from the HOMO of catechol to the conduction band of TiO2. Time courses for the adsorption of catechol on mesoporous TiO2 nanocrystalline film-coated glass was traced by measuring the change in the absorbance of the CT band, and analyzed on the basis of the Langmuir model. This study would present a new simple technique for sensing of important biomolecules bearing the catechol moiety. Copyright © 2015. Published by Elsevier Inc.

  7. Role of surface and subsurface lateral water flows on summer precipitation in a complex terrain region: A WRF-Hydro case-study for Southern Germany (United States)

    Rummler, Thomas; Arnault, Joel; Gochis, David; Kunstmann, Harald


    Recent developments in hydrometeorological modeling aim towards more sophisticated treatment of terrestrial hydrologic processes. The standard version of the Weather Research and Forecasting (WRF) model describes terrestrial water transport as a purely vertical process. The hydrologically enhanced version of WRF, namely WRF-Hydro, does account for lateral terrestrial water flows, which allows for a more comprehensive process description of the interdependencies between water- and energy fluxes at the land-atmosphere interface. In this study, WRF and WRF-Hydro are applied to the Bavarian Alpine region in southern Germany, a complex terrain landscape in a relatively humid, mid-latitude climate. Simulation results are validated with gridded and station observation of precipitation, temperature and river discharge. Differences between WRF and WRF-Hydro results are investigated with a joint atmospheric-terrestrial water budget analysis. Changes in the partitioning in (near-) surface runoff and percolation are prominent. However, values for evapotranspiration ET feature only marginal variations, suggesting that soil moisture content is not a limiting factor of ET in this specific region. Simulated precipitation fields during isolated summertime events still show appreciable differences, while differences in large-scale, multi-day rainy periods are less substantial. These differences are mainly related to differences in the moisture in- and outflow terms of the atmospheric water budget induced by the surface and sub-surface lateral redistribution of soil moisture in WRF-Hydro.

  8. Quantitative analysis of surface deformation and ductile flow in complex analogue geodynamic models based on PIV method. (United States)

    Krýza, Ondřej; Lexa, Ondrej; Závada, Prokop; Schulmann, Karel; Gapais, Denis; Cosgrove, John


    Recently, a PIV (particle image velocimetry) analysis method is optical method abundantly used in many technical branches where material flow visualization and quantification is important. Typical examples are studies of liquid flow through complex channel system, gas spreading or combustion problematics. In our current research we used this method for investigation of two types of complex analogue geodynamic and tectonic experiments. First class of experiments is aimed to model large-scale oroclinal buckling as an analogue of late Paleozoic to early Mesozoic evolution of Central Asian Orogenic Belt (CAOB) resulting from nortward drift of the North-China craton towards the Siberian craton. Here we studied relationship between lower crustal and lithospheric mantle flows and upper crustal deformation respectively. A second class of experiments is focused to more general study of a lower crustal flow in indentation systems that represent a major component of some large hot orogens (e.g. Bohemian massif). The most of simulations in both cases shows a strong dependency of a brittle structures shape, that are situated in upper crust, on folding style of a middle and lower ductile layers which is influenced by rheological, geometrical and thermal conditions of different parts across shortened domain. The purpose of PIV application is to quantify material redistribution in critical domains of the model. The derivation of flow direction and calculation of strain-rate and total displacement field in analogue experiments is generally difficult and time-expensive or often performed only on a base of visual evaluations. PIV method operates with set of images, where small tracer particles are seeded within modeled domain and are assumed to faithfully follow the material flow. On base of pixel coordinates estimation the material displacement field, velocity field, strain-rate, vorticity, tortuosity etc. are calculated. In our experiments we used velocity field divergence to

  9. Contrasting rock permeability in the aureole of the Ballachulish igneous complex, Scottish Highlands: the influence of surface energy? (United States)

    Holness, M. B.

    The Ballachulish igneous complex in the Scottish Highlands, part of a widespread group of late Caledonian calcalkaline intrusions, was emplaced at a depth of 10km into Dalradian metasediments resulting in melting of the country rocks near the intrusive contact. The greatest extent of melting occurred in the Leven schist in the 400m wide so-called Chaotic Zone which experienced infiltration of aqueous fluids from the pluton. In contrast, adjacent to the Chaotic Zone, the feldspar-bearing Appin quartzite underwent significant melting only within a few metres of the intrusion, despite both being in contact with the same fluid source as the Leven schist and having a similar (wet) melting point. The permeability of the Appin quartzite and quartz horizons in the Leven schist to pervasive grain-edge infiltration of aqueous fluids was determined by measuring the equilibrium quartz-H2O dihedral angle for the P-T conditions of contact metamorphism. Addition of powdered samples of both rock types to the pure quartz-H2O system results in a linear decrease of the quartz-H2O dihedral angle with increasing temperature. The rate of this decrease for the Leven schist is greater than that for the Appin quartzite, and the angle decreases below 60° some 30°C below the wet solidus (670°C at 0.3GPa). Charges bearing Appin quartzite had dihedral angles greater than 60° at all temperatures below the wet solidus (690°C at 0.3GPa). These results demonstrate that quartz-rich horizons in the Leven schist would have been permeable to infiltration of aqueous fluids close to the solidus, permitting extensive H2O-fluxed melting to occur. The Appin quartzite would have remained impermeable to grain-edge flow, consistent with the observed differences in the extent of partial melting of the two lithologies.

  10. Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components

    Energy Technology Data Exchange (ETDEWEB)

    Makarewicz, Jan, E-mail:; Shirkov, Leonid [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland)


    The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy D{sub e} of 392 cm{sup −1} is close to that of 387 cm{sup −1} calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, D{sub e} for PAr becomes slightly lower than D{sub e} for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

  11. Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components. (United States)

    Makarewicz, Jan; Shirkov, Leonid


    The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy De of 392 cm(-1) is close to that of 387 cm(-1) calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, De for PAr becomes slightly lower than De for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

  12. Efficient biological conversion of carbon monoxide (CO) to carbon dioxide (CO2) and for utilization in bioplastic production by Ralstonia eutropha through the display of an enzyme complex on the cell surface. (United States)

    Hyeon, Jeong Eun; Kim, Seung Wook; Park, Chulhwan; Han, Sung Ok


    An enzyme complex for biological conversion of CO to CO2 was anchored on the cell surface of the CO2-utilizing Ralstonia eutropha and successfully resulted in a 3.3-fold increase in conversion efficiency. These results suggest that this complexed system may be a promising strategy for CO2 utilization as a biological tool for the production of bioplastics.

  13. Lactobacillus plantarum gene clusters encoding putative cell-surface protein complexes for carbohydrate utilization are conserved in specific gram-positive bacteria

    Directory of Open Access Journals (Sweden)

    Muscariello Lidia


    D proteins form cell-surface protein complexes and play a role in carbon source acquisition. Primary occurrence in plant-associated gram-positive bacteria suggests a possible role in degradation and utilization of plant oligo- or poly-saccharides.

  14. Second-sphere complexation of thorium(IV) by cucurbit[6]uril with included perrhenate counterions. Crystal structure and Hirshfeld surface analysis

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, Pierre [CEA, IRAMIS, UMR 3685 NIMBE, Laboratoire de Chimie Moleculaire et Catalyse pour l' Energie (LCMCE), Gif-sur-Yvette (France)


    The reaction of thorium(IV) nitrate with cucurbit[6]uril (CB6) in the presence of perrhenic acid in water gives the complex [Th(NO{sub 3})(H{sub 2}O){sub 8}][(ReO{sub 4})(CB6)](ReO{sub 4}){sub 2}.3H{sub 2}O (1). Aquated cations are held at both CB6 portals by ion-dipole and hydrogen-bonding interactions, and one of the ReO{sub 4}{sup -} anions is included in the CB6 cavity. The packing displays columns of alternate cations and encapsulated anions. Hirshfeld surfaces are used to visualize short contacts between the species present. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin


    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Surface-driven, one-step chemical vapor deposition of γ-Al{sub 4}Cu{sub 9} complex metallic alloy film

    Energy Technology Data Exchange (ETDEWEB)

    Prud’homme, Nathalie [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France); Université Paris-Sud 11, LEMHE/ICMMO, Bat 410, 91405 Orsay Cedex (France); Duguet, Thomas, E-mail: [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France); Samélor, Diane; Senocq, François; Vahlas, Constantin [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France)


    The present paper is a paradigm for the one-step formation of complex intermetallic coatings by chemical vapor deposition. It genuinely addresses the challenge of depositing an intermetallic coating with comparable contents of Cu and Al. Depending on processing conditions, a pure γ-Al{sub 4}Cu{sub 9} and multi-phase Al-Cu films are grown with wetting properties of the former being similar to its bulk counterpart. The deposition process and its parametric investigation are detailed. Two metalorganic precursors are used taking into account their transport and chemical properties, and deposition temperature ranges. On line and ex situ characterizations enlighten the competition which occurs at the growing surface between molecular fragments, and which limits growth rates. Notably, introducing a partial pressure of hydrogen gas during deposition reduces Al growth rate from dimethylethylamine alane (DMEAA), by displacing the hydrogen desorption equilibrium. This Al partial growth rate decrease is not sufficient to achieve a Cu/Al atomic ratio that is high enough for the formation of intermetallics with close Al and Cu compositions. A fivefold increase of the flux of the gaseous copper(I) cyclopentadienyl triethylphosphine CpCuPEt{sub 3}, whereas the DMEAA flux remains constant, results in the targeted Al/Cu atomic ratio equal to 44/56. Nevertheless, the global growth rate is rendered extremely low by the deposition inhibition caused by a massive phosphine adsorption (-PEt{sub 3}). Despite these limitations, the results pave the way towards the conformal coating of complex surface geometries by such intermetallic compounds.

  17. A Hirshfeld surface analysis, synthesis, structure and characterization of a new Ni(II) diamagnetic complex with the bidentate ligand homopiperazine (United States)

    Klai, Kacem; Kaabi, Kamel; Jelsch, Christian; Wenger, Emmanuel; Lefebvre, Frédéric; Ben Nasr, Cherif


    A new Ni(II) complex with the bidentate ligand homopiperazine, [Ni(C5H12N2)2](CH3COO)2.4H2O, has been prepared and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. The basic coordination patterns of the homopiperazine coordinated metal cations are slightly distorted square planar. In the atomic arrangement, the cationic complexes [Ni(C5H12N2)2]2+ are interconnected by the CH3COO-anions via Nsbnd H⋯O and Csbnd H⋯O hydrogen bonds to form layers parallel to the (a, b) plane. These layers are connected by hydrogen bonds generated with water molecules to build a three dimensional network. The charge density of the compound could be refined from X-ray diffraction data measured at cryogenic temperature. Intermolecular interactions were investigated by Hirshfeld surfaces. The title compound is diamagnetic as confirmed by theoretical calculations, allowing its 13C and 15N solid-state NMR spectra to be recorded. Absorption bands were identified by infrared spectroscopy. Electronic properties such as HOMO and LUMO energies were also obtained.

  18. Immobilized molybdenum–thiosemicarbazide Schiff base complex on the surface of magnetite nanoparticles as a new nanocatalyst for the epoxidation of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadikish, M., E-mail: [Department of Chemistry, Faculty of Sciences, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Masteri-Farahani, M.; Mahdavi, S. [Faculty of Chemistry, Kharazmi University, Tehran (Iran, Islamic Republic of)


    In this work, a new magnetically recoverable nanocatalyst was developed by immobilization of thiosemicarbazide ligand on the surface of silica coated magnetite nanoparticles (SCMNPs) through Schiff base condensation and followed complexation with MoO{sub 2}(acac){sub 2}. Characterization of the prepared nanocatalyst was performed with different physicochemical methods such as Fourier transform infrared (FT-IR) and atomic absorption spectroscopies, X-ray diffraction (XRD), vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The prepared catalyst catalyzed the epoxidation of olefins and allyl alcohols with tert-butyl hydroperoxide (TBHP) and cumene hydroperoxide (CHP) quantitatively with excellent selectivity toward the corresponding epoxides under mild reaction conditions. - Highlights: • Silica coated magnetite nanoparticles were modified with a thiosemicarbazide-Schiff base ligand. • Complexation of the supported ligand with molybdenum resulted in preparation of a new hybrid nanomaterial. • The prepared hybrid nanomaterial acted as an efficient and reusable catalyst in the epoxidation of olefins.

  19. Research on the Influence of Cutting Rates on Macrogeometry Deflections of Surfaces under Processing Complex form Products Made of Aluminium Aloys

    Directory of Open Access Journals (Sweden)

    Ieva Švagždytė


    Full Text Available The article reviews the influence of cutting rates on macrogeometry deflection of milling complex form products and turning an outside surface. For that purpose, one of the most popular aluminium alloys 6082 has been chosen. A ball nose mill of 8 mm in diameter has been milled employing CNC vertical centre HAAS MINI MILL and applying CNC lathe HAAS ST 20 for turning. Measurements have been carried out using coordinate measuring machine DEA micro-hite DCC, applying the probe sphere of 3mm in diameter and the probe equipped with a needle. A deviation of the surface profile from tangent to therophore parabola has been investigated. The determinants R2 of the obtained regressive equation have disclosed that the depth of the cut has the biggest influence on macrogeometry deflections, whereas feed rate has a slighter influence and cutting speed has no radical influence. For the turning process, the depth of the cut has the strongest influence on circularity while cilindrisity has been mainly affected by cutting speed.

  20. Disease-causing mutations affecting surface residues of mitochondrial glutaryl-CoA dehydrogenase impair stability, heteromeric complex formation and mitochondria architecture. (United States)

    Schmiesing, Jessica; Lohmöller, Benjamin; Schweizer, Michaela; Tidow, Henning; Gersting, Søren W; Muntau, Ania C; Braulke, Thomas; Mühlhausen, Chris


    The neurometabolic disorder glutaric aciduria type 1 (GA1) is caused by mutations in the GCDH gene encoding the mitochondrial matrix protein glutaryl-CoA dehydrogenase (GCDH), which forms homo- and heteromeric complexes. Twenty percent of all pathogenic mutations affect single amino acid residues on the surface of GCDH resulting in a severe clinical phenotype. We report here on heterologous expression studies of 18 missense mutations identified in GA1 patients affecting surface amino acids. Western blot and pulse chase experiments revealed that the stability of half of the GCDH mutants was significantly reduced. In silico analyses showed that none of the mutations impaired the 3D structure of GCDH. Immunofluorescence co-localisation studies in HeLa cells demonstrated that all GCDH mutants were correctly translocated into mitochondria. Surprisingly, the expression of p.Arg88Cys GCDH as well as further substitutions by alanine, lysine, or methionine but not histidine or leucine resulted in the disruption of mitochondrial architecture forming longitudinal structures composed of stacks of cristae and partial loss of the outer mitochondrial membrane. The expression of mitochondrial fusion or fission proteins was not affected in these cells. Bioluminescence resonance energy transfer analyses revealed that all GCDH mutants exhibit an increased binding affinity to electron transfer flavoprotein beta, whereas only p.Tyr155His GCDH showed a reduced interaction with dihydrolipoamide succinyl transferase. Our data underscore the impact of GCDH protein interactions mediated by amino acid residues on the surface of GCDH required for proper enzymatic activity. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email:

  1. Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films (United States)

    Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.


    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

  2. Evaluating the suitability of the SWAN/COSMO-2 model system to simulate short-crested surface waves for a narrow lake with complex bathymetry

    Directory of Open Access Journals (Sweden)

    Michael Graf


    Full Text Available The spectral wave model SWAN (Simulating Waves Nearshore was applied to Lake Zurich, a narrow pre-Alpine lake in Switzerland. The aim of the study is to investigate whether the model system consisting of SWAN and the numerical weather prediction model COSMO-2 is a suitable tool for wave forecasts for the pre-Alpine Lake Zurich. SWAN is able to simulate short-crested wind-generated surface waves. The model was forced with a time varying wind field taken from COSMO-2 with hourly outputs. Model simulations were compared with measured wave data at one near-shore site during a frontal passage associated with strong on-shore winds. The overall course of the measured wave height is well captured in the SWAN simulation: the wave amplitude significantly increases during the frontal passage followed by a transient drop in amplitude. The wave pattern on Lake Zurich is quite complex. It strongly depends on the inherent variability of the wind field and on the external forcing due to the surrounding complex topography. The influence of the temporal wind resolution is further studied with two sensitivity experiments. The first one considers a low-pass filtered wind field, based on a 2-h running mean of COSMO-2 output, and the second experiment uses simple synthetic gusts, which are implemented into the SWAN model and take into account short-term fluctuations of wind speed at 1-sec resolution. The wave field significantly differs for the 1-h and 2-h simulations, but is only negligibly affected by the gusts.

  3. Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex (United States)

    Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana


    Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

  4. Transforming Growth Factor-β2 Downregulates Major Histocompatibility Complex (MHC) I and MHC II Surface Expression on Equine Bone Marrow-Derived Mesenchymal Stem Cells Without Altering Other Phenotypic Cell Surface Markers. (United States)

    Berglund, Alix K; Fisher, Matthew B; Cameron, Kristin A; Poole, Emma J; Schnabel, Lauren V


    Allogeneic mesenchymal stem cells (MSCs) are a promising cell source for treating musculoskeletal injuries in horses. Effective and safe allogeneic therapy may be hindered, however, by recipient immune recognition and rejection of major histocompatibility complex (MHC)-mismatched MSCs. Development of strategies to prevent immune rejection of MHC-mismatched MSCs in vivo is necessary to enhance cell survival and potentially increase the efficacy and safety of allogeneic MSC therapy. The purposes of this study were to evaluate if transforming growth factor-β2 (TGF-β2) downregulated MHC expression on equine MSCs and to determine if TGF-β2 treatment altered the phenotype of MSCs. Equine bone marrow-derived MSCs from 12 horses were treated with 1, 5, or 10 ng/ml TGF-β2 from initial isolation until MHC expression analysis. TGF-β2-treated MSCs had reduced MHC I and MHC II surface expression compared to untreated controls. TGF-β2 treatment also partially blocked IFN-γ-induced upregulation of MHC I and MHC II. Constitutive and IFN-γ-induced MHC I and MHC II expression on equine MSCs was dynamic and highly variable, and the effect of TGF-β2 was significantly dependent on the donor animal and baseline MHC expression. TGF-β2 treatment did not appear to change morphology, surface marker expression, MSC viability, or secretion of TGF-β1, but did significantly increase the number of cells obtained from culture. These results indicate that TGF-β2 treatment has promise for regulating MHC expression on MSCs to facilitate allogeneic therapy, but further work is needed to maintain MHC stability when exposed to an inflammatory stimulus.

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

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

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

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

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


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

  7. Surface complexation modeling of groundwater arsenic mobility: Results of a forced gradient experiment in a Red River flood plain aquifer, Vietnam (United States)

    Jessen, Søren; Postma, Dieke; Larsen, Flemming; Nhan, Pham Quy; Hoa, Le Quynh; Trang, Pham Thi Kim; Long, Tran Vu; Viet, Pham Hung; Jakobsen, Rasmus


    Three surface complexation models (SCMs) developed for, respectively, ferrihydrite, goethite and sorption data for a Pleistocene oxidized aquifer sediment from Bangladesh were used to explore the effect of multicomponent adsorption processes on As mobility in a reduced Holocene floodplain aquifer along the Red River, Vietnam. The SCMs for ferrihydrite and goethite yielded very different results. The ferrihydrite SCM favors As(III) over As(V) and has carbonate and silica species as the main competitors for surface sites. In contrast, the goethite SCM has a greater affinity for As(V) over As(III) while PO43- and Fe(II) form the predominant surface species. The SCM for Pleistocene aquifer sediment resembles most the goethite SCM but shows more Si sorption. Compiled As(III) adsorption data for Holocene sediment was also well described by the SCM determined for Pleistocene aquifer sediment, suggesting a comparable As(III) affinity of Holocene and Pleistocene aquifer sediments. A forced gradient field experiment was conducted in a bank aquifer adjacent to a tributary channel to the Red River, and the passage in the aquifer of mixed groundwater containing up to 74% channel water was observed. The concentrations of As (SCM correctly predicts desorption for As(III) but for Si and PO43- it predicts an increased adsorption instead of desorption. The goethite SCM correctly predicts desorption of both As(III) and PO43- but failed in the prediction of Si desorption. These results indicate that the prediction of As mobility, by using SCMs for synthetic Fe-oxides, will be strongly dependent on the model chosen. The SCM based on the Pleistocene aquifer sediment predicts the desorption of As(III), PO43- and Si quite superiorly, as compared to the SCMs for ferrihydrite and goethite, even though Si desorption is still somewhat under-predicted. The observation that a SCM calibrated on a different sediment can predict our field results so well suggests that sediment based SCMs may be a

  8. Complex T-wave morphology in body surface potential mapping in prediction of arrhythmic events in patients with acute myocardial infarction and cardiac dysfunction. (United States)

    Korhonen, Petri; Husa, Terhi; Konttila, Teijo; Tierala, Ilkka; Mäkijärvi, Markku; Väänänen, Heikki; Toivonen, Lauri


    Heterogeneous ventricular repolarization is associated with sudden cardiac death after myocardial infarction (MI). This prospective study investigated repolarization disparity with parameters based on T-wave morphology in body surface potential mapping (BSPM) in the assessment of arrhythmia risk in patients with a recent MI and cardiac dysfunction. Patients (n = 158) had 120-lead BSPM and 12-lead electrocardiogram (ECG) registered soon after acute MI. Principal component analysis (PCA) of the T-wave and T-wave vector loop descriptors were applied to compute parameters describing T-wave morphology and its variation. The study endpoints were arrhythmic events and all-cause mortality. During a mean follow-up of 50 months, 30 patients (19%) died and 16 (10%) had an arrhythmic event. Most of the parameters differed significantly between patients with and without arrhythmic events. In univariate analysis, T-wave vector loop length (TLL) and PCA parameter PCA(3) in BSPM and TLL in ECG were significant predictors of arrhythmic events. In multivariate analysis including several clinical variables, these parameters also showed an independent prediction, with parameters in BSPM performing somewhat better. None of the parameters predicted all-cause mortality. Complex T-wave morphology in BSPM is a marker of arrhythmia propensity in patients with a recent MI and cardiac dysfunction.

  9. Synthesis, spectra and X-ray crystallography of dipyridin-2-ylmethanone oxime and its CuX2(oxime)2 complexes: Thermal, Hirshfeld surface and DFT analysis (United States)

    Warad, Ismail; Abdoh, Muneer; Al Ali, Anas; Shivalingegowda, Naveen; Kumara, Karthik; Zarrouk, Abdelkader; Lokanath, Neartur Krishnappagowda


    Dipyridin-2-ylmethanone oxime (C11H9N3O), was prepared using di-2-pyridyl ketone. The oxime ligand and its neutral CuX2 (oxime)2 (X = Cl or Br) complexes have been identified with the aid of several spectroscopic techniques such as: IR, EI-MS, EA, UV-visible, TG, 1H-NMR and finally the structure of the free oxime ligand was confirmed by X-ray diffraction studies. The oxime crystallizes in the monoclinic space group P21/c, with cell parameters a = 8.8811 (8) Å, b = 10.6362 (8) Å, c = 11.2050 (8) Å, β = 109.085 (4) º, V = 1000.26 (14) Å3 and Z = 4. The molecular conformation is stabilized by a strong intramolecular Osbnd H⋯N hydrogen bonding between the hydroxyl group of the oxime moiety and the nitrogen of the pyridine ring. Since the oxime structure was solved by XRD, the ligand structure parameters like bond length and angles were compared to the DFT computed one, the UV-visible to TD-SCF and Hirshfeld surface to MEP analysis.

  10. Complex organic pollutant mixtures originating from industrial and municipal emissions in surface waters of the megacity Jakarta-an example of a water pollution problem in emerging economies. (United States)

    Dsikowitzky, Larissa; Hagemann, Lukas; Dwiyitno; Ariyani, Farida; Irianto, Hari Eko; Schwarzbauer, Jan


    During the last decades, the global industrial production partly shifted from industrialized nations to emerging and developing countries. In these upcoming economies, the newly developed industrial centers are generally located in densely populated areas, resulting in the discharge of often only partially treated industrial and municipal wastewaters into the surface waters. There is a huge gap of knowledge about the composition of the complex organic pollutant mixtures occurring in such heavily impacted areas. Therefore, we applied a non-target screening to comprehensively assess river pollution in a large industrial area located in the megacity Jakarta. More than 100 structurally diverse organic contaminants were identified, some of which were reported here for the first time as environmental contaminants. The concentrations of paper manufacturing chemicals in river water-for example, of the endocrine-disrupting compound bisphenol A (50-8000 ng L -1 )-were as high as in pure untreated paper industry wastewaters. The non-target screening approach is the adequate tool for the identification of water contaminants in the new global centers of industrial manufacturing-as the first crucial step towards the evaluation of as yet unrecognized environmental risks.

  11. X-ray fluorescence investigation of heavy-metal contamination on metal surfaces in the Pilot Plant Complex, Aberdeen Proving Ground, Maryland

    Energy Technology Data Exchange (ETDEWEB)

    Brubaker, K.L.; Draugelis, A.K.; Schneider, J.F.; Billmark, K.A.; Zimmerman, R.E.


    A field program using a portable x-ray fluorescence (XRF) instrument was carried out to obtain data on loadings of RCRA-regulated heavy metals in paint on metal surfaces within the Pilot Plant Complex at Aberdeen Proving Ground, Maryland. Measured loadings of heavy metals were sufficiently small that they do not present problems for either human exposure or the disposition of building demolition rubble. An attempt to develop an external calibration of the XRF instrument for cadmium, chromium, and lead was unsuccessful. Significant substrate effects were observed for cadmium and chromium; for accurate results for these elements, it appears necessary to calibrate by using a sample of the actual metal substrate on which the paint is located. No substrate effects were observed for lead, but the use of lead L-shell x-ray emission lines in the instrument mode utilized in this study appears to result in a significant underestimate of the lead loading due to self-absorption of these emissions.

  12. Equivalent complex conductivities representing the effects of T-tubules and folded surface membranes on the electrical admittance and impedance of skeletal muscles measured by external-electrode method (United States)

    Sekine, Katsuhisa


    In order to represent the effects of T-tubules and folded surface membranes on the electrical admittance and impedance of skeletal muscles measured by the external-electrode method, analytical relations for the equivalent complex conductivities of hypothetical smooth surface membranes were derived. In the relations, the effects of each tubule were represented by the admittance of a straight cable. The effects of the folding of a surface membrane were represented by the increased area of surface membranes. The equivalent complex conductivities were represented as summation of these effects, and the effects of the T-tubules were different between the transversal and longitudinal directions. The validity of the equivalent complex conductivities was supported by the results of finite-difference method (FDM) calculations made using three-dimensional models in which T-tubules and folded surface membranes were represented explicitly. FDM calculations using the equivalent complex conductivities suggested that the electrically inhomogeneous structure due to the existence of muscle cells with T-tubules was sufficient for explaining the experimental results previously obtained using the external-electrode method. Results of FDM calculations in which the structural changes caused by muscle contractions were taken into account were consistent with the reported experimental results.

  13. Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites (United States)

    Glynn, P.D.


    One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the

  14. Installation of a permeable reactive barrier at the mining complex facility in Los Gigantes - Cordoba : Monitoring plan of surface and underground water

    International Nuclear Information System (INIS)

    Grande Cobian, Juan D.; Sanchez Proano, Paula; Cicerone, Daniel S.


    The Argentine National Atomic Energy Commission declares under its Environmental policy the commitment to restore those sites where activities concerning Uranium mining were developed. It makes it beyond the scope of the Project of Environmental Restitution of the Uranium Mining (PRAMU from its Spanish abbreviation). The Chemistry of Water and Soil Division at the Environmental Chemistry and Energy Generation Department belonging to the Chemistry Management Office assist the PRAMU on the installation of an hydroxyapatite permeable reactive barrier (PRB) inside the Mining Complex facility placed at Los Gigantes in the Argentine province of Cordoba (in advance named the site). Among the preliminary assessment activities that are being carried out before the installation of the PRB, it has been prepared a monitoring program of surface water and groundwater useful to develop an environmental baseline suitable for the efficiency assessment of the corrective action to be applied. An exploratory campaign was conducted in the site with the aim of establishing a monitoring net of meteorological and hydrological, as well as physical, chemical and biological parameters in matrixes of sediments, water and suspended particulate matter collected on a regular time basis from its surface water and groundwater bodies. The processed results turn into useful environmental information to: a) determine the status of the environmental baseline of the site, b) establish a water quality index (WQI) to manage the natural resource quality according to a rational basis, c) plan experiments related to the design process of a biogenic hydroxyapatite PRB and d) apply chemometric and mechanistic models to forecast the contaminants mobilization through different scenarios and improve the engineering design of the PRB. Once achieved the hydrogeological characterisation of the site and taking into account the originality of the system the following results have been reached: 1) The boundaries of

  15. From source to sink: Unravelling the complex in situ cosmogenic 10Be-14C signature in eroding bedrock surfaces and river sediment from the Bolivian Altiplano (United States)

    Hippe, Kristina; Lupker, Maarten; Gordijn, Tiemen; Ivy-Ochs, Susan; Kober, Florian; Christl, Marcus; Wacker, Lukas; Hajdas, Irka; Wieler, Rainer


    Sediment storage is a critical component of fluvial sedimentary systems. By interrupting transport processes, intermittent sediment storage can effectively decouple source from sink and buffer the transmission of signals of environmental change (e.g., in climate, vegetation, human impact) through the fluvial system. Combined in situ cosmogenic 14C-10Be analysis in fluvial sediment provides a unique method to simultaneously assess sediment transit times (in situ 14C signal) and long-term sediment production rates from bedrock erosion (10Be signal). The key is the much shorter half-life of in situ 14C compared to 10Be which causes a rapid decrease of the in situ 14C concentration when sediment is buried during sediment storage and creates an offset to 10Be. Here, we use the in situ 14C-10Be chronometer to determine changes in surface erosion and estimate absolute rates of sediment transfer in a catchment on the Bolivian Altiplano. Previous research in the study area has found a significant offset in the in situ 14C-10Be inventories from river sediments with much lower in situ 14C concentrations than expected from the 10Be content for steady-state conditions. This offset has been interpreted to reflect sediment storage over the past 11-20 ka [1]. Additional analyses of in situ 14C and 10Be in a dense network of sediment samples from the main channel and tributaries agree with previous data and yield very low in situ 14C concentrations that suggest an increase in storage duration by a few ka with downstream distance. However, analyses of in situ 14C-10Be in hilltop samples from the eroding source area reveal an almost as large offset as in the river sediments. Such complex in situ 14C-10Be inventories in the source area have a severe impact on the quantification of sediment storage times and strongly challenge previous data interpretation. The most straightforward explanation for the in situ 14C-10Be offset at hilltop locations is a change in denudation rate during the

  16. Lessons from the Crystal Structure of the S. aureus Surface Protein Clumping Factor A in Complex With Tefibazumab, an Inhibiting Monoclonal Antibody

    Directory of Open Access Journals (Sweden)

    Vannakambadi K. Ganesh


    Full Text Available The Staphylococcus aureus fibrinogen binding MSCRAMM (Microbial Surface Components Recognizing Adhesive Matrix Molecules, ClfA (clumping factor A is an important virulence factor in staphylococcal infections and a component of several vaccines currently under clinical evaluation. The mouse monoclonal antibody aurexis (also called 12-9, and the humanized version tefibazumab are therapeutic monoclonal antibodies targeting ClfA that in combination with conventional antibiotics were effective in animal models but showed less impressive efficacy in a limited Phase II clinical trial. We here report the crystal structure and a biochemical characterization of the ClfA/tefibazumab (Fab complex. The epitope for tefibazumab is located to the “top” of the N3 subdomain of ClfA and partially overlaps with a previously unidentified second binding site for fibrinogen. A high-affinity binding of ClfA to fibrinogen involves both an interaction at the N3 site and the previously identified docking of the C-terminal segment of the fibrinogen γ-chain in the N2N3 trench. Although tefibazumab binds ClfA with high affinity we observe a modest IC50 value for the inhibition of fibrinogen binding to the MSCRAMM. This observation, paired with a common natural occurring variant of ClfA that is not effectively recognized by the mAb, may partly explain the modest effect tefibazumab showed in the initial clinic trail. This information will provide guidance for the design of the next generation of therapeutic anti-staphylococcal mAbs targeting ClfA.

  17. Interseismic and coseismic surface deformation deduced from space geodetic observations : with inferences on seismic hazard, tectonic processes, earthquake complexity, and slip distribution

    NARCIS (Netherlands)

    Bos, A.G. (Annemarie Gerredina)


    In this thesis I am concerned with modeling the kinematics of surface deformation using space geodetic observations in order to advance insight in both interseismic and coseismic surface response. To model the surface deformation field I adopt the method of Spakman and Nyst (2002) which resolves the

  18. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin


    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  19. Complex chemistry with complex compounds

    Directory of Open Access Journals (Sweden)

    Eichler Robert


    Full Text Available In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the investigation of fragile single molecular species by gas-phase chromatography. The latest success with the heaviest group 6 transactinide seaborgium is highlighted. The formation of a very volatile hexacarbonyl compound Sg(CO6 was observed similarly to its lighter homologues molybdenum and tungsten. The interactions of these gaseous carbonyl complex compounds with quartz surfaces were investigated by thermochromatography. Second-generation experiments are under way to investigate the intramolecular bond between the central metal atom of the complexes and the ligands addressing the influence of relativistic effects in the heaviest compounds. Our contribution comprises some aspects of the ongoing challenging experiments as well as an outlook towards other interesting compounds related to volatile complex compounds in the gas phase.

  20. Synthesis and crystal structure of copper (II) uracil ternary polymeric complex with 1,10-phenanthroline along with the Hirshfeld surface analysis of the metal binding sites for the uracil ligand (United States)

    Patil, Yogesh Prakash; Nethaji, Munirathinam


    The study of models for "metal-enzyme-substrate" interaction has been a proactive area of research owing to its biological and pharmacological importance. In this regard the ternary copper uracil complex with 1,10-phenanthroline represents metal-enzyme-substrate system for DNA binding enzymes. The synthesis of the complex, followed by slow evaporation of the reaction mixture forms two concomitant solvatomorph crystals viz., {[Cu(phen)(μ-ura)(H2O)]n·H2O (1a)} and {[Cu(phen)(μ-ura)(H2O)]n·CH3OH (1b)}. Both complexes are structurally characterized, while elemental analysis, IR and EPR spectra were recorded for 1b (major product). In both complexes, uracil coordinates uniquely via N1 and N3 nitrogen atom acting as a bidentate bridging ligand forming a 1-D polymer. The two solvatomorphs were quantitatively analyzed for the differences with the aid of Hirshfeld surface analysis.

  1. MODIS Land Surface Temperature time series reconstruction with Open Source GIS: A new quality of temperature based ecological indicators in complex terrain (Invited) (United States)

    Neteler, M.


    In complex terrain like the Central European Alps, meteorological stations and ground surveys are usually sparsely and/or irregularly distributed and often favor agricultural areas. The application of traditional geospatial interpolation methods in complex terrain remains challenging and difficult to optimize. An alternative data source is remote sensing: high temporal resolution satellite data are continuously gaining interest since these data are intrinsically spatialized: continuous field of observations is obtained with this tool instead of point data. The increasing data availability suggests using these time series as surrogate to certain measures from meteorological stations, especially for temperature and related derivatives. The Terra and Aqua satellites with the Moderate Resolution Imaging Spectroradiometer (MODIS) provide four Earth coverages per day at various resolutions. We analyzed 8 years (2000 to 2008) of daily land surface temperature (LST) data from MODIS in an area located in the Southern European Alps. A method was developed to reconstruct incomplete maps (cloud coverage, invalid pixels) based on image statistics and on a model that includes additional GIS layers. The original LST map resolution of 1000m could be improved to 200m in this process which renders the resulting LST maps applicable at regional scales. We propose the use of these reconstructed daily LST time series as surrogate to meteorological observations especially in the area of epidemiological modeling where data are typically aggregated to decadal indicators. From these daily LST map series, derivable indicators include: 1) temperatures minima, means and maxima for annual/monthly/decadal periods; 2) unusual hot summers;3) the calculation of growing degree days, and 4) spring temperature increase or autumnal temperature decrease. Since more than 8 years of MODIS LST data are available today, even preliminary gradients can be extracted to assess multi-annual temperature trends

  2. Microsolvation of the water cation in neon: Infrared spectra and potential energy surface of the H2O+-Ne open-shell ionic complex (United States)

    Dopfer, Otto; Roth, Doris; Maier, John P.


    The intermolecular potential of the H2O+-Ne open-shell ionic dimer in its doublet electronic ground state has been investigated by infrared spectroscopy in the vicinity of the O-H stretch vibrations (ν1 and ν3) and ab initio calculations at the unrestricted Møller-Plesset second-order (MP2) level with a basis set of aug-cc-pVTZ quality. The rovibrational structure of the photodissociation spectrum is consistent with a proton-bound planar H-O-H-Ne structure and a Ne-H separation of R0=1.815(5) Å. The complexation-induced redshifts are Δν1=-69 cm-1 and Δν3=-6 cm-1, respectively. Tunneling splittings observed in the perpendicular component of the ν3 hybrid band of H2O+-Ne are attributed to hindered internal rotation between the two equivalent proton-bound equilibrium structures. The interpretation of the H2O+-Ne spectrum is supported by the spectrum of the monodeuterated species, for which both the proton-bound and the deuteron-bound isomers are observed (DOH+-Ne, HOD+-Ne). The equilibrium structure of the calculated potential energy surface of H2O+-Ne has a slightly translinear proton bond, which is characterized by a Ne-H separation of Re=1.77 Å, a bond angle of φe=174°, and dissociation energies of De=756 cm-1 and D0=476 cm-1. According to the calculated potential, the exchange tunneling between the two equivalent minima occurs via the planar bridged transition state with C2v symmetry and a barrier of 340 cm-1. In general, the calculated properties of H2O+-Ne show good agreement with the experimental data. Initial steps in the microsolvation of the water cation in neon are discussed by comparing the calculated and experimental properties of H2O+-Nen (n=0-2) with neon matrix isolation data (n→∞).

  3. The murine cytomegalovirus immune evasion protein m4/gp34 forms biochemically distinct complexes with class I MHC at the cell surface and in a pre-Golgi compartment. (United States)

    Kavanagh, D G; Koszinowski, U H; Hill, A B


    We have recently demonstrated that the murine CMV (MCMV) gene m4 is an immune evasion gene that protects MCMV-infected targets from some virus-specific CTL clones. m4 encodes m4/gp34, a 34-kDa glycoprotein that binds to major histocompatibility complex class I in the endoplasmic reticulum and forms a detergent-stable complex that is exported to the surface of the cell. To investigate how m4/gp34 promotes CTL evasion, we analyzed the assembly and export of m4/gp34-K(b) complexes. We found that 50-70% of K(b) exported over the course of MCMV infection was m4/gp34 associated. Because these complexes are present at the cell surface, it is possible that m4 mediates CTL evasion by interfering with contact between class I and receptors on the T cell. In addition, we found that K(b) retained by the MCMV immune evasion gene m152 formed a novel type of complex with Endo H-sensitive m4/gp34; these complexes are distinguished from the exported complexes by being stable in 1% digitonin and unstable in 1% Nonidet P-40. Because this association occurs in a pre-Golgi compartment, m4/gp34 might also interfere with Ag presentation by affecting some aspect of class I assembly, such as peptide loading. Although m4/gp34 requires beta(2)-microglobulin to bind class I, there was no significant binding of m4/gp34 to beta(2)-microglobulin in the absence of class I H chain, demonstrating that m4/gp34 forms Nonidet P-40-stable complexes specifically with folded conformations of class I. We conclude that m4/gp34 promotes immune evasion by a novel mechanism involving altered assembly and/or T cell recognition of class I molecules.

  4. Assembly, intracellular processing, and expression at the cell surface of the human alpha beta T cell receptor/CD3 complex. Function of the CD3-zeta chain

    DEFF Research Database (Denmark)

    Geisler, C; Kuhlmann, J; Rubin, B


    complex, the role of the CD3 chains for the TCR/CD3 expression have not been experimentally addressed in human T cells. In this study the function of the CD3-zeta chain for the assembly, intracellular processing, and expression of the TCR/CD3 complex in the human leukemic T cell line Jurkat...

  5. Films prepared from poly(vinyl alcohol) and amylose-fatty acid salt inclusion complexes with increased surface hydrophobicity and high elongation (United States)

    In this study, water-soluble amylose-inclusion complexes were prepared from high amylose corn starch and sodium salts of lauric, palmitic, and stearic acid by steam jet cooking. Cast films were prepared by combining the amylose complexes with poly(vinyl alcohol)(PVOH) solution at ratios varying from...

  6. An Electrochemical and Raman Spectroscopy Study of the Surface Behaviour of Mononuclear Ruthenium and Osmium Polypyridyl Complexes Based on Pyridyl- and Thiophene-Based Linkers

    NARCIS (Netherlands)

    Halpin, Yvonne; Logtenberg, Hella; Cleary, Laura; Schenk, Stephan; Schulz, Martin; Draksharapu, Apparao; Browne, Wesley R.; Vos, Johannes G.


    The utility of a thiophene anchor unit as an alternative for thiols in the immobilisation of ruthenium and osmium complexes on gold and platinum is examined with special attention focused on the relative contributions of physi- and chemisorption of the complexes and the chemical stability of the

  7. Complex Systems

    Directory of Open Access Journals (Sweden)

    Yi Zhao


    Full Text Available Quantum instanton (QI approximation is recently proposed for the evaluations of the chemical reaction rate constants with use of full dimensional potential energy surfaces. Its strategy is to use the instanton mechanism and to approximate time-dependent quantum dynamics to the imaginary time propagation of the quantities of partition function. It thus incorporates the properties of the instanton idea and the quantum effect of partition function and can be applied to chemical reactions of complex systems. In this paper, we present the QI approach and its applications to several complex systems mainly done by us. The concrete systems include, (1 the reaction of H+CH4→H2+CH3, (2 the reaction of H+SiH4→H2+SiH3, (3 H diffusion on Ni(100 surface; and (4 surface-subsurface transport and interior migration for H/Ni. Available experimental and other theoretical data are also presented for the purpose of comparison.

  8. Identification of an hexapeptide that binds to a surface pocket in cyclin A and inhibits the catalytic activity of the complex cyclin-dependent kinase 2-cyclin A. (United States)

    Canela, Núria; Orzáez, Mar; Fucho, Raquel; Mateo, Francesca; Gutierrez, Ricardo; Pineda-Lucena, Antonio; Bachs, Oriol; Pérez-Payá, Enrique


    The protein-protein complexes formed between different cyclins and cyclin-dependent kinases (CDKs) are central to cell cycle regulation. These complexes represent interesting points of chemical intervention for the development of antineoplastic molecules. Here we describe the identification of an all d-amino acid hexapeptide, termed NBI1, that inhibits the kinase activity of the cyclin-dependent kinase 2 (cdk2)-cyclin A complex through selective binding to cyclin A. The mechanism of inhibition is non-competitive for ATP and non-competitive for protein substrates. In contrast to the existing CDKs peptide inhibitors, the hexapeptide NBI1 interferes with the formation of the cdk2-cyclin A complex. Furthermore, a cell-permeable derivative of NBI1 induces apoptosis and inhibits proliferation of tumor cell lines. Thus, the NBI1-binding site on cyclin A may represent a new target site for the selective inhibition of activity cdk2-cyclin A complex.

  9. Influence of structural and surface properties of whey-derived peptides on zinc-chelating capacity, and in vitro gastric stability and bioaccessibility of the zinc-peptide complexes. (United States)

    Udechukwu, M Chinonye; Downey, Brianna; Udenigwe, Chibuike C


    Gastrointestinal stability of zinc-peptide complexes is essential for zinc delivery. As peptide surface charge can influence their metal complex stability, we evaluated the zinc-chelating capacity and stability of zinc complexes of whey protein hydrolysates (WPH), produced with Everlase (WPH-Ever; ζ-potential, -39mV) and papain (WPH-Pap; ζ-potential, -7mV), during simulated digestion. WPH-Ever had lower amount of zinc-binding amino acids but showed higher zinc-chelating capacity than WPH-Pap. This is attributable to the highly anionic surface charge of WPH-Ever for electrostatic interaction with zinc. Release of zinc during peptic digestion was lower for WPH-Ever-zinc, and over 50% of zinc remained bound in both peptide complexes after peptic-pancreatic digestion. Fourier transform infrared spectroscopy suggests the involvement of carboxylate ion, and sidechain carbon-oxygen of aspartate/glutamate and serine/threonine in zinc-peptide complexation. The findings indicate that strong zinc chelation can promote gastric stability and impede intestinal release, for peptides intended for use as dietary zinc carriers. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. The glycoprotein Ib-IX-V complex contributes to tissue factor-independent thrombin generation by recombinant factor VIIa on the activated platelet surface

    NARCIS (Netherlands)

    Weeterings, Cees; de Groot, Philip G.; Adelmeijer, Jelle; Lisman, Ton


    Several lines of evidence suggest that recombinant factor VIIa (rFVIIa) is able to activate factor X on an activated platelet, in a tissue factor-independent manner. We hypothesized that, besides the anionic surface, a receptor on the activated platelet surface is involved in this process. Here, we

  11. The use of a well-defined surface organometallic complex as a probe molecule: [(≡SiO)TaVCl2Me2] shows different isolated silanol sites on the silica surface

    KAUST Repository

    Chen, Yin


    TaVCl2Me3 reacts with silica(700) and produces two different [(≡SiO)TaVCl2Me2] surface organometallic species, suggesting a heterogeneity of the highly dehydroxylated silica surface, which was studied with a combined experimental and theoretical approach. This journal is © the Partner Organisations 2014.

  12. Inefficient entry of vicriviroc-resistant HIV-1 via the inhibitor-CCR5 complex at low cell surface CCR5 densities


    Pugach, Pavel; Ray, Neelanjana; Klasse, Per Johan; Ketas, Thomas J.; Michael, Elizabeth; Doms, Robert W.; Lee, Benhur; Moore, John P.


    HIV-1 variants resistant to small molecule CCR5 inhibitors such as vicriviroc (VVC) have modified Env complexes that can use both the inhibitor-bound and -free forms of the CCR5 co-receptor to enter target cells. However, entry via the inhibitor-CCR5 complex is inefficient in some, but not all, cell types, particularly cell lines engineered to express CCR5. We investigated the effect of increasing CCR5 expression, and hence the density of the inhibitor-CCR5 complex when a saturating inhibitor...

  13. Active faulting Vs other surface displacing complex geomorphic phenomena. Case studies from a tectonically active area, Abruzzi Region, central Apennines, Italy (United States)

    Lo Sardo, Lorenzo; Gori, Stefano; Falcucci, Emanuela; Saroli, Michele; Moro, Marco; Galadini, Fabrizio; Lancia, Michele; Fubelli, Giandomenico; Pezzo, Giuseppe


    How can be univocally inferred the genesis of a linear surface scarp as the result of an active and capable fault (FAC) in tectonically active regions? Or, conversely, how it is possible to exclude that a scarp is the result of a capable fault activation? Trying to unravel this open questions, we show two ambiguous case studies about the problem of the identification of active and capable faults in a tectonically active area just based on the presence of supposed fault scarps at surface. The selected cases are located in the area comprised between the Middle Aterno Valley Fault (MAVF) and the Campo Imperatore Plain (Abruzzi Region, central Apennines), nearby the epicentral area of the April 6th, 2009 L'Aquila earthquake. In particular, the two case studies analysed are located in a region characterized by a widespread Quaternary faults and by several linear scarps: the case studies of (i) Prata D'Ansidonia area and (ii) Santo Stefano di Sessanio area. To assess the origin and the state of activity of the investigated geomorphic features, we applied a classical geological and geomorphological approach, based on the analysis of the available literature, the interpretation of the aerial photographs, field surveying and classical paleoseismological approach, the latter consisting in digging excavations across the analysed scarps. These analysis were then integrated by morphometrical analyses. As for case (i), we focused on determining the geomorphic "meaning" of linear scarps carved onto fluvial-deltaic conglomerates (dated to the Early Pleistocene; Bertini and Bosi, 1993), up to 3 meters high and up to 1,5 km long, that border a narrow, elongated and flat-bottom depressions, filled by colluvial deposits. These features groove the paleo-landsurface of Valle Daria (Bosi and Bertini, 1970), wide landsurface located between Barisciano and Prata D'Ansidonia. Entwining paleoseismological trenching with geophysical analyses (GPR, ERT and microgravimetrical prospections), it

  14. Ab initio study of the intermolecular potential energy surface in the ion-induced-dipole hydrogen-bonded O2(-)(X2Πg)-H2(X1Σg(+)) complex. (United States)

    Fawzy, Wafaa M


    This work presents the first investigation on the intermolecular potential energy surface of the ground electronic state of the O2(-)(2Πg)-H2(1Σg(+)) complex. High level correlated ab initio calculations were carried out using the Hartree-Fock spin-unrestricted coupled cluster singles and doubles including perturbative triples correction [RHF-UCCSD(T)]/aug-cc-pVXZ levels of calculations, where XZ = DZ, TZ, QZ, and 5Z. Results of full geometry optimization and the intermolecular potential energy surface (IPES) calculations show four equivalent minimum energy structures of L-shaped geometry with Cs symmetry at equilibrium along the 2A″ surface of the complex. For these equilibrium minimum energy structures, the most accurate value for the dissociation energy (De) was calculated as 1407.7 cm(-1), which was obtained by extrapolating the counterpoise (CP) corrected De values to the complete basis set (CBS) limit. This global minimum energy structure is stabilized by an ion-induced-dipole hydrogen bond. Detailed investigations of the IPES show that the collinear structure is unstable, while the C2v geometries present saddle points along the 2A″ surface. The barrier height between the two equivalent structures that differs in whether the hydrogen-bonded hydrogen atom is above or below the axis that connects centers of masses of the H2 and O2(-) moieties within the complex was calculated as 70 cm(-1). This suggests that the complex exhibits large amplitude motion. The barrier height to rotation of the H2 moiety by 180° within the complex is 1020 cm(-1). Anharmonic oscillator calculations predicted a strong H-H stretch fundamental transition at 3807 cm(-1). Results of the current work are expected to stimulate further theoretical and experimental investigations on the nature of intermolecular interactions in complexes that contain the superoxide radical and various closed-shell molecules that model atmospheric and biological molecules. These studies are fundamental

  15. Coordination chemistry for antibacterial materials: a monolayer of a Cu(2+) 2,2'-bipyridine complex grafted on a glass surface. (United States)

    Pallavicini, Piersandro; Dacarro, Giacomo; Grisoli, Pietro; Mangano, Carlo; Patrini, Maddalena; Rigoni, Federica; Sangaletti, Luigi; Taglietti, Angelo


    A propyltrimethoxysilane-modified 2,2'-bipyridine ligand is synthesized and its acetonitrile solutions are used to prepare monolayers of the molecule on glass surfaces. Absorption and X-ray photoelectron spectroscopy demonstrate that the modified glass surfaces bind Cu(2+) with a 1:1 ratio with respect to the 2,2'-bipyridine moieties under the chosen preparative conditions, producing materials bearing 0.016 μg cm(-2) of copper. Although in trace amounts, the bound Cu(2+) cations exert a significant microbicidal effect against Escherichia coli and Staphylococcus aureus.

  16. Ab Initio Calculations of the Electronic Properties of Polypyridine Transition Metal Complexes and Their Adsorption on Metal Surfaces in the Presence of Solvent and Counterions

    DEFF Research Database (Denmark)

    Jónsson, E. Ö.; Thygesen, Kristian Sommer; Ulstrup, Jens


    of the complexes in the presence of the solvent, are conserved upon adsorption, whereas the structural features of the different oxidation states are completely lost upon adsorption under vacuum conditions. Detailed microscopic insight such as offered by the present study will be important in molecular...

  17. Regular square planer bis-(4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione)/copper(II) complex: Trans/cis-DFT isomerization, crystal structure, thermal, solvatochromism, hirshfeld surface and DNA-binding analysis (United States)

    Hema, M. K.; Karthik, C. S.; Warad, Ismail; Lokanath, N. K.; Zarrouk, Abdelkader; Kumara, Karthik; Pampa, K. J.; Mallu, P.


    Trans-[Cu(O∩O)2] complex, O∩O = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione was reported with high potential toward CT-DNA binder. The solved XRD-structure of complex indicated a perfect regular square-planer geometry around the Cu(II) center. The trans/cis-DFT-isomerization calculation supported the XRD seen in reflecting the trans-isomer as the kinetic-favor isomer. The desired complex structure was also characterized by conductivity measurement, CHN-elemental analyses, MS, EDX, SEM, UV-Vis., FT-IR, HAS and TG/DTG. The Solvatochromism behavior of the complex was evaluated using four different polar solvents. MPE and Hirshfeld surface analysis (HSA) come to an agreement that fluoride and thiophene protons atoms are with suitable electro-potential environment to form non-classical H-bonds of type CThsbnd H⋯F. The DNA-binding properties were investigated by viscosity tests and spectrometric titrations, the results revealed the complex as strong calf-thymus DNA binder. High intrinsic-binding constants value ∼1.8 × 105 was collected.

  18. Sonochemical synthesis of a new cobalt(II) complex: Crystal structure, thermal behavior, Hirshfeld surface analysis and its usage as precursor for preparation of CoO/Co3O4 nanoparticles. (United States)

    Montazerozohori, Morteza; Masoudiasl, Ardavan; Farokhiyani, Sara; Joohari, Shiva; McArdle, Patrick


    A bidentate Schiff base ligand and its nano-structured cobalt(II) complex were synthesized under ultrasound irradiation and then their structures were identified by physical and spectral techniques SEM and XRD techniques were used to confirm the nanostructure character of the complex. Single crystal X-ray diffraction analysis showed that the complex crystallizes in the triclinic system with space group of P1¯ and two crystallographically independent molecules participate in its asymmetric unit. In the structure of complex, cobalt center is four-coordinated by two iminic nitrogens of bidentate Schiff base ligand and two bromide anions in a distorted tetrahedral geometry. Crystal packing analysis well indicates that C-H⋯Br, C-H⋯π and π⋯π are the most intermolecular interactions. Moreover Hirshfeld surface analysis and 2D Fingerprint plots were applied for more investigation of intermolecular interactions. In addition, sonochemically prepared cobalt(II) bromide complex was subjected to calcination process under air atmosphere for preparation of cobalt oxide nanoparticles. The XRD pattern confirmed the simultaneous formation of CoO and Co 3 O 4 nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Complex differential geometry

    CERN Document Server

    Zheng, Fangyang


    The theory of complex manifolds overlaps with several branches of mathematics, including differential geometry, algebraic geometry, several complex variables, global analysis, topology, algebraic number theory, and mathematical physics. Complex manifolds provide a rich class of geometric objects, for example the (common) zero locus of any generic set of complex polynomials is always a complex manifold. Yet complex manifolds behave differently than generic smooth manifolds; they are more coherent and fragile. The rich yet restrictive character of complex manifolds makes them a special and interesting object of study. This book is a self-contained graduate textbook that discusses the differential geometric aspects of complex manifolds. The first part contains standard materials from general topology, differentiable manifolds, and basic Riemannian geometry. The second part discusses complex manifolds and analytic varieties, sheaves and holomorphic vector bundles, and gives a brief account of the surface classifi...

  20. On the characterization of host-guest complexes : Surface tension, calorimetry, and molecular dynamics of cyclodextrins with a non-ionic surfactant

    NARCIS (Netherlands)

    Pineiro, Angel; Banquy, Xavier; Perez-Casas, Silvia; Tovar, Edgar; Garcia, Abel; Villa, Alessandra; Amigo, Alfredo; Mark, Alan E.; Costas, Miguel


    Three host-guest systems have been characterized using surface tension (sigma), calorimetry, and molecular dynamics simulations (MD). The hosts were three native cyclodextrins (CD) and the guest the non-ionic carbohydrate surfactant octyl-beta-d-glucopyranoside. It is shown that, for any host-guest

  1. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

    Directory of Open Access Journals (Sweden)

    Martin Popr


    Full Text Available The thermal stability of the monosubstituted cationic cyclodextrin (CD derivatives PEMEDA-β-CD and PEMPDA-β-CD, which differ in their substituent linker length (ethylene and propylene, respectively, was studied via 1H NMR experiments. PEMPDA-β-CD exhibited higher resistance towards the Hofmann degradation and was chosen as a more suitable host molecule for further studies. Inclusion properties of PEMPDA-β-CD in solution with a series of simple aromatic guests (salicylic acid, p-methoxyphenol and p-nitroaniline were determined by isothermal titration calorimetry (ITC and compared to the native β-CD. Permanently charged cationic CD derivatives were successfully deposited on the anionic solid surface of polymeric Nafion® 117 membrane via electrostatic interactions. Deposition kinetics and coverage of the surface were determined by ELSD. Finally, the ability of the CD derivatives bound to the solid surface to encapsulate aromatic compounds from aqueous solution was measured by UV–vis spectroscopy. The obtained results are promising for future industrial applications of the monosubstituted β-CD derivatives, because the preparation of cationic CD derivatives is applicable in large scale, without the need of chromatographic purification. Their ionic deposition on a solid surface is simple, yet robust and a straightforward process as well.

  2. Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

    Czech Academy of Sciences Publication Activity Database

    Popr, M.; Filippov, Sergey K.; Matushkin, Nikolai; Dian, J.; Jindřich, J.


    Roč. 11, February (2015), s. 192-199 ISSN 1860-5397 R&D Projects: GA ČR GAP108/12/0640 Institutional support: RVO:61389013 Keywords : cyclodextrins * inclusion properties * solid surface Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.697, year: 2015

  3. Metal-metal bonding and structures of metal string complexes Cr3(dpa)4Cl2, Cr3(dpa)4(NCS)2, and [Cr3(dpa)4Cl2](PF6) from IR, Raman, and surface-enhanced Raman spectra. (United States)

    Hsiao, Chung-Jen; Lai, Szu-Hsueh; Chen, I-Chia; Wang, Wen-Zhen; Peng, Shie-Ming


    We recorded infrared, Raman, and surface-enhanced Raman scattering (SERS) spectra of metal-string complexes Cr(3)(dpa)(4)X(2) (dpa = di(2-pyridyl)amido, X = Cl, NCS) and [Cr(3)(dpa)(4)Cl(2)](PF(6)) and dipyridylamine (Hdpa) to determine their vibrational frequencies and to study their structures. For the SERS measurements these complexes were adsorbed on silver nanoparticles in aqueous solution to eliminate the constraints of a crystal lattice. From the results of analysis of the vibrational normal modes we assign the infrared band at 346 cm(-1) to the Cr(3) asymmetric stretching vibration of the symmetric form and the Raman line at 570 cm(-1) to the Cr-Cr stretching mode for the unsymmetric form of Cr(3)(dpa)(4)Cl(2). Complex Cr(3)(dpa)(4)Cl(2) exhibits both symmetric (s-) and unsymmetric (u-) forms in solution but Cr(3)(dpa)(4)(NCS)(2) only the s-form. The structures for both complexes in their ground states have the s-form. The oxidized complex [Cr(3)(dpa)(4)Cl(2)](PF(6)) has only a u-form for which the Cr-Cr stretching mode is assigned to the band at 570 cm(-1). From the variation with temperature from 23 to 60 degrees C of the intensity of this line, we obtained the proportion of the u-form Cr(3)(dpa)(4)Cl(2); the enthalpy change is thus obtained to be DeltaH = 46.2 +/- 3.3 kJ mol(-1) and the entropy change is DeltaS = 138 +/- 10.3 J K(-1) mol(-1) for the reaction u-Cr(3)(dpa)(4)Cl(2) s-Cr(3)(dpa)(4)Cl(2). From the spectral intensities and band frequencies in SERS spectra, Hdpa is expected to adsorb on a silver nanoparticle with the amido nitrogen and pyridyl rings tilted from the silver surface, whereas the trichromium complex with the chromium ion line is orthogonal to the silver surface normal in aqueous silver solution.

  4. Surface energy-driven growth of crystalline PbS octahedra and dendrites in the presence of cyclodextrin–surfactant supramolecular complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Pradip, E-mail:; Kim, Whi Dong; Lee, Seokwon; Lee, Dennis T. [Korea Advanced Institute of Science and Technology (KAIST), Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (Korea, Republic of); Lee, Kangtaek [Yonsei University, Department of Chemical and Biomolecular Engineering (Korea, Republic of); Lee, Doh C., E-mail: [Korea Advanced Institute of Science and Technology (KAIST), Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (Korea, Republic of)


    PbS crystals of cubic, octahedral, and dendritic shapes are synthesized in an aqueous solution that contains supramolecular complexes of β-cyclodextrin (CD) and hexadecyltrimethylammonium bromide (CTAB). The morphology of the PbS crystals depends on the concentration of CD or CTAB in the reaction solution; for example, the branched dendritic structures evolve with an appropriate molar ratio of CD/CTAB supramolecular complexes and reaction time. Regardless of the CD/CTAB molar ratios, octahedral PbS crystals are observed at all compositions of CD/CTAB for the reaction times of 1–5 h, while self-assembled branched/dendritic structures are obtained only for CD/CTAB molar ratios of 0.5, 1, and 2 after a prolonged reaction, e.g., for 24–48 h. Systematic investigation reveals that both reaction time and CD/CTAB molar ratio are responsible for self-assembled branched/dendritic structures of octahedral crystals.

  5. Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Yeqing Tao

    Full Text Available Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18 is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA, a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

  6. Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry. (United States)

    Tao, Yeqing; Fang, Pengfei; Kim, Sunghoon; Guo, Min; Young, Nicolas L; Marshall, Alan G


    Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18) is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA), a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX) for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

  7. In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal and Surface Complexation Using Soft X-Ray

    International Nuclear Information System (INIS)

    Myneni, Satish C.


    Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

  8. Impact of surface water recharge on the design of a groundwater monitoring system for the Radioactive Waste Management Complex, Idaho National Engineering Laboratory

    International Nuclear Information System (INIS)

    Wood, T.R.


    Recent hydrogeologic studies have been initiated to characterize the hydrogeologic conditions at the Radioactive Waste Management Complex (RWMC) at the Idaho National Engineering Laboratory (INEL). Measured water levels in wells penetrating the Snake River Plain aquifer near the RWMC and the corresponding direction of flow show change over time. This change is related to water table mounding caused by recharge from excess water diverted from the Big Lost River for flood protection during high flows. Water levels in most wells near the RWMC rise on the order of 10 ft (3 m) in response to recharge, with water in one well rising over 60 ft (18 m). Recharge changes the normal south-southwest direction of flow to the east. Design of the proposed groundwater monitoring network for the RWMC must account for the variable directions of groundwater flow. 11 refs., 9 figs., 2 tabs

  9. Fluorescent detection of apoptotic cells using a family of zinc coordination complexes with selective affinity for membrane surfaces that are enriched with phosphatidylserine.

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Bradley D. (University of Notre Dame, Notre Dame, Indiana); Lambert, Timothy N.; Lakshmi, C. (University of Notre Dame, Notre Dame, Indiana); Hanshaw, Roger, G. (University of Notre Dame, Notre Dame, Indiana)


    The appearance of phosphatidylserine on the membrane surface of apoptotic cells (Jurkat, CHO, HeLa) is monitored by using a family of bis(Zn{sup 2+}-2,2{prime}-dipicolylamine) coordination compounds with appended fluorescein or biotin groups as reporter elements. The phosphatidylserine affinity group is also conjugated directly to a CdSe/CdS quantum dot to produce a probe suitable for prolonged observation without photobleaching. Apoptosis can be detected under a wide variety of conditions, including variations in temperature, incubation time, and binding media. Binding of each probe appears to be restricted to the cell membrane exterior, because no staining of organelles or internal membranes is observed.

  10. Personal care products in surface, ground and wastewater of a complex aquifer system, a potential planning tool for contemporary urban settings. (United States)

    Palmiotto, Marinella; Castiglioni, Sara; Zuccato, Ettore; Manenti, Angela; Riva, Francesco; Davoli, Enrico


    The use and discharge of personal care products (PCPs) result in their presence in the aquatic environment. This study investigates the occurrence and fate of some PCPs in wastewater, surface and groundwater in an urbanized area in the North of Italy. We investigated four UV filters: phenylbenzimidazole sulfonic acid (PBSA), benzophenone-3 (BP3), benzophenone-4 (BP4) and 4 methyl-benzilidine-camphor (4-MBC), and two antibacterial agents: triclosan (TCS) and triclocarban (TCC). BP3, BP4 and PBSA were detected in all WWTPs and concentrations ranged 27-822 ng/L (BP4 > PBSA > BP3). TCS was the only disinfectant detected in wastewater and ranged from urban trends and suggesting paths for the planning in urban regions and for appropriate investment and rehabilitation strategies of infrastructure. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Complexity explained

    CERN Document Server

    Erdi, Peter


    This book explains why complex systems research is important in understanding the structure, function and dynamics of complex natural and social phenomena. Readers will learn the basic concepts and methods of complex system research.

  12. Holocene surface-faulting earthquakes at the Spring Lake and North Creek Sites on the Wasatch Fault Zone: Evidence for complex rupture of the Nephi Segment (United States)

    Duross, Christopher; Hylland, Michael D.; Hiscock, Adam; Personius, Stephen; Briggs, Richard; Gold, Ryan D.; Beukelman, Gregg; McDonald, Geg N; Erickson, Ben; McKean, Adam; Angster, Steve; King, Roselyn; Crone, Anthony J.; Mahan, Shannon


    The Nephi segment of the Wasatch fault zone (WFZ) comprises two fault strands, the northern and southern strands, which have evidence of recurrent late Holocene surface-faulting earthquakes. We excavated paleoseismic trenches across these strands to refine and expand their Holocene earthquake chronologies; improve estimates of earthquake recurrence, displacement, and fault slip rate; and assess whether the strands rupture separately or synchronously in large earthquakes. Paleoseismic data from the Spring Lake site expand the Holocene record of earthquakes on the northern strand: at least five to seven earthquakes ruptured the Spring Lake site at 0.9 ± 0.2 ka (2σ), 2.9 ± 0.7 ka, 4.0 ± 0.5 ka, 4.8 ± 0.8 ka, 5.7 ± 0.8 ka, 6.6 ± 0.7 ka, and 13.1 ± 4.0 ka, yielding a Holocene mean recurrence of ~1.2–1.5 kyr and vertical slip rate of ~0.5–0.8 mm/yr. Paleoseismic data from the North Creek site help refine the Holocene earthquake chronology for the southern strand: at least five earthquakes ruptured the North Creek site at 0.2 ± 0.1 ka (2σ), 1.2 ± 0.1 ka, 2.6 ± 0.9 ka, 4.0 ± 0.1 ka, and 4.7 ± 0.7 ka, yielding a mean recurrence of 1.1–1.3 kyr and vertical slip rate of ~1.9–2.0 mm/yr. We compare these Spring Lake and North Creek data with previous paleoseismic data for the Nephi segment and report late Holocene mean recurrence intervals of ~1.0–1.2 kyr for the northern strand and ~1.1–1.3 kyr for the southern strand. The northern and southern strands have similar late Holocene earthquake histories, which allow for models of both independent and synchronous rupture. However, considering the earthquake timing probabilities and per-event vertical displacements, we have the greatest confidence in the simultaneous rupture of the strands, including rupture of one strand with spillover rupture to the other. Ultimately, our results improve the surface-faulting earthquake history of the Nephi segment and enhance our understanding of how structural barriers

  13. Use of synthetic peptides to represent surface-exposed epitopes defined by neutralizing dengue complex- and flavivirus group-reactive monoclonal antibodies on the native dengue type-2 virus envelope glycoprotein. (United States)

    Falconar, Andrew K I


    The reactions of neutralizing monoclonal antibodies (mAbs) that defined dengue virus (DENV) complex, flavivirus subgroup or group neutralizing epitopes were tested against synthetic peptide sequences from domains I, II and III of the envelope (E) glycoproteins of different DENV-2 genotypes/strains. The DENV complex-reactive mAb identified the surface-exposed 304-GKFKV/IVKEIA-313 peptides and the DENV complex-conserved 393-KKGSSIGQ/KM-401 peptides in domain III, which were located adjacently in the native glycoprotein. Both flavivirus group-reactive mAbs reacted most strongly with fusion sequence peptides from domain II when they contained a cysteine (C) by glycine (G) substitution (underlined) (101-WGNGGGLFG-109) to represent the native rotated C side chain. The 393-401 sequence represents a newly identified epitope, present as a highly flexible coil located between the 385 and 393 cell-binding sequence and the 401 and 413 sequence involved in the E glycoprotein homo-trimer formation. The 101-109 sequence containing 105-C by G substitution and the 393-401 sequence are good candidates for diagnostic assays and cross-protection experiments.

  14. Surface deformation time series and source modeling for a volcanic complex system based on satellite wide swath and image mode interferometry: The Lazufre system, central Andes (United States)

    Anderssohn, J.; Motagh, M.; Walter, T. R.; Rosenau, M.; Kaufmann, H.; Oncken, O.


    The variable spatio-temporal scales of Earth's surface deformation in potentially hazardous volcanic areas pose a challenge for observation and assessment. Here we used Envisat data acquired in Wide Swath Mode (WSM) and Image Mode (IM) from ascending and descending geometry, respectively, to study time-dependent ground uplift at the Lazufre volcanic system in Chile and Argentina. A least-squares adjustment was performed on 65 IM interferograms that covered the time period of 2003-2008. We obtained a clear trend of uplift reaching 15-16 cm in this 5-year interval. Using a joint inversion of ascending and descending interferograms, we evaluated the geometry and time-dependent progression of a horizontally extended pressurized source beneath the Lazufre volcanic system. Our results hence indicate that an extended magma body at a depth between 10 and 15 km would account for most of the ground uplift. The maximum inflation reached up to ~40 cm during 2003-2008. The lateral propagation velocity of the intrusion was estimated to be nearly constant at 5-10 km/yr during the observation time, which has important implications for the physical understanding of magma intrusion processes.

  15. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon


    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  16. Relation of hydrologic processes to groundwater and surface-water levels and flow directions in a dune-beach complex at Indiana Dunes National Lakeshore and Beverly Shores, Indiana (United States)

    Buszka, Paul M.; Cohen, David A.; Lampe, David C.; Pavlovic, Noel B.


    The potential for high groundwater levels to cause wet basements (groundwater flooding) is of concern to residents of communities in northwestern Indiana. Changes in recharge from precipitation increases during 2006-9, water-level changes from restoration of nearby wetlands in the Great Marsh in 1998-2002, and changes in recharge due to the end of groundwater withdrawals for water supply since 2005 in a community at Beverly Shores, Ind., were suspected as factors in increased groundwater levels in an unconfined surficial aquifer beneath nearby parts of a dune-beach complex. Results of this study indicate that increased recharge from precipitation and snowmelt was the principal cause of raised water levels in the dune-beach complex from 2006 to 2009. Annual precipitation totals in 2006-9 ranged from 43.88 to 55.75 inches per year (in/yr) and were substantially greater than the median 1952-2009 precipitation of 36.35 in/yr. Recharge to groundwater from precipitation in 2006-9 ranged from 13.5 to 22 in/yr; it was higher than the typical 11 in/yr because of large precipitation events and precipitation amounts received during non-growing-season months. An estimated increase in net recharge from reduced groundwater use in Beverly Shores since 2005 ranged from 1.6 in/yr in 2006 to 1.9 in/yr in 2009. Surface-water levels in the wetland were as much as about 1.1 feet higher in 2007-9 (after the 1998-2002 wetland restoration) than during seasonally wet periods in 1979-89. Similar surface-water levels and ponded water were likely during winter and spring wet periods before and after wetland restoration. High water levels similar to those in 2009 were measured elsewhere in the dune-beach complex near a natural wetland during the spring months in 1991 and 1993 after receipt of near record precipitation. Recharge from similarly high precipitation amounts in 2008-9 was also a likely cause of high groundwater levels in other parts of the dune-beach complex, such as at Beverly

  17. Optical momentum and angular momentum in complex media: from the Abraham–Minkowski debate to unusual properties of surface plasmon-polaritons (United States)

    Bliokh, Konstantin Y.; Bekshaev, Aleksandr Y.; Nori, Franco


    We examine the momentum and angular momentum (AM) properties of monochromatic optical fields in dispersive and inhomogeneous isotropic media, using the Abraham- and Minkowski-type approaches, as well as the kinetic (Poynting-like) and canonical (with separate spin and orbital degrees of freedom) pictures. While the kinetic Abraham–Poynting momentum describes the energy flux and the group velocity of the wave, the Minkowski-type quantities, with proper dispersion corrections, describe the actual momentum and AM carried by the wave. The kinetic Minkowski-type momentum and AM densities agree with phenomenological results derived by Philbin. Using the canonical spin–orbital decomposition, previously used for free-space fields, we find the corresponding canonical momentum, spin and orbital AM of light in a dispersive inhomogeneous medium. These acquire a very natural form analogous to the Brillouin energy density and are valid for arbitrary structured fields. The general theory is applied to a non-trivial example of a surface plasmon-polariton (SPP) wave at a metal-vacuum interface. We show that the integral momentum of the SPP per particle corresponds to the SPP wave vector, and hence exceeds the momentum of a photon in the vacuum. We also provide the first accurate calculation of the transverse spin and orbital AM of the SPP. While the intrinsic orbital AM vanishes, the transverse spin can change its sign depending on the SPP frequency. Importantly, we present both macroscopic and microscopic calculations, thereby proving the validity of the general phenomenological results. The microscopic theory also predicts a transverse magnetization in the metal (i.e. a magnetic moment for the SPP) as well as the corresponding direct magnetization current, which provides the difference between the Abraham and Minkowski momenta.

  18. Optical momentum and angular momentum in complex media: from the Abraham-Minkowski debate to unusual properties of surface plasmon-polaritons (United States)

    Y Bliokh, Konstantin; Y Bekshaev, Aleksandr; Nori, Franco


    We examine the momentum and angular momentum (AM) properties of monochromatic optical fields in dispersive and inhomogeneous isotropic media, using the Abraham- and Minkowski-type approaches, as well as the kinetic (Poynting-like) and canonical (with separate spin and orbital degrees of freedom) pictures. While the kinetic Abraham-Poynting momentum describes the energy flux and the group velocity of the wave, the Minkowski-type quantities, with proper dispersion corrections, describe the actual momentum and AM carried by the wave. The kinetic Minkowski-type momentum and AM densities agree with phenomenological results derived by Philbin. Using the canonical spin-orbital decomposition, previously used for free-space fields, we find the corresponding canonical momentum, spin and orbital AM of light in a dispersive inhomogeneous medium. These acquire a very natural form analogous to the Brillouin energy density and are valid for arbitrary structured fields. The general theory is applied to a non-trivial example of a surface plasmon-polariton (SPP) wave at a metal-vacuum interface. We show that the integral momentum of the SPP per particle corresponds to the SPP wave vector, and hence exceeds the momentum of a photon in the vacuum. We also provide the first accurate calculation of the transverse spin and orbital AM of the SPP. While the intrinsic orbital AM vanishes, the transverse spin can change its sign depending on the SPP frequency. Importantly, we present both macroscopic and microscopic calculations, thereby proving the validity of the general phenomenological results. The microscopic theory also predicts a transverse magnetization in the metal (i.e. a magnetic moment for the SPP) as well as the corresponding direct magnetization current, which provides the difference between the Abraham and Minkowski momenta.

  19. Reconstruction Using Witness Complexes (United States)

    Oudot, Steve Y.


    We present a novel reconstruction algorithm that, given an input point set sampled from an object S, builds a one-parameter family of complexes that approximate S at different scales. At a high level, our method is very similar in spirit to Chew’s surface meshing algorithm, with one notable difference though: the restricted Delaunay triangulation is replaced by the witness complex, which makes our algorithm applicable in any metric space. To prove its correctness on curves and surfaces, we highlight the relationship between the witness complex and the restricted Delaunay triangulation in 2d and in 3d. Specifically, we prove that both complexes are equal in 2d and closely related in 3d, under some mild sampling assumptions. PMID:21643440

  20. 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. (United States)

    Erales, Jenny; Beltrandi, Matilde; Roche, Jennifer; Maté, Maria; Longhi, Sonia


    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.

  1. The effect of ionic strength on the adsorption of H{sup +}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+} by Bacillus subtilis and Bacillus licheniformis: A surface complexation model

    Energy Technology Data Exchange (ETDEWEB)

    Daughney, C.J. [McGill Univ., Montreal, Quebec (Canada). Earth and Planetary Sciences; Fein, J.B. [Univ. of Notre Dame, IN (United States)


    To quantify metal adsorption onto bacterial surfaces, recent studies have applied surface complexation theory to model the specific chemical and electrostatic interactions occurring at the solution-cell wall interface. However, to date, the effect of ionic strength on these interactions has not been investigated. In this study, the authors perform acid-base titrations of suspensions containing Bacillus subtilis or Bacillus licheniformis in 0.01 or 0.1 M NaNO{sub 3}, and they evaluate the constant capacitance and basic Stern double-layer models for their ability to describe ionic-strength-dependent behavior. The constant capacitance model provides the best description of the experimental data. The constant capacitance model parameters vary between independently grown bacterial cultures, possibly due to cell wall variation arising from genetic exchange during reproduction. The authors perform metal-B. subtilis and metal-B. licheniformis adsorption experiments using Cd, Pb, and Cu, and they solve for stability constants describing metal adsorption onto distinct functional groups on the bacterial cell walls. They find that these stability constants vary substantially but systematically between the two bacterial species at the two different ionic strengths.

  2. Intermolecular configurations dominated by quadrupole-quadrupole electrostatic interactions: explicit correlation treatment of the five-dimensional potential energy surface and infrared spectra for the CO-N2 complex. (United States)

    Liu, Jing-Min; Zhai, Yu; Zhang, Xiao-Long; Li, Hui


    A thorough understanding of the intermolecular configurations of van der Waals complexes is a great challenge due to their weak interactions, floppiness and anharmonic nature. Although high-resolution microwave or infrared spectroscopy provides one of the most direct and precise pieces of experimental evidence, the origin and key role in determining such intermolecular configurations of a van der Waals system strongly depend on its highly accurate potential energy surface (PES) and a detailed analysis of its ro-vibrational wavefunctions. Here, a new five-dimensional potential energy surface for the van der Waals complex of CO-N 2 which explicitly incorporates the dependence on the stretch coordinate of the CO monomer is generated using the explicitly correlated couple cluster (CCSD(T)-F12) method in conjunction with a large basis set. Analytic four-dimensional PESs are obtained by the least-squares fitting of vibrationally averaged interaction energies for v = 0 and v = 1 to the Morse/Long-Range potential mode (V MLR ). These fits to 7966 points have root-mean-square deviations (RMSD) of 0.131 cm -1 and 0.129 cm -1 for v = 0 and v = 1, respectively, with only 315 parameters. Energy decomposition analysis is carried out, and it reveals that the dominant factor in controlling intermolecular configurations is quadrupole-quadrupole electrostatic interactions. Moreover, the rovibrational levels and wave functions are obtained for the first time. The predicted infrared transitions and intensities for the ortho-N 2 -CO complex as well as the calculated energy levels for para-N 2 -CO are in good agreement with the available experimental data with RMSD discrepancies smaller than 0.068 cm -1 . The calculated infrared band origin shift associated with the fundamental band frequency of CO is -0.721 cm -1 for ortho-N 2 -CO which is in excellent agreement with the experimental value of -0.739 cm -1 . The agreement with experimental values validates the high quality of the PESs

  3. Complex Narratives

    NARCIS (Netherlands)

    Simons, J.; Buckland, W.


    In the opening chapter, "Complex Narratives," Jan Simons brings together narratology, game theory, and complexity theory to untangle the intricate nature of complex narratives in contemporary cinema. He presents an overview of the different concepts - forking path narratives, mind-game films,

  4. phenanthroline complex

    Indian Academy of Sciences (India)



    Feb 28, 2018 ... complex in a unique binding motif and provide additional stability to the compound in the solid state. This iron(II) complex is able to catalyze the cleavage of aromatic C-C linkage of 2,5-dihydroxybenzoic acid (Gentisic acid,. GA) in oxygen environment. The iron(II) complex in the presence of two equivalent ...

  5. (II) complexes

    African Journals Online (AJOL)

    activities of Schiff base tin (II) complexes. Neelofar1 ... Conclusion: All synthesized Schiff bases and their Tin (II) complexes showed high antimicrobial and ...... Singh HL. Synthesis and characterization of tin (II) complexes of fluorinated Schiff bases derived from amino acids. Spectrochim Acta Part A: Molec Biomolec.

  6. Jet-Cooled Infrared Laser Spectroscopy in the Umbrella νb{2} Vibration Region of NH_3: Improving the Potential Energy Surface Model of the NH_3-Ar Van Der Waals Complex (United States)

    Asselin, Pierre; Jabri, Atef; Potapov, Alexey; Loreau, Jérome; van der Avoird, Ad


    Taking advantage of our sensitive laser spectrometer coupled to a pulsed slit jet, we recorded near the νb{2} vibration a series of rovibrational transitions of the NH_3-Ar van der Waals (vdW) complex. These transitions involve in the ground vibrational state several internal rotor states corresponding to the ortho{NH_3} and para{NH_3} spin modifications of the complex. They are labeled by Σ_{a}(j,k), Σ_{s}(j,k), Π_{a}(j,k) and Π_{s}(j,k) where Σ(K=0) and Π(K=1) indicate the projection K of the total rotational angular momentum J on the vdW axis, the superscripts s and a designate a symmetric or antisymmetric NH_3 inversion wave function, and j, k quantum numbers indicate the correlation between the internal-rotor state of the complex and the j, k rotational state of the free NH_3 monomer. Five bands have been identified, only one of which was partly observed before. They include transitions starting from the Σ_{a}(j=0 or j=1) state without any internal angular momentum, consequently they can be assigned from the band contour of a linear-molecule-like K=0, ΔJ=1 transition. The energies and splittings of the rovibrational levels of the νb{2}=1←0 spectrum derived from the analysis of the Π_{s}, Σ_{s}(j=1)← Σ_{a}(j=0), k=0 bands and mostly of the Σ_{s}, Π_{s} and Σ_{a}(j=1)←Σ_{a}(j=1), k=1 bands bring relevant information about the νb{2} dependence of the NH_3-Ar interaction, the rovibrational dynamics of the NH_3-Ar complex and provide a sensitive test of a recently developed 4D potential energy surface that includes explicitly its dependence on the umbrella motion. P. Asselin, Y. Berger, T. R. Huet, R. Motiyenko, L. Margulès, R. J. Hendricks, M. R. Tarbutt, S. Tokunaga, B. Darquié, PCCP 19, 4576 (2017), G. T. Fraser, A.S. Pine and W. A. Kreiner, J. Chem. Phys. 94, 7061 (1991). J. Loreau, J. Liévin, Y. Scribano and A. van der Avoird, J. Chem. Phys. 141, 224303 (2014).

  7. Complexity Plots

    KAUST Repository

    Thiyagalingam, Jeyarajan


    In this paper, we present a novel visualization technique for assisting the observation and analysis of algorithmic complexity. In comparison with conventional line graphs, this new technique is not sensitive to the units of measurement, allowing multivariate data series of different physical qualities (e.g., time, space and energy) to be juxtaposed together conveniently and consistently. It supports multivariate visualization as well as uncertainty visualization. It enables users to focus on algorithm categorization by complexity classes, while reducing visual impact caused by constants and algorithmic components that are insignificant to complexity analysis. It provides an effective means for observing the algorithmic complexity of programs with a mixture of algorithms and black-box software through visualization. Through two case studies, we demonstrate the effectiveness of complexity plots in complexity analysis in research, education and application. © 2013 The Author(s) Computer Graphics Forum © 2013 The Eurographics Association and Blackwell Publishing Ltd.

  8. Meteorite Impact "Earthquake" Features (Rock Liquefaction, Surface Wave Deformations, Seismites) from Ground Penetrating Radar (GPR) and Geoelectric Complex Resistivity/Induced Polarization (IP) Measurements, Chiemgau (Alpine Foreland, Southeast Germany) (United States)

    Ernstson, K.; Poßekel, J.


    Densely spaced GPR and complex resistivity measurements on a 30,000 square meters site in a region of enigmatic sinkhole occurrences in unconsolidated Quaternary sediments have featured unexpected and highlighting results from both a meteorite impact research and an engineering geology point of view. The GPR measurements and a complex resistivity/IP electrical imaging revealed extended subrosion depressions related with a uniformly but in various degrees of intensity deformed loamy and gravelly ground down to at least 10 m depth. Two principle observations could be made from both the GPR high-resolution measurements and the more integrating resistivity and IP soundings with both petrophysical evidences in good complement. Subrosion can be shown to be the result of prominent sandy-gravelly intrusions and extrusions typical of rock liquefaction processes well known to occur during strong earthquakes. Funnel-shaped structures with diameters up to 25 m near the surface and reaching down to the floating ground water level at 10 m depth were measured. GPR radargrams could trace prominent gravelly-material transport bottom-up within the funnels. Seen in both GPR tomography and resistivity/IP sections more or less the whole investigated area is overprinted by wavy deformations of the unconsolidated sediments with wavelengths of the order of 5 - 10 m and amplitudes up to half a meter, likewise down to 10 m depth. Substantial earthquakes are not known in this region. Hence, the observed heavy underground disorder is considered the result of the prominent earthquake shattering that must have occurred during the Holocene (Bronze Age/Celtic era) Chiemgau meteorite impact event that produced a 60 km x 30 km sized crater strewn field directly hosting the investigated site. Depending on depth and size of floating aquifers local concentrations of rock liquefaction and seismic surface waves (probably LOVE waves) to produce the wavy deformations could develop, when the big

  9. Complex odontoma. (United States)

    Preetha, A; Balikai, Bharati S; Sujatha, D; Pai, Anuradha; Ganapathy, K S


    Odontomas are hamartomatous lesions or malformations composed of mature enamel, dentin, and pulp. They may be compound or complex, depending on the extent of morphodifferentiation or their resemblance to normal teeth. The etiology of odontoma is unknown, although several theories have been proposed. This article describes a case of a large infected complex odontoma in the residual mandibular ridge, resulting in considerable mandibular expansion.

  10. Complex narratives

    NARCIS (Netherlands)

    Simons, J.


    This paper brings together narratology, game theory, and complexity theory to untangle the intricate nature of complex narratives in contemporary cinema. It interrogates the different terms - forking-path narratives, mind-game films, modular narratives, multiple-draft films, database narratives,

  11. Complexity Theory (United States)

    Lee, William H K.


    A complex system consists of many interacting parts, generates new collective behavior through self organization, and adaptively evolves through time. Many theories have been developed to study complex systems, including chaos, fractals, cellular automata, self organization, stochastic processes, turbulence, and genetic algorithms.

  12. Complex variables

    CERN Document Server

    Fisher, Stephen D


    The most important topics in the theory and application of complex variables receive a thorough, coherent treatment in this introductory text. Intended for undergraduates or graduate students in science, mathematics, and engineering, this volume features hundreds of solved examples, exercises, and applications designed to foster a complete understanding of complex variables as well as an appreciation of their mathematical beauty and elegance. Prerequisites are minimal; a three-semester course in calculus will suffice to prepare students for discussions of these topics: the complex plane, basic

  13. Managing Complexity

    DEFF Research Database (Denmark)

    Maylath, Bruce; Vandepitte, Sonia; Minacori, Patricia


    This article discusses the largest and most complex international learning-by-doing project to date- a project involving translation from Danish and Dutch into English and editing into American English alongside a project involving writing, usability testing, and translation from English into Dutch...... and into French. The complexity of the undertaking proved to be a central element in the students' learning, as the collaboration closely resembles the complexity of international documentation workplaces of language service providers. © Association of Teachers of Technical Writing....

  14. Complex Covariance

    Directory of Open Access Journals (Sweden)

    Frieder Kleefeld


    Full Text Available According to some generalized correspondence principle the classical limit of a non-Hermitian quantum theory describing quantum degrees of freedom is expected to be the well known classical mechanics of classical degrees of freedom in the complex phase space, i.e., some phase space spanned by complex-valued space and momentum coordinates. As special relativity was developed by Einstein merely for real-valued space-time and four-momentum, we will try to understand how special relativity and covariance can be extended to complex-valued space-time and four-momentum. Our considerations will lead us not only to some unconventional derivation of Lorentz transformations for complex-valued velocities, but also to the non-Hermitian Klein-Gordon and Dirac equations, which are to lay the foundations of a non-Hermitian quantum theory.

  15. Communication Complexity

    Indian Academy of Sciences (India)

    Jaikumar Radhakrishnan

    Alice and Bob are randomized agents. They exchange messages in order to compute a function f(x, y). We allow a small probability of error. Goal: minimize the total number of bits transmitted. Jaikumar Radhakrishnan. Communication Complexity ...

  16. Complex matrix model duality

    Energy Technology Data Exchange (ETDEWEB)

    Brown, T.W.


    The same complex matrix model calculates both tachyon scattering for the c=1 non-critical string at the self-dual radius and certain correlation functions of half-BPS operators in N=4 super- Yang-Mills. It is dual to another complex matrix model where the couplings of the first model are encoded in the Kontsevich-like variables of the second. The duality between the theories is mirrored by the duality of their Feynman diagrams. Analogously to the Hermitian Kontsevich- Penner model, the correlation functions of the second model can be written as sums over discrete points in subspaces of the moduli space of punctured Riemann surfaces. (orig.)

  17. On real quadric line complexes

    International Nuclear Information System (INIS)

    Krasnov, Vyacheslav A


    We describe the topological types of the real parts of the Kummer surfaces associated with real three-dimensional quadric line complexes. The topological type of the real part of such a surface is shown to depend on the number of real singular points: it is determined by the number of such points if any exist, and otherwise the real part of the Kummer surface is either empty or consists of one or two tori.

  18. DC-SIGN, C1q, and gC1qR form a trimolecular receptor complex on the surface of monocyte-derived immature dendritic cells (United States)

    Hosszu, Kinga K.; Valentino, Alisa; Vinayagasundaram, Uma; Vinayagasundaram, Rama; Joyce, M. Gordon; Ji, Yan; Peerschke, Ellinor I. B.


    C1q modulates the differentiation and function of cells committed to the monocyte-derived dendritic cell (DC) lineage. Because the 2 C1q receptors found on the DC surface—gC1qR and cC1qR—lack a direct conduit into intracellular elements, we postulated that the receptors must form complexes with transmembrane partners. In the present study, we show that DC-SIGN, a C-type lectin expressed on DCs, binds directly to C1q, as assessed by ELISA, flow cytometry, and immunoprecipitation experiments. Surface plasmon resonance analysis revealed that the interaction was specific, and both intact C1q and the globular portion of C1q bound to DC-SIGN. Whereas IgG reduced this binding significantly, the Arg residues (162-163) of the C1q-A chain, which are thought to contribute to the C1q-IgG interaction, were not required for C1q binding to DC-SIGN. Binding was reduced significantly in the absence of Ca2+ and by preincubation of DC-SIGN with mannan, suggesting that C1q binds to DC-SIGN at its principal Ca2+-binding pocket, which has increased affinity for mannose residues. Antigen-capture ELISA and immunofluorescence microscopy revealed that C1q and gC1qR associate with DC-SIGN on blood DC precursors and immature DCs. The results of the present study suggest that C1q/gC1qR may regulate DC differentiation and function through the DC-SIGN–mediated induction of cell-signaling pathways. PMID:22700724

  19. Complex conductivity of soils

    DEFF Research Database (Denmark)

    Revil, A.; Coperey, A.; Shao, Z.


    The complex conductivity of soil remains poorly known despite the growing importance of this method in hyrogeophysics. In order to fill this gap of knowledge, we investigate the complex conductivity of 71 soils samples (including 4 peat samples) and one clean sand in the frequency range 0.1 Hertz...... to 45 kHz. The soil samples are saturated with 6 different NaCl brines with conductivities (0.031, 0.53, 1.15, 5.7, 14.7, and 22 S m-1, NaCl, 25°C) in order to determine their intrinsic formation factor and surface conductivity. This dataset is used to test the predictions of the dynamic Stern...... polarization model of porous media in terms of relationship between the quadrature conductivity and the surface conductivity. We also investigate the relationship between the normalized chargeability (the difference of in phase conductivity between two frequencies) and the quadrature conductivity...

  20. Complex analysis

    CERN Document Server

    Freitag, Eberhard


    The guiding principle of this presentation of ``Classical Complex Analysis'' is to proceed as quickly as possible to the central results while using a small number of notions and concepts from other fields. Thus the prerequisites for understanding this book are minimal; only elementary facts of calculus and algebra are required. The first four chapters cover the essential core of complex analysis: - differentiation in C (including elementary facts about conformal mappings) - integration in C (including complex line integrals, Cauchy's Integral Theorem, and the Integral Formulas) - sequences and series of analytic functions, (isolated) singularities, Laurent series, calculus of residues - construction of analytic functions: the gamma function, Weierstrass' Factorization Theorem, Mittag-Leffler Partial Fraction Decomposition, and -as a particular highlight- the Riemann Mapping Theorem, which characterizes the simply connected domains in C. Further topics included are: - the theory of elliptic functions based on...

  1. Complex Analysis

    CERN Document Server

    Stein, Elias M


    With this second volume, we enter the intriguing world of complex analysis. From the first theorems on, the elegance and sweep of the results is evident. The starting point is the simple idea of extending a function initially given for real values of the argument to one that is defined when the argument is complex. From there, one proceeds to the main properties of holomorphic functions, whose proofs are generally short and quite illuminating: the Cauchy theorems, residues, analytic continuation, the argument principle.With this background, the reader is ready to learn a wealth of additional m

  2. Complex manifolds

    CERN Document Server

    Morrow, James


    This book, a revision and organization of lectures given by Kodaira at Stanford University in 1965-66, is an excellent, well-written introduction to the study of abstract complex (analytic) manifolds-a subject that began in the late 1940's and early 1950's. It is largely self-contained, except for some standard results about elliptic partial differential equations, for which complete references are given. -D. C. Spencer, MathSciNet The book under review is the faithful reprint of the original edition of one of the most influential textbooks in modern complex analysis and geometry. The classic

  3. Introduction to Complex Plasmas

    CERN Document Server

    Bonitz, Michael; Ludwig, Patrick


    Complex plasmas differ from traditional plasmas in many ways: these are low-temperature high pressure systems containing nanometer to micrometer size particles which may be highly charged and strongly interacting. The particles may be chemically reacting or be in contact with solid surfaces, and the electrons may show quantum behaviour. These interesting properties have led to many applications of complex plasmas in technology, medicine and science. Yet complex plasmas are extremely complicated, both experimentally and theoretically, and require a variety of new approaches which go beyond standard plasma physics courses. This book fills this gap presenting an introduction to theory, experiment and computer simulation in this field. Based on tutorial lectures at a very successful recent Summer Institute, the presentation is ideally suited for graduate students, plasma physicists and experienced undergraduates.

  4. Communication Complexity

    Indian Academy of Sciences (India)

    Jaikumar Radhakrishnan

    Communication complexity. Motivation . . . An abstract model to study the communicaiton required for computation. A tool for showing lower bounds in several computational models. The study often requires deep understanding of computation using tools from combinatorics, coding theory, algebra, analysis, etc. Jaikumar ...

  5. Lecithin Complex

    African Journals Online (AJOL)

    1Department of Food Science and Engineering, Xinyang College of Agriculture and Forestry, Xinyang 464000, 2Henan. Economy and Trade ... Methanol of HPLC grade was purchased from Tedia (USA). Other chemicals used were of analytical grade. Preparation of polydatin-lecithin complex. Polydatin (200 mg) and ...

  6. Complex Networks

    CERN Document Server

    Evsukoff, Alexandre; González, Marta


    In the last decade we have seen the emergence of a new inter-disciplinary field focusing on the understanding of networks which are dynamic, large, open, and have a structure sometimes called random-biased. The field of Complex Networks is helping us better understand many complex phenomena such as the spread of  deseases, protein interactions, social relationships, to name but a few. Studies in Complex Networks are gaining attention due to some major scientific breakthroughs proposed by network scientists helping us understand and model interactions contained in large datasets. In fact, if we could point to one event leading to the widespread use of complex network analysis is the availability of online databases. Theories of Random Graphs from Erdös and Rényi from the late 1950s led us to believe that most networks had random characteristics. The work on large online datasets told us otherwise. Starting with the work of Barabási and Albert as well as Watts and Strogatz in the late 1990s, we now know th...

  7. binary complexes

    African Journals Online (AJOL)

    Preferred Customer

    the temperature constant, two hollow metallic plates coated with thin plastic paper on the outer surface were used ... of metal carbonates from 0.1 M solution of sodium carbonate (Analytical Reagent grade, BDH,. UK). ... different pH values of the background electrolyte (variation in pH was made by addition of caustic soda ...

  8. Lipid bilayers decorated with photosensitive ruthenium complexes

    NARCIS (Netherlands)

    Bahreman, Azadeh


    In this thesis the thermal- and photo-substitution behavior of polypyridyl ruthenium complexes is described at the surface of lipid bilayers and in homogeneous solutions. It is shown that the successive thermal binding and light-induced unbinding of the cationic ruthenium complex at the surface of

  9. Managing Complexity

    Energy Technology Data Exchange (ETDEWEB)

    Chassin, David P.; Posse, Christian; Malard, Joel M.


    Physical analogs have shown considerable promise for understanding the behavior of complex adaptive systems, including macroeconomics, biological systems, social networks, and electric power markets. Many of today’s most challenging technical and policy questions can be reduced to a distributed economic control problem. Indeed, economically-based control of large-scale systems is founded on the conjecture that the price-based regulation (e.g., auctions, markets) results in an optimal allocation of resources and emergent optimal system control. This paper explores the state of the art in the use physical analogs for understanding the behavior of some econophysical systems and to deriving stable and robust control strategies for them. In particular we review and discussion applications of some analytic methods based on the thermodynamic metaphor according to which the interplay between system entropy and conservation laws gives rise to intuitive and governing global properties of complex systems that cannot be otherwise understood.

  10. Time complexity and gate complexity

    International Nuclear Information System (INIS)

    Koike, Tatsuhiko; Okudaira, Yosuke


    We formulate and investigate the simplest version of time-optimal quantum computation theory (TO-QCT), where the computation time is defined by the physical one and the Hamiltonian contains only one- and two-qubit interactions. This version of TO-QCT is also considered as optimality by sub-Riemannian geodesic length. The work has two aims: One is to develop a TO-QCT itself based on a physically natural concept of time, and the other is to pursue the possibility of using TO-QCT as a tool to estimate the complexity in conventional gate-optimal quantum computation theory (GO-QCT). In particular, we investigate to what extent is true the following statement: Time complexity is polynomial in the number of qubits if and only if gate complexity is also. In the analysis, we relate TO-QCT and optimal control theory (OCT) through fidelity-optimal computation theory (FO-QCT); FO-QCT is equivalent to TO-QCT in the limit of unit optimal fidelity, while it is formally similar to OCT. We then develop an efficient numerical scheme for FO-QCT by modifying Krotov's method in OCT, which has a monotonic convergence property. We implemented the scheme and obtained solutions of FO-QCT and of TO-QCT for the quantum Fourier transform and a unitary operator that does not have an apparent symmetry. The former has a polynomial gate complexity and the latter is expected to have an exponential one which is based on the fact that a series of generic unitary operators has an exponential gate complexity. The time complexity for the former is found to be linear in the number of qubits, which is understood naturally by the existence of an upper bound. The time complexity for the latter is exponential in the number of qubits. Thus, both the targets seem to be examples satisfyng the preceding statement. The typical characteristics of the optimal Hamiltonians are symmetry under time reversal and constancy of one-qubit operation, which are mathematically shown to hold in fairly general situations.

  11. Welding complex

    Energy Technology Data Exchange (ETDEWEB)

    Lebedev, V.K.; Kuchuk-Yatsenko, S.I.; Sakharnov, V.A.; Galyan, B.A.; Krivenko, V.G.; Asoyants, G.B.


    A welding complex for construction of a continuous underwater pipeline is adapted to be installed aboard a ship. The complex includes a welding machine positionable at a joint of the pipeline with a pipe section to be welded, burr-removing trimmers positionable coaxially with the pipeline for displacement relative to the pipeline in the joint area, and a support device for the end part of the pipeline. A rotatably mounted holding device for setting, holding, and retaining the pipe section to be welded, the welding machine, and the trimmers is axially aligned with the end part of the pipeline. An accumulator is provided for storing and delivering successive pipe sections at a loading position laterally offset from the common axis of the pipeline and of the pipe section to be welded to it. The holding device includes a platform movable along the common axis of the pipeline and of the pipe section to be welded to it by a resistance butt welding machine, and a plate with a means for carrying the pipe section to be welded which is mounted on a pivot carried by the platform for rotation between the loading position and the aligning position. The welding complex of the invention provides for implementing resistance butt welding in construction of continuous underwater pipelines and ensures the accuracy of alignment and permanence of the gap between the edges being welded. The welding complex's structure allows handling of longer pipe sections, thus reducing the overall number of joints to be welded. 7 figs.

  12. Estudo voltamétrico do complexo de cobre(II com o ligante vermelho de alizarina S, adsorvido na superfície do eletrodo de grafite pirolítico Voltammetric study of complex of copper (II with alizarin red S ligand, absorbed on surface of pyrolytic graphite electrode

    Directory of Open Access Journals (Sweden)

    Victor E. Mouchrek Filho


    Full Text Available The alizarin red S (ARS has been used as a spectrophotometric reagent of several metals for a long time. Now this alizarin has been used as modifier agent of electrodes, for voltammetric analyses. In this work cyclic voltammetry experiments was accomplished on closed circuit, with the objective of studying the voltammetric behavior of alizarin red S adsorbed and of its copper complex, on the surface of the pyrolytic graphite electrode. These studies showed that ARS strongly adsorbs on the surface of this electrode. This adsorption was used to immobilize ions copper(II from the solution.

  13. Complex variables

    CERN Document Server

    Flanigan, Francis J


    A caution to mathematics professors: Complex Variables does not follow conventional outlines of course material. One reviewer noting its originality wrote: ""A standard text is often preferred [to a superior text like this] because the professor knows the order of topics and the problems, and doesn't really have to pay attention to the text. He can go to class without preparation."" Not so here-Dr. Flanigan treats this most important field of contemporary mathematics in a most unusual way. While all the material for an advanced undergraduate or first-year graduate course is covered, discussion

  14. Super Riemann surfaces

    International Nuclear Information System (INIS)

    Rogers, Alice


    A super Riemann surface is a particular kind of (1,1)-dimensional complex analytic supermanifold. From the point of view of super-manifold theory, super Riemann surfaces are interesting because they furnish the simplest examples of what have become known as non-split supermanifolds, that is, supermanifolds where the odd and even parts are genuinely intertwined, as opposed to split supermanifolds which are essentially the exterior bundles of a vector bundle over a conventional manifold. However undoubtedly the main motivation for the study of super Riemann surfaces has been their relevance to the Polyakov quantisation of the spinning string. Some of the papers on super Riemann surfaces are reviewed. Although recent work has shown all super Riemann surfaces are algebraic, some areas of difficulty remain. (author)

  15. Complex dynamics

    CERN Document Server

    Carleson, Lennart


    Complex dynamics is today very much a focus of interest. Though several fine expository articles were available, by P. Blanchard and by M. Yu. Lyubich in particular, until recently there was no single source where students could find the material with proofs. For anyone in our position, gathering and organizing the material required a great deal of work going through preprints and papers and in some cases even finding a proof. We hope that the results of our efforts will be of help to others who plan to learn about complex dynamics and perhaps even lecture. Meanwhile books in the field a. re beginning to appear. The Stony Brook course notes of J. Milnor were particularly welcome and useful. Still we hope that our special emphasis on the analytic side will satisfy a need. This book is a revised and expanded version of notes based on lectures of the first author at UCLA over several \\Vinter Quarters, particularly 1986 and 1990. We owe Chris Bishop a great deal of gratitude for supervising the production of cour...

  16. Cosmic Complexity (United States)

    Mather, John C.


    What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and

  17. Minimal surfaces

    CERN Document Server

    Dierkes, Ulrich; Sauvigny, Friedrich; Jakob, Ruben; Kuster, Albrecht


    Minimal Surfaces is the first volume of a three volume treatise on minimal surfaces (Grundlehren Nr. 339-341). Each volume can be read and studied independently of the others. The central theme is boundary value problems for minimal surfaces. The treatise is a substantially revised and extended version of the monograph Minimal Surfaces I, II (Grundlehren Nr. 295 & 296). The first volume begins with an exposition of basic ideas of the theory of surfaces in three-dimensional Euclidean space, followed by an introduction of minimal surfaces as stationary points of area, or equivalently

  18. Rumble surfaces

    CSIR Research Space (South Africa)

    National Institute for Transport and Road


    Full Text Available Rumble surfaces are intermittent short lengths of coarse-textured road surfacings on which vehicle tyres produce a rumbling sound. used in conjunction with appropriate roadsigns and markings, they can reduce accidents on rural roads by alerting...

  19. Adsorption of O2 and C2Hn (n = 2, 4, 6) on the Al9Co2(0 0 1) and o-Al13Co4(1 0 0) complex metallic alloy surfaces

    International Nuclear Information System (INIS)

    Wardé, M.; Herinx, M.; Ledieu, J.; Serkovic Loli, L.N.; Fournée, V.; Gille, P.; Le Moal, S.; Barthés-Labrousse, M.-G.


    Highlights: • Oxidation mechanisms on Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) CMA surfaces. • Oxidation kinetics dependent on oxygen partial pressure; no aluminium segregation. • Lack of aluminium segregation ascribed to strong covalent bonds within the crystals. • Competition between oxide film growth or dissolution, O 2 desorption or dissolution. • C 2 H n (n = 2, 4, 6) not adsorbed on Al 13 Co 4 (1 0 0). - Abstract: Oxidation of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been performed in a wide range of temperatures at 2 × 10 −8 or 1 × 10 −7 mbar oxygen pressure. Only Al−O bonding is observed. The oxidation kinetics are controlled by the quantity of oxygen sticking on the surface. Oxidation results from a competition between several effects: formation of an oxide film, dissolution of the film, oxygen desorption and oxygen dissolution into the bulk. For temperatures lower than 710 K for the Al 9 Co 2 (0 0 1) surface and 925 K for the Al 13 Co 4 (1 0 0) surface, a ∼5 Å thick oxide film is formed which does not show any long-range order and desorbs upon annealing. When oxidation is performed at higher temperatures, oxygen diffusion into the bulk is observed. A poorly ordered oxide film having a sixton structure is formed on the Al 9 Co 2 (0 0 1) surface when oxidation is performed at 775 K, which is dissolved when annealing at higher temperatures. On the Al 13 Co 4 (1 0 0) surface, only a weak streaky polar circle is observed following annealing at 925 K the film formed at room temperature, which corresponds to an hexagonal network of O atoms into small ultrathin oxide layers domains. The oxidation behaviour of the Al 9 Co 2 (0 0 1) and Al 13 Co 4 (1 0 0) surfaces has been ascribed to the strong covalent character of bonds present in these Al−Co phases, which prevents aluminium diffusion. C 2 H n molecules (n = 2, 4, 6) do not adsorb on the Al 13 Co 4 (1 0 0) surface in the experimental conditions used in this study, thus

  20. Surface thermodynamics

    International Nuclear Information System (INIS)

    Garcia-Moliner, F.


    Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions

  1. Complexity and synchronization in stochastic chaotic systems (United States)

    Son Dang, Thai; Palit, Sanjay Kumar; Mukherjee, Sayan; Hoang, Thang Manh; Banerjee, Santo


    We investigate the complexity of a hyperchaotic dynamical system perturbed by noise and various nonlinear speech and music signals. The complexity is measured by the weighted recurrence entropy of the hyperchaotic and stochastic systems. The synchronization phenomenon between two stochastic systems with complex coupling is also investigated. These criteria are tested on chaotic and perturbed systems by mean conditional recurrence and normalized synchronization error. Numerical results including surface plots, normalized synchronization errors, complexity variations etc show the effectiveness of the proposed analysis.

  2. Control of complex systems

    CERN Document Server

    Albertos, Pedro; Blanke, Mogens; Isidori, Alberto; Schaufelberger, Walter; Sanz, Ricardo


    The world of artificial systems is reaching complexity levels that es­ cape human understanding. Surface traffic, electricity distribution, air­ planes, mobile communications, etc. , are examples that demonstrate that we are running into problems that are beyond classical scientific or engi­ neering knowledge. There is an ongoing world-wide effort to understand these systems and develop models that can capture its behavior. The reason for this work is clear, if our lack of understanding deepens, we will lose our capability to control these systems and make they behave as we want. Researchers from many different fields are trying to understand and develop theories for complex man-made systems. This book presents re­ search from the perspective of control and systems theory. The book has grown out of activities in the research program Control of Complex Systems (COSY). The program has been sponsored by the Eu­ ropean Science Foundation (ESF) which for 25 years has been one of the leading players in stimula...

  3. Note on subregion holographic complexity (United States)

    Roy, Pratim; Sarkar, Tapobrata


    The volume inside a Ryu-Takayanagi surface has been conjectured to be related to the complexity of subregions of the boundary field theory. Here, we study the behavior of this volume analytically, when the entangling surface has a strip geometry. We perform systematic expansions in the low- and high-temperature regimes for AdS-Schwarzschild and RN-AdS black holes. In the latter regime, we point out spurious divergences that might occur due to the limitations of a near horizon expansion. A similar analysis is performed for extremal black holes and, at large charge, we find that there might be some new features of the volume as compared to the area. Finally, we numerically study a four-dimensional RN-AdS black hole in global AdS, the entangling surface being a sphere. We find that the holographic complexity captures essentially the same information as the entanglement entropy, as far as phase transitions are concerned.

  4. Plasma-surface interactions

    International Nuclear Information System (INIS)

    Goeckner, M J; Nelson, C T; Sant, S P; Jindal, A K; Joseph, E A; Zhou, B S; Padron-Wells, G; Jarvis, B; Pierce, R; Overzet, L J


    Materials processing is at a crossroads. Currently a large fraction of industrially viable materials processing is via plasmas. Until recently it has been economical to just examine the influence the plasma properties on the desired surface processes and through this ultimately optimize manufacturing. For example, it is well known that the surface processes (etch or deposition), occur in the top few mono-layers of the surface. Thus, in film growth one requires that molecules from the gas-phase land and bond on the surface. However as processing has reached the nano-scale, development of viable processes has become more and more difficult. In part, this is because of all of the free parameters that exist in plasmas. To overcome this economic issue, tool vendors and semiconductor companies have turned to complex computational models of processing plasmas. For those models to work, one requires a through understanding of all of the gas-phase and surface-phase processes that are exhibited in plasmas. Unfortunately, these processes, particularly those at the surface, are not well understood. In this article we describe a viable model of the surface-phase based on cross sections for processes that occur. While originally developed of fluorocarbon systems, the model also appears to be applicable to hydrocarbon systems.

  5. Caractérisation d’inhibiteurs d’anhydrase carbonique IX, études de complexes supramoléculaires et interactions moléculaires par résonance plasmonique de surface


    Florent, Tiphaine


    Carbonic anhydrase (CA) IX expression is increased upon hypoxia and has been proposed as a therapeutic target since it has been associated with poor prognosis, tumor progression and pH regulation. A new class of human carbonic anhydrase IX (hCA IX) inhibitors, diarylpyrazole sulfonamide derivatives, has been synthesized in our team. These compounds have a very limited water solubility which limits their pharmaceutical development. The complexation with cyclodextrins (CDs) offers the possibili...

  6. Template synthesis of two new supramolecular zinc(II) complexes containing pentadentate N.sub.3./sub.O.sub.2./sub. semicarbazone ligand: Nanostructure synthesis, Hirshfeld surface analysis, and DFT studies

    Czech Academy of Sciences Publication Activity Database

    Tyula, Y.A.; Zabardasti, A.; Goudarziafshar, H.; Roudsari, M.S.; Dušek, Michal; Eigner, Václav


    Roč. 1150, Dec (2017), s. 383-394 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : sonochemical synthesis * Hirshfeld surface analysis * DFT calculations * bis(semicarbazone) * pentagonal-bipyramidal Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.753, year: 2016

  7. Controlled/living surface-initiated ATRP of antifouling polymer brushes from gold in PBS and blood sera as a model study for polymer modifications in complex biological media

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, Cesar; Hasan, E.; Pop-Georgievski, Ognen; Houska, Milan; Brynda, Eduard; Bologna Alles, A.


    Roč. 12, č. 4 (2012), s. 525-532 ISSN 1616-5187 R&D Projects: GA AV ČR KAN200670701; GA ČR GAP503/10/0664 Institutional research plan: CEZ:AV0Z40500505 Keywords : antifouling surfaces * atom-transfer radical polymerization ( ATRP ) * biocompatibility Subject RIV: EE - Microbiology, Virology Impact factor: 3.742, year: 2012

  8. Horizontal gene transfer contributed to the evolution of extracellular surface structures: the freshwater polyp Hydra is covered by a complex fibrous cuticle containing glycosaminoglycans and proteins of the PPOD and SWT (sweet tooth families.

    Directory of Open Access Journals (Sweden)

    Angelika Böttger

    Full Text Available The single-cell layered ectoderm of the fresh water polyp Hydra fulfills the function of an epidermis by protecting the animals from the surrounding medium. Its outer surface is covered by a fibrous structure termed the cuticle layer, with similarity to the extracellular surface coats of mammalian epithelia. In this paper we have identified molecular components of the cuticle. We show that its outermost layer contains glycoproteins and glycosaminoglycans and we have identified chondroitin and chondroitin-6-sulfate chains. In a search for proteins that could be involved in organising this structure we found PPOD proteins and several members of a protein family containing only SWT (sweet tooth domains. Structural analyses indicate that PPODs consist of two tandem β-trefoil domains with similarity to carbohydrate-binding sites found in lectins. Experimental evidence confirmed that PPODs can bind sulfated glycans and are secreted into the cuticle layer from granules localized under the apical surface of the ectodermal epithelial cells. PPODs are taxon-specific proteins which appear to have entered the Hydra genome by horizontal gene transfer from bacteria. Their acquisition at the time Hydra evolved from a marine ancestor may have been critical for the transition to the freshwater environment.

  9. Horizontal gene transfer contributed to the evolution of extracellular surface structures: the freshwater polyp Hydra is covered by a complex fibrous cuticle containing glycosaminoglycans and proteins of the PPOD and SWT (sweet tooth) families. (United States)

    Böttger, Angelika; Doxey, Andrew C; Hess, Michael W; Pfaller, Kristian; Salvenmoser, Willi; Deutzmann, Rainer; Geissner, Andreas; Pauly, Barbara; Altstätter, Johannes; Münder, Sandra; Heim, Astrid; Gabius, Hans-Joachim; McConkey, Brendan J; David, Charles N


    The single-cell layered ectoderm of the fresh water polyp Hydra fulfills the function of an epidermis by protecting the animals from the surrounding medium. Its outer surface is covered by a fibrous structure termed the cuticle layer, with similarity to the extracellular surface coats of mammalian epithelia. In this paper we have identified molecular components of the cuticle. We show that its outermost layer contains glycoproteins and glycosaminoglycans and we have identified chondroitin and chondroitin-6-sulfate chains. In a search for proteins that could be involved in organising this structure we found PPOD proteins and several members of a protein family containing only SWT (sweet tooth) domains. Structural analyses indicate that PPODs consist of two tandem β-trefoil domains with similarity to carbohydrate-binding sites found in lectins. Experimental evidence confirmed that PPODs can bind sulfated glycans and are secreted into the cuticle layer from granules localized under the apical surface of the ectodermal epithelial cells. PPODs are taxon-specific proteins which appear to have entered the Hydra genome by horizontal gene transfer from bacteria. Their acquisition at the time Hydra evolved from a marine ancestor may have been critical for the transition to the freshwater environment.

  10. Superhydrophobic surfaces (United States)

    Wang, Evelyn N; McCarthy, Matthew; Enright, Ryan; Culver, James N; Gerasopoulos, Konstantinos; Ghodssi, Reza


    Surfaces having a hierarchical structure--having features of both microscale and nanoscale dimensions--can exhibit superhydrophobic properties and advantageous condensation and heat transfer properties. The hierarchical surfaces can be fabricated using biological nanostructures, such as viruses as a self-assembled nanoscale template.

  11. Spherical Surfaces

    DEFF Research Database (Denmark)

    Brander, David


    We study surfaces of constant positive Gauss curvature in Euclidean 3-space via the harmonicity of the Gauss map. Using the loop group representation, we solve the regular and the singular geometric Cauchy problems for these surfaces, and use these solutions to compute several new examples. We give...

  12. A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction (United States)

    Cho, S. Y.; Yetter, R. A.; Dryer, F. L.


    Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

  13. 2-surface twistors, embeddings and symmetries

    International Nuclear Information System (INIS)

    Jeffryes, B.P.


    2-Surface twistor space was introduced in connection with a proposal for a quasi-local definition of mass and angular momentum within general relativity. Properties of the 2-surface twistor space are related to the possibilities for embedding the 2-surface in real and complex conformally flat spaces. The additional properties of the twistor space resulting from symmetries of the 2-surface are discussed, with particular detail on axisymmetric 2-surfaces. (author)

  14. Progressive Response Surfaces (United States)

    Romero, V. J.; Swiler, L. P.


    Response surface functions are often used as simple and inexpensive replacements for computationally expensive computer models that simulate the behavior of a complex system over some parameter space. Progressive response surfaces are ones that are built up progressively as global information is added from new sample points in the parameter space. As the response surfaces are globally upgraded based on new information, heuristic indications of the convergence of the response surface approximation to the exact (fitted) function can be inferred. Sampling points can be incrementally added in a structured fashion, or in an unstructured fashion. Whatever the approach, at least in early stages of sampling it is usually desirable to sample the entire parameter space uniformly. At later stages of sampling, depending on the nature of the quantity being resolved, it may be desirable to continue sampling uniformly over the entire parameter space (Progressive response surfaces), or to switch to a focusing/economizing strategy of preferentially sampling certain regions of the parameter space based on information gained in early stages of sampling (Adaptive response surfaces). Here we consider Progressive response surfaces where a balanced indication of global response over the parameter space is desired.We use a variant of Moving Least Squares to fit and interpolate structured and unstructured point sets over the parameter space. On a 2-D test problem we compare response surface accuracy for three incremental sampling methods: Progressive Lattice Sampling; Simple-Random Monte Carlo; and Halton Quasi-Monte-Carlo sequences. We are ultimately after a system for constructing efficiently upgradable response surface approximations with reliable error estimates.

  15. Rapid degradation of the complex organic molecules in Martian surface rocks due to exposure to cosmic rays. Implications to the search of 'extinct' life on Mars by MSL and ExoMars (United States)

    Pavlov, A.; Eigenbrode, J. L.; Glavin, D. P.; Floyd, M.; Mahaffy, P. R.


    Until recently, long-term exposure to cosmic rays has not been recognized as a major environmental factor, which can alter and destroy organic molecules in the Martian surface rocks. Recent modeling studies (e.g. Pavlov et al., 2012) suggested that organic molecules with masses >100 amu would be degraded in less than 1 billion years in the top 5 cm of the Martian rocks. That poses a serious challenge to the search of ancient molecules in the shallow subsurface of Mars. However, Pavlov et al. calculated the fraction of the survived organic molecules using conservative radiolysis constants derived from the gamma irradiation experiments on pure dry amino acid mixtures (Kminek and Bada, 2006). In this study we conducted a series of gamma irradiations of amino acids and carboxylic acids mixed with silica powder. We report that the addition of silicates dramatically increased the rate of organic degradation under gamma radiation. Using the newly derived radiolysis constants for amino acids and carboxylic acids in mineral mixtures, we recalculated the rate of organic degradation in the Martian rocks as a function of rocks' depth, chemical composition and weathering rates. Our results suggest that isolated organic molecules (acids) are likely to be altered or fully degraded in the surface rocks on Mars by cosmic rays in less than 10 million years unless some additional protective mechanisms are in place. We will discuss possible strategies for the MSL's search of the elusive ancient organic molecules to overcome the adverse effects of cosmic rays in the surface Martian rocks. References. Pavlov et al., 2012 GEOPHYSICAL RESEARCH LETTERS, doi:10.1029/2012GL052166 Kminek, G., and J. Bada (2006), Earth Planet. Sci. Lett., 245, 1-5, doi:10.1016/j.epsl.2006.03.008.

  16. Complex algebraic geometry

    CERN Document Server

    Kollár, János


    This volume contains the lectures presented at the third Regional Geometry Institute at Park City in 1993. The lectures provide an introduction to the subject, complex algebraic geometry, making the book suitable as a text for second- and third-year graduate students. The book deals with topics in algebraic geometry where one can reach the level of current research while starting with the basics. Topics covered include the theory of surfaces from the viewpoint of recent higher-dimensional developments, providing an excellent introduction to more advanced topics such as the minimal model program. Also included is an introduction to Hodge theory and intersection homology based on the simple topological ideas of Lefschetz and an overview of the recent interactions between algebraic geometry and theoretical physics, which involve mirror symmetry and string theory.

  17. Iridium complexes for electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Sheehan, Stafford Wheeler; Hintermair, Ulrich; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H


    Solution-phase (e.g., homogeneous) or surface-immobilized (e.g., heterogeneous) electrode-driven oxidation catalysts based on iridium coordination compounds which self-assemble upon chemical or electrochemical oxidation of suitable precursors and methods of making and using thereof are. Iridium species such as {[Ir(LX).sub.x(H.sub.2O).sub.y(.mu.-O)].sub.z.sup.m+}.sub.n wherein x, y, m are integers from 0-4, z and n from 1-4 and LX is an oxidation-resistant chelate ligand or ligands, such as such as 2(2-pyridyl)-2-propanolate, form upon oxidation of various molecular iridium complexes, for instance [Cp*Ir(LX)OH] or [(cod)Ir(LX)] (Cp*=pentamethylcyclopentadienyl, cod=cis-cis,1,5-cyclooctadiene) when exposed to oxidative conditions, such as sodium periodate (NaIO.sub.4) in aqueous solution at ambient conditions.

  18. Complex Algebraic Varieties

    CERN Document Server

    Peternell, Thomas; Schneider, Michael; Schreyer, Frank-Olaf


    The Bayreuth meeting on "Complex Algebraic Varieties" focussed on the classification of algebraic varieties and topics such as vector bundles, Hodge theory and hermitian differential geometry. Most of the articles in this volume are closely related to talks given at the conference: all are original, fully refereed research articles. CONTENTS: A. Beauville: Annulation du H(1) pour les fibres en droites plats.- M. Beltrametti, A.J. Sommese, J.A. Wisniewski: Results on varieties with many lines and their applications to adjunction theory.- G. Bohnhorst, H. Spindler: The stability of certain vector bundles on P(n) .- F. Catanese, F. Tovena: Vector bundles, linear systems and extensions of (1).- O. Debarre: Vers uns stratification de l'espace des modules des varietes abeliennes principalement polarisees.- J.P. Demailly: Singular hermitian metrics on positive line bundles.- T. Fujita: On adjoint bundles of ample vector bundles.- Y. Kawamata: Moderate degenerations of algebraic surfaces.- U. Persson: Genus two fibra...

  19. From single-site tantalum complexes to nanoparticles of TaxNy and TaOxNy supported on silica: elucidation of synthesis chemistry by dynamic nuclear polarization surface enhanced NMR spectroscopy and X-ray absorption spectroscopy

    KAUST Repository

    Mohandas, Janet Chakkamadathil


    Air-stable catalysts consisting of tantalum nitride nanoparticles represented as a mixture of TaxNy and TaOxNy with diameters in the range of 0.5 to 3 nm supported on highly dehydroxylated silica were synthesized from TaMe5 (Me = methyl) and dimeric Ta-2(OMe)(10) with guidance by the principles of surface organometallic chemistry (SOMC). Characterization of the supported precursors and the supported nanoparticles formed from them was carried out by IR, NMR, UV-Vis, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopies complemented with XRD and high-resolution TEM, with dynamic nuclear polarization surface enhanced NMR spectroscopy being especially helpful by providing enhanced intensities of the signals of H-1, C-13, Si-29, and N-15 at their natural abundances. The characterization data provide details of the synthesis chemistry, including evidence of (a) O-2 insertion into Ta-CH3 species on the support and (b) a binuclear to mononuclear transformation of species formed from Ta-2(OMe)(10) on the support. A catalytic test reaction, cyclooctene epoxidation, was used to probe the supported nanoparticles, with 30% H2O2 serving as the oxidant. The catalysts gave selectivities up to 98% for the epoxide at conversions as high as 99% with a 3.4 wt% loading of Ta present as TaxNy/TaOxNy.

  20. Smooth embeddings with Stein surface images


    Gompf, Robert E.


    A simple characterization is given of open subsets of a complex surface that smoothly perturb to Stein open subsets. As applications, complex 2-space C^2 contains domains of holomorphy (Stein open subsets) that are exotic R^4's, and others homotopy equivalent to the 2-sphere but cut out by smooth, compact 3-manifolds. Pseudoconvex embeddings of Brieskorn spheres and other 3-manifolds into complex surfaces are constructed, as are pseudoconcave holomorphic fillings (with disagreeing contact and...

  1. Inclusion complexation of tetrabutylammonium iodide by cyclodextrins

    Indian Academy of Sciences (India)

    Host-guest inclusion complex of an ionic solid (tetrabutyl ammonium iodide) with α- and β- cyclodextrin has been explored by various physicochemical and spectroscopic methods. Surface tension and conductivity studies indicated 1:1 stoichiometry of the inclusion complexes and ¹H NMR and FT-IR studies substantiated ...

  2. Polyoxometalate coordinated transition metal complexes as ...

    Indian Academy of Sciences (India)

    Keywords. Heptamolybdate type polyoxometalate cluster anion; transition metal coordination complexes; ... industrial chemistry. This oxidation can be divided into three categories: (i) the cleavage of the C=C bond by using the surface of the metal oxide, e.g., osmium or .... supported cobalt complexes (catalysts 1 and 2) pro-.

  3. The structure and singularities of arc complexes

    DEFF Research Database (Denmark)

    Penner, Robert

    A classical combinatorial fact is that the simplicial complex consisting of disjointly embedded chords in a convex planar polygon is a sphere. For any surface F with non-empty boundary, there is an analogous complex Arc(F) consisting of suitable equivalence classes of arcs in F connecting its bou...

  4. Spectra of Velocity components over Complex Terrain

    DEFF Research Database (Denmark)

    Panofsky, H. A.; Larko, D.; Lipschut, R.


    Spectra have been measured over a variety of types of complex terrain: on tops of hills and escarpments, over land downstream of a water surface, and over rolling terrain. Differences between spectra over many types of complex terrain, and over uniform terrain, can be explained by these hypothese...

  5. Surface boxplots

    KAUST Repository

    Genton, Marc G.


    In this paper, we introduce a surface boxplot as a tool for visualization and exploratory analysis of samples of images. First, we use the notion of volume depth to order the images viewed as surfaces. In particular, we define the median image. We use an exact and fast algorithm for the ranking of the images. This allows us to detect potential outlying images that often contain interesting features not present in most of the images. Second, we build a graphical tool to visualize the surface boxplot and its various characteristics. A graph and histogram of the volume depth values allow us to identify images of interest. The code is available in the supporting information of this paper. We apply our surface boxplot to a sample of brain images and to a sample of climate model outputs.

  6. Convex surfaces

    CERN Document Server

    Busemann, Herbert


    This exploration of convex surfaces focuses on extrinsic geometry and applications of the Brunn-Minkowski theory. It also examines intrinsic geometry and the realization of intrinsic metrics. 1958 edition.

  7. Thinking Forbidden Thoughts: The Oedipus Complex as a Complex of Knowing. (United States)

    Schein, Michael


    The Oedipus complex, considered by Freud the "nuclear complex of development," played a central role in the evolution of psychoanalytic thought. This paper returns to the point of transition from the seduction theory, Freud's initial theorem, to the oedipal model, and suggests that the Oedipus complex is first and foremost a text and as such contains a multiplicity of narratives. In particular, the author articulates the close relation between the Oedipus complex and the subject of knowing, postulating that underlying its surface level, the deep-level structure of this complex is one of knowing. As a complex of knowing it is of dual quality, both promoting and impeding the ability to know.

  8. Surface decontamination

    International Nuclear Information System (INIS)

    Silva, S. da; Teixeira, M.V.


    The general methods of surface decontamination used in laboratory and others nuclear installations areas, as well as the procedures for handling radioactive materials and surfaces of work are presented. Some methods for decontamination of body external parts are mentioned. The medical supervision and assistance are required for internal or external contamination involving or not lesion in persons. From this medical radiation protection decontamination procedures are determined. (M.C.K.) [pt

  9. Surface phonons

    CERN Document Server

    Wette, Frederik


    In recent years substantial progress has been made in the detection of surface phonons owing to considerable improvements in inelastic rare gas scattering tech­ niques and electron energy loss spectroscopy. With these methods it has become possible to measure surface vibrations in a wide energy range for all wave vectors in the two-dimensional Brillouin zone and thus to deduce the complete surface phonon dispersion curves. Inelastic atomic beam scattering and electron energy loss spectroscopy have started to play a role in the study of surface phonons similar to the one played by inelastic neutron scattering in the investigation of bulk phonons in the last thirty years. Detailed comparison between experimen­ tal results and theoretical studies of inelastic surface scattering and of surface phonons has now become feasible. It is therefore possible to test and to improve the details of interaction models which have been worked out theoretically in the last few decades. At this point we felt that a concise, co...

  10. Complex Interfaces Under Change

    DEFF Research Database (Denmark)

    Rosbjerg, Dan

    The hydrosphere is dynamic across the major compartments of the Earth system: the atmosphere, the oceans and seas, the land surface water, and the groundwater within the strata below the two last compartments. The global geography of the hydrosphere essentially depends on thermodynamic and mechan...... these interfaces and interfaced compartments and processes. Climate, sea-level, oceanographic currents and hydrological processes are all affected, while anthropogenic changes are often intense in the geographic settings corresponding to such interfaces.......The hydrosphere is dynamic across the major compartments of the Earth system: the atmosphere, the oceans and seas, the land surface water, and the groundwater within the strata below the two last compartments. The global geography of the hydrosphere essentially depends on thermodynamic...... and mechanical processes that develop within this structure. Water-related processes at the interfaces between the compartments are complex, depending both on the interface itself, and on the characteristics of the interfaced compartments. Various aspects of global change directly or indirectly impact...

  11. A second course in complex analysis

    CERN Document Server

    Veech, William A


    A clear, self-contained treatment of important areas in complex analysis, this text is geared toward upper-level undergraduates and graduate students. The material is largely classical, with particular emphasis on the geometry of complex mappings.Author William A. Veech, the Edgar Odell Lovett Professor of Mathematics at Rice University, presents the Riemann mapping theorem as a special case of an existence theorem for universal covering surfaces. His focus on the geometry of complex mappings makes frequent use of Schwarz's lemma. He constructs the universal covering surface of an arbitrary pl

  12. Workbench surface editor of brain cortical surface (United States)

    Dow, Douglas E.; Nowinski, Wieslaw L.; Serra, Luis


    We have developed a 3D reach-in tool to manually reconstruct 3D cortical surface patches from 2D brain atlas images. The first application of our cortex editor is building 3D functional maps, specifically Brodmann's areas. This tool may also be useful in clinical practice to adjust incorrectly mapped atlas regions due to the deforming effect of lesions. The cortex editor allows a domain expert to control the correlation of control points across slices. Correct correlation has been difficult for 3D reconstruction algorithms because the atlas slices are far apart and because of the complex topology of the cortex which differs so much from slice to slice. Also, higher precision of the resulting surfaces is demanded since these define 3D brain atlas features upon which future stereotactic surgery may be based. The cortex editor described in this paper provides a tool suitable for a domain expert to use in defining the 3D surface of a Brodmann's area.

  13. The crystal structure of a coxsackievirus B3-RD variant and a refined 9-angstrom cryo-electron microscopy reconstruction of the virus complexed with decay-accelerating factor (DAF) provide a new footprint of DAF on the virus surface. (United States)

    Yoder, Joshua D; Cifuente, Javier O; Pan, Jieyan; Bergelson, Jeffrey M; Hafenstein, Susan


    The coxsackievirus-adenovirus receptor (CAR) and decay-accelerating factor (DAF) have been identified as cellular receptors for coxsackievirus B3 (CVB3). The first described DAF-binding isolate was obtained during passage of the prototype strain, Nancy, on rhabdomyosarcoma (RD) cells, which express DAF but very little CAR. Here, the structure of the resulting variant, CVB3-RD, has been solved by X-ray crystallography to 2.74 Å, and a cryo-electron microscopy reconstruction of CVB3-RD complexed with DAF has been refined to 9.0 Å. This new high-resolution structure permits us to correct an error in our previous view of DAF-virus interactions, providing a new footprint of DAF that bridges two adjacent protomers. The contact sites between the virus and DAF clearly encompass CVB3-RD residues recently shown to be required for binding to DAF; these residues interact with DAF short consensus repeat 2 (SCR2), which is known to be essential for virus binding. Based on the new structure, the mode of the DAF interaction with CVB3 differs significantly from the mode reported previously for DAF binding to echoviruses.

  14. Ice Surfaces (United States)

    Shultz, Mary Jane


    Ice is a fundamental solid with important environmental, biological, geological, and extraterrestrial impact. The stable form of ice at atmospheric pressure is hexagonal ice, Ih. Despite its prevalence, Ih remains an enigmatic solid, in part due to challenges in preparing samples for fundamental studies. Surfaces of ice present even greater challenges. Recently developed methods for preparation of large single-crystal samples make it possible to reproducibly prepare any chosen face to address numerous fundamental questions. This review describes preparation methods along with results that firmly establish the connection between the macroscopic structure (observed in snowflakes, microcrystallites, or etch pits) and the molecular-level configuration (detected with X-ray or electron scattering techniques). Selected results of probing interactions at the ice surface, including growth from the melt, surface vibrations, and characterization of the quasi-liquid layer, are discussed.

  15. Surface Detection using Round Cut

    DEFF Research Database (Denmark)

    Dahl, Vedrana Andersen; Dahl, Anders Bjorholm; Larsen, Rasmus


    We propose an iterative method for detecting closed surfaces in a volumetric data, where an optimal search is performed in a graph build upon a triangular mesh. Our approach is based on previous techniques for detecting an optimal terrain-like or tubular surface employing a regular grid. Unlike...... similar adaptations for triangle meshes, our method is capable of capturing complex geometries by iteratively refining the surface, where we obtain a high level of robustness by applying explicit mesh processing to intermediate results. Our method uses on-surface data support, but it also exploits data...... information about the region inside and outside the surface. This provides additional robustness to the algorithm. We demonstrate the capabilities of the approach by detecting surfaces of CT scanned objects....

  16. Glycoprotein on cell surfaces

    International Nuclear Information System (INIS)

    Muramatsu, T.


    There are conjugated polysaccharides in cell membranes and outside of animal cells, and they play important role in the control of cell behavior. In this paper, the studies on the glycoprotein on cell surfaces are reported. It was found that the glycoprotein on cell surfaces have both N-glycoside type and O-glycoside type saccharic chains. Therefore it can be concluded that the basic structure of the saccharic chains in the glycoprotein on cell surfaces is similar to that of blood serum and body fluid. The main glycoprotein in the membranes of red blood corpuscles has been studied most in detail, and it also has both types of saccharic chains. The glycoprotein in liver cell membranes was found to have only the saccharic chains of acid type and to be in different pattern from that in endoplasmic reticula and nuclear membranes, which also has the saccharic chains of neutral type. The structure of the saccharic chains of H-2 antigen, i.e. the peculiar glycoprotein on the surfaces of lymph system cells, has been studied, and it is similar to the saccharic chains of glycoprotein in blood serum. The saccharic chain structures of H-2 antigen and TL antigen are different. TL, H-2 (D), Lna and H-2 (K) are the glycoprotein on cell surfaces, and are independent molecules. The analysis of the saccharic chain patterns on cell surfaces was carried out, and it was shown that the acid type saccharic chains were similar to those of ordinary glycoprotein, because the enzyme of pneumococci hydrolyzed most of the acid type saccharic chains. The change of the saccharic chain patterns of glycoprotein on cell surfaces owing to canceration and multiplication is complex matter. (Kako, I.)

  17. Heterolytic cleavage of ammonia N-H bond by bifunctional activation in silica-grafted single site Ta(V) imido amido surface complex. Importance of the outer sphere NH3 assistance

    KAUST Repository

    Gouré, Eric


    Ammonia N-H bond is cleaved at room temperature by the silica-supported tantalum imido amido complex [(≡SiO)2Ta(NH)(-NH2)], 2, if excess ammonia is present, but requires 150 °C to achieve the same reaction if only one equivalent NH3 is added to 2. MAS solid-state 15N NMR and in situ IR spectroscopic studies of the reaction of either 15N or 2H labeled ammonia with 2 show that initial coordination of the ammonia is followed by scrambling of either 15N or 2H among ammonia, amido and imido groups. Density functional theory (DFT) calculations with a cluster model [{(μ-O)[(H3SiO) 2SiO]2}Ta(NH)(-NH2)(NH3)], 2 q·NH3, show that the intramolecular H transfer from Ta-NH2 to TaNH is ruled out, but the H transfers from the coordinated ammonia to the amido and imido groups have accessible energy barriers. The energy barrier for the ammonia N-H activation by the Ta-amido group is energetically preferred relative to the Ta-imido group. The importance of excess NH3 for getting full isotope scrambling is rationalized by an outer sphere assistance of ammonia acting as proton transfer agent, which equalizes the energy barriers for H transfer from coordinated ammonia to the amido and imido groups. In contrast, additional coordinated ammonia does not favor significantly the H transfer. These results rationalize the experimental conditions used. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011.

  18. Complexation thermodynamics of modified cyclodextrins

    DEFF Research Database (Denmark)

    Schönbeck, Jens Christian Sidney; Westh, Peter; Holm, Rene


    Inclusion complexes between two bile salts and a range of differently methylated β-cyclodextrins were studied in an attempt to rationalize the complexation thermodynamics of modified cyclodextrins. Calorimetric titrations at a range of temperatures provided precise values of the enthalpies (ΔH......°), entropies (ΔS°), and heat capacities (ΔCp) of complexation, while molecular dynamics simulations assisted the interpretation of the obtained thermodynamic parameters. As previously observed for several types of modified cyclodextrins, the substituents at the rims of the cyclodextrin induced large changes......° and then a strong decrease when the degree of substitution exceeded some threshold. Exactly the same trend was observed for ΔCp. The dehydration of nonpolar surface, as quantified by the simulations, can to a large extent explain the variation in the thermodynamic parameters. The methyl substituents form additional...

  19. Surfacing Moves

    DEFF Research Database (Denmark)

    Lutz, Peter


    such as schedules, machines, and aging bodies. To this end, the article also experiments with ‘surfacing’ as an ethnographic heuristic for figuring these different ‘spatial-timings’. The article concludes that surfacing matters not only in senior home care but also in the field-desks of ethnographic analysis....

  20. Attack surfaces

    DEFF Research Database (Denmark)

    Gruschka, Nils; Jensen, Meiko


    The new paradigm of cloud computing poses severe security risks to its adopters. In order to cope with these risks, appropriate taxonomies and classification criteria for attacks on cloud computing are required. In this work-in-progress paper we present one such taxonomy based on the notion...... of attack surfaces of the cloud computing scenario participants....

  1. Holographic complexity for time-dependent backgrounds

    Energy Technology Data Exchange (ETDEWEB)

    Momeni, Davood, E-mail: [Eurasian International Center for Theoretical Physics and Department of General Theoretical Physics, Eurasian National University, Astana 010008 (Kazakhstan); Faizal, Mir, E-mail: [Irving K. Barber School of Arts and Sciences, University of British Columbia, Okanagan, 3333 University Way, Kelowna, British Columbia V1V 1V7 (Canada); Department of Physics and Astronomy, University of Lethbridge, Lethbridge, Alberta, T1K 3M4 (Canada); Bahamonde, Sebastian, E-mail: [Department of Mathematics, University College London, Gower Street, London, WC1E 6BT (United Kingdom); Myrzakulov, Ratbay [Eurasian International Center for Theoretical Physics and Department of General Theoretical Physics, Eurasian National University, Astana 010008 (Kazakhstan)


    In this paper, we will analyze the holographic complexity for time-dependent asymptotically AdS geometries. We will first use a covariant zero mean curvature slicing of the time-dependent bulk geometries, and then use this co-dimension one spacelike slice of the bulk spacetime to define a co-dimension two minimal surface. The time-dependent holographic complexity will be defined using the volume enclosed by this minimal surface. This time-dependent holographic complexity will reduce to the usual holographic complexity for static geometries. We will analyze the time-dependence as a perturbation of the asymptotically AdS geometries. Thus, we will obtain time-dependent asymptotically AdS geometries, and we will calculate the holographic complexity for such time-dependent geometries.

  2. Complex analysis and geometry

    CERN Document Server

    Silva, Alessandro


    The papers in this wide-ranging collection report on the results of investigations from a number of linked disciplines, including complex algebraic geometry, complex analytic geometry of manifolds and spaces, and complex differential geometry.

  3. Complex Systems: An Introduction

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 9. Complex Systems: An Introduction - Anthropic Principle, Terrestrial Complexity, Complex Materials. V K Wadhawan. General Article Volume 14 Issue 9 September 2009 pp 894-906 ...

  4. Surface fertigation: a review, gaps and needs


    Hamed Ebrahimian; Mohammad R. Keshavarz; Enrique Playán


    Surface fertigation is a common choice when it comes to applying fertilizers in surface irrigated crops. The inherent complexity of the concepts and equations governing surface fertigation has made this technique a challenging research issue in the past decades. A number of researchers have used field experiments and/or modelling results to develop recommendations aiming at improving surface fertigation management. In this paper, these recommendations are reviewed and classified considering t...

  5. The Mitochondrial Complex(Ity of Cancer

    Directory of Open Access Journals (Sweden)

    Félix A. Urra


    Full Text Available Recent evidence highlights that the cancer cell energy requirements vary greatly from normal cells and that cancer cells exhibit different metabolic phenotypes with variable participation of both glycolysis and oxidative phosphorylation. NADH–ubiquinone oxidoreductase (Complex I is the largest complex of the mitochondrial electron transport chain and contributes about 40% of the proton motive force required for mitochondrial ATP synthesis. In addition, Complex I plays an essential role in biosynthesis and redox control during proliferation, resistance to cell death, and metastasis of cancer cells. Although knowledge about the structure and assembly of Complex I is increasing, information about the role of Complex I subunits in tumorigenesis is scarce and contradictory. Several small molecule inhibitors of Complex I have been described as selective anticancer agents; however, pharmacologic and genetic interventions on Complex I have also shown pro-tumorigenic actions, involving different cellular signaling. Here, we discuss the role of Complex I in tumorigenesis, focusing on the specific participation of Complex I subunits in proliferation and metastasis of cancer cells.

  6. Changes on Titan's surface (United States)

    Solomonidou, A.; Lopes, R. M. C.; Coustenis, A.; Malaska, M. J.; Sotin, C.; Rodriguez, S.; Janssen, M. A.; Drossart, P.; Lawrence, K. J.; Matsoukas, C. K.; Hirtzig, M.; Le Mouelic, S.; Jaumann, R.; Brown, R. H.; Bratsolis, E.


    Cassini's Visual and Infrared Mapping Spectrometer (VIMS) and the Titan Radar Mapper have investigated Titan's surface since 2004, unveiling a complex, dynamic and Earth-like surface. Understanding the distribution and interplay of geologic processes is important for constraining models of its interior, surface-atmospheric interactions, and climate evolution. We focus on understanding the origin of the major geomorphological units identified by Lopes et al. (2010, 2015) [1,2], Malaska et al. (2015) [3] and regions we studied in Solomonidou et al. (2014; 2015) [4,5]. Here, we investigate the nature of: Undifferentiated Plains, Hummocky/Mountainous terrains, candidate cryovolcanic sites, Labyrinth, and Dunes in terms of surface albedo behavior and spectral evolution with time to identify possible changes. Using a radiative transfer code, we find that temporal variations of surface albedo occur for some areas. Tui Regio and Sotra Patera, both candidate cryovolcanic regions, change with time, becoming darker and brighter respectively in surface albedo. In contrast, we find that the Undifferentiated Plains and the suggested evaporitic areas [6] in the equatorial regions do not present any significant changes. We are able to report the differences and similarities among the various regions and provide constraints on their chemical composition and specific processes of origin. Our results support the hypothesis that both endogenic and exogenic processes have played important roles in shaping Titan's geologic evolution. Such a variety of geologic processes and their relationship to the methane cycle make Titan important for astrobiology and habitability studies and particularly significant in solar system studies. [1] Lopes, R.M.C., et al.: Icarus, 205, 540-588, 2010; [2] Lopes, R.M.C., et al.: JGR, 118, 416-435, 2013; [3] Malaska, M., et al : Icarus, submitted, 2015;[4] Solomonidou et al.: JGR, 119, 1729-1747, 2014; [5] Solomonidou, A., et al.: In press, 2015; [6] Barnes

  7. Cortical complexity in cetacean brains. (United States)

    Hof, Patrick R; Chanis, Rebecca; Marino, Lori


    Cetaceans (dolphins, whales, and porpoises) have a long, dramatically divergent evolutionary history compared with terrestrial mammals. Throughout their 55-60 million years of evolution, cetaceans acquired a compelling set of characteristics that include echolocation ability (in odontocetes), complex auditory and communicative capacities, and complex social organization. Moreover, although cetaceans have not shared a common ancestor with primates for over 90 million years, they possess a set of cognitive attributes that are strikingly convergent with those of many primates, including great apes and humans. In contrast, cetaceans have evolved a highly unusual combination of neurobiological features different from that of primates. As such, cetacean brains offer a critical opportunity to address questions about how complex behavior can be based on very different neuroanatomical and neurobiological evolutionary products. Cetacean brains and primate brains are arguably most meaningfully conceived as alternative evolutionary routes to neurobiological and cognitive complexity. In this article, we summarize data on brain size and hemisphere surface configuration in several cetacean species and present an overview of the cytoarchitectural complexity of the cerebral cortex of the bottlenose dolphin. (c) 2005 Wiley-Liss, Inc.

  8. Surface segregation during irradiation

    International Nuclear Information System (INIS)

    Rehn, L.E.; Lam, N.Q.


    Gibbsian adsorption is known to alter the surface composition of many alloys. During irradiation, four additional processes that affect the near-surface alloy composition become operative: preferential sputtering, displacement mixing, radiation-enhanced diffusion and radiation-induced segregation. Because of the mutual competition of these five processes, near-surface compositional changes in an irradiation environment can be extremely complex. Although ion-beam induced surface compositional changes were noted as long as fifty years ago, it is only during the past several years that individual mechanisms have been clearly identified. In this paper, a simple physical description of each of the processes is given, and selected examples of recent important progress are discussed. With the notable exception of preferential sputtering, it is shown that a reasonable qualitative understanding of the relative contributions from the individual processes under various irradiation conditions has been attained. However, considerably more effort will be required before a quantitative, predictive capability can be achieved. 29 refs., 8 figs

  9. Paneling architectural freeform surfaces

    KAUST Repository

    Eigensatz, Michael


    The emergence of large-scale freeform shapes in architecture poses big challenges to the fabrication of such structures. A key problem is the approximation of the design surface by a union of patches, socalled panels, that can be manufactured with a selected technology at reasonable cost, while meeting the design intent and achieving the desired aesthetic quality of panel layout and surface smoothness. The production of curved panels is mostly based on molds. Since the cost of mold fabrication often dominates the panel cost, there is strong incentive to use the same mold for multiple panels. We cast the major practical requirements for architectural surface paneling, including mold reuse, into a global optimization framework that interleaves discrete and continuous optimization steps to minimize production cost while meeting user-specified quality constraints. The search space for optimization is mainly generated through controlled deviation from the design surface and tolerances on positional and normal continuity between neighboring panels. A novel 6-dimensional metric space allows us to quickly compute approximate inter-panel distances, which dramatically improves the performance of the optimization and enables the handling of complex arrangements with thousands of panels. The practical relevance of our system is demonstrated by paneling solutions for real, cutting-edge architectural freeform design projects. © 2010 ACM.

  10. Paneling architectural freeform surfaces

    KAUST Repository

    Eigensatz, Michael


    The emergence of large-scale freeform shapes in architecture poses big challenges to the fabrication of such structures. A key problem is the approximation of the design surface by a union of patches, so-called panels, that can be manufactured with a selected technology at reasonable cost, while meeting the design intent and achieving the desired aesthetic quality of panel layout and surface smoothness. The production of curved panels is mostly based on molds. Since the cost of mold fabrication often dominates the panel cost, there is strong incentive to use the same mold for multiple panels. We cast the major practical requirements for architectural surface paneling, including mold reuse, into a global optimization framework that interleaves discrete and continuous optimization steps to minimize production cost while meeting user-specified quality constraints. The search space for optimization is mainly generated through controlled deviation from the design surface and tolerances on positional and normal continuity between neighboring panels. A novel 6-dimensional metric space allows us to quickly compute approximate inter-panel distances, which dramatically improves the performance of the optimization and enables the handling of complex arrangements with thousands of panels. The practical relevance of our system is demonstrated by paneling solutions for real, cutting-edge architectural freeform design projects.

  11. Biocatalytic Route to Surface Active Lipid

    DEFF Research Database (Denmark)

    Cheong, Ling-Zhi; Xu, Xuebing

    Lipid can be structurally modified in order to attain improved functional properties. This work look into the possibilities of developing surface active lipids with improved functional properties through biocatalytic route. Biocatalytic route to surface active lipid are usually complex involving ...... distinct self assembling property and find useful application in surfactant industry.......Lipid can be structurally modified in order to attain improved functional properties. This work look into the possibilities of developing surface active lipids with improved functional properties through biocatalytic route. Biocatalytic route to surface active lipid are usually complex involving...

  12. New complex exact travelling wave solutions for the generalized-Zakharov equation with complex structures

    Directory of Open Access Journals (Sweden)

    Haci Mehmet Baskonus


    Full Text Available In this paper, we apply the sine-Gordon expansion method which is one of the powerful methods to the generalized-Zakharov equation with complex structure. This algorithm yields new complex hyperbolic function solutions to the generalized-Zakharov equation with complex structure. Wolfram Mathematica 9 has been used throughout the paper for plotting two- and three-dimensional surface of travelling wave solutions obtained.

  13. Hydrodynamic size and charge of polyelectrolyte complexes. (United States)

    Böhme, Ute; Scheler, Ulrich


    Polyelectrolyte complexes have a wide range of applications for surface modification and flocculation and sorption of organic molecules from solutions. As an example, complexes between poly(diallyl dimethyl ammonium chloride) and poly(styrene sulfonate) have been investigated by diffusion and electrophoresis NMR. The formation of primary or soluble complexes is monitored. The hydrodynamic size is characterized by the hydrodynamic radius, calculated from the diffusion coefficient determined by pulsed field gradient NMR. In the combination with electrophoresis NMR, the effective charge of the molecules and complexes is determined. The hydrodynamic size of the primary complex is smaller than that of the pure polyelectrolyte of the larger molecular weight, in the present case poly(styrene sulfonate), in solution, since charges are compensated by the oppositely charged polyelectrolyte and hence the repelling forces diminish. The effective charge of the complexes is drastically reduced.

  14. Complex Chemistry on Interstellar Grains (United States)

    Widicus Weaver, Susanna L.; Kelley, Matthew J.; Blake, Geoffrey A.

    Early interstellar chemical models considered complex molecule formation on grains [Allen & Robinson (1977)], but current models assume that simple molecules form on grains and subsequent gas phase ion-molecule reactions produce the more complex species [Ruffle & Herbst (2001), Charnley (2001)]. It has been shown, however, that gas phase ion-molecule reactions are insufficient for the production of such complex organic species as ethanol (CH3CH2OH) and methyl formate (CH3OCHO) [Horn et al. (2004)]. Organics such as acetaldehyde (CH3CHO), ethanol, methyl formate, acetic acid (CH3COOH), and glycolaldehyde (CH2OHCHO) have also been detected in high abundance in regions of grain mantle disruption or evaporation, indicating that these species are formed on grain surfaces [see Chengalur & Kanekar (2003), Bottinelli et al. (2004), Hollis et al. (2001)]. The mechanisms for complex molecule production on grains are clearly much more important, and much more complex, than has been recognized. Recent observational studies of these types of species have offered insight into the mechanisms for their possible grain surface synthesis. The relative hot core abundances of the 2C structural isomers methyl formate, acetic acid, and glycolaldehyde (52:2:1, respectively [Hollis et al. (2001)]) indicate that if they form on grains it is not from kinetically-controlled single-atom addition reactions. Likewise, the 3C aldose sugar, glyceraldehyde (CH2OHCHOHCHO), was not detected in Sgr B2(N-LMH) [Hollis et al. (2004)] while the 3C ketose sugar, dihydroxyacetone (CO(CH2OH)2) was detected in this source [Widicus Weaver & Blake (2005)]. Chemical pathways favoring the more stable carbonates over acids and aldehydes are required to explain these results. Interestingly, all of these species can be formed from reactions involving the abundant grain mantle constituents CO, HCOOH, and CH3OH and their radical precursors. A model has been developed to investigate this type of chemical network, and

  15. Complex structures in the Nash-Moser category

    DEFF Research Database (Denmark)

    Gravesen, Jens


    Working in the Nash-Moser category, it is shown that the harmonic and holomorphic differentials and the Weierstrass points on a closed Riemann surface depend smoothly on the complex structure. It is also shown that the space of complex structures on any compact surface forms a principal bundle over...... the Teichmüller space and hence that the uniformization maps of the closed disk and the sphere depend smoothly on the complex structure....

  16. Optical Feather and Foil for Shape and Dynamic Load Sensing of Critical Flight Surfaces, Phase I (United States)

    National Aeronautics and Space Administration — Future flight vehicles may comprise complex flight surfaces requiring coordinated in-situ sensing and actuation. Inspired by the complexity of the flight surfaces on...

  17. Radioisotope trithiol complexes (United States)

    Jurisson, Silvia S.; Cutler, Cathy S.; Degraffenreid, Anthony J.


    The present invention is directed to a series of stable radioisotope trithiol complexes that provide a simplified route for the direct complexation of radioisotopes present in low concentrations. In certain embodiments, the complex contains a linking domain configured to conjugate the radioisotope trithiol complex to a targeting vector. The invention is also directed to a novel method of linking the radioisotope to a trithiol compound to form the radioisotope trithiol complex. The inventive radioisotope trithiol complexes may be utilized for a variety of applications, including diagnostics and/or treatment in nuclear medicine.

  18. Complex and symplectic geometry

    CERN Document Server

    Medori, Costantino; Tomassini, Adriano


    This book arises from the INdAM Meeting "Complex and Symplectic Geometry", which was held in Cortona in June 2016. Several leading specialists, including young researchers, in the field of complex and symplectic geometry, present the state of the art of their research on topics such as the cohomology of complex manifolds; analytic techniques in Kähler and non-Kähler geometry; almost-complex and symplectic structures; special structures on complex manifolds; and deformations of complex objects. The work is intended for researchers in these areas.

  19. Implant surfaces and interface processes. (United States)

    Kasemo, B; Gold, J


    The past decades and current R&D of biomaterials and medical implants show some general trends. One major trend is an increased degree of functionalization of the material surface, better to meet the demands of the biological host system. While the biomaterials of the past and those in current use are essentially bulk materials (metals, ceramics, polymers) or special compounds (bioglasses), possibly with some additional coating (e.g., hydroxyapatite), the current R&D on surface modifications points toward much more complex and multifunctional surfaces for the future. Such surface modifications can be divided into three classes, one aiming toward an optimized three-dimensional physical microarchitecture of the surface (pore size distributions, "roughness", etc.), the second one focusing on the (bio) chemical properties of surface coatings and impregnations (ion release, multi-layer coatings, coatings with biomolecules, controlled drug release, etc.), and the third one dealing with the viscoelastic properties (or more generally the micromechanical properties) of material surfaces. These properties are expected to affect the interfacial processes cooperatively, i.e., there are likely synergistic effects between and among them: The surface is "recognized" by the biological system through the combined chemical and topographic pattern of the surface, and the viscoelastic properties. In this presentation, the development indicated above is discussed briefly, and current R&D in this area is illustrated with a number of examples from our own research. The latter include micro- and nanofabrication of surface patterns and topographies by the use of laser machining, photolithographic techniques, and electron beam and colloidal lithographies to produce controlled structures on implant surfaces in the size range 10 nm to 100 microns. Examples of biochemical modifications include mono- or lipid membranes and protein coatings on different surfaces. A new method to evaluate, e

  20. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.


    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  1. Mycobacterium Avium Complex (MAC) (United States)

    ... 30, 2014 Select a Language: Fact Sheet 514 Mycobacterium Avium Complex (MAC) WHAT IS MAC? HOW DO ... INTERACTION PROBLEMS THE BOTTOM LINE WHAT IS MAC? Mycobacterium Avium Complex (MAC) is a serious illness caused ...

  2. Complex sulfides and thiosalts

    International Nuclear Information System (INIS)

    Uehlls, A.


    Different types of the structures of complex sulfides, thiosalts of alkali, alkaline earth, rare earth, transition and actinide metals are considered in the review of the papers published before 1980 and devoted to the crystal structure of complex sulfides

  3. Holograms as complex media (United States)

    Caulfield, H. John


    Complex media can be grown, found in nature, or manufactured.. Holography is one way of fabricating such media. Here I review some examples of holographically manufactured complex media and speculate about some that could be made.

  4. A Transient UWB Antenna Array Used with Complex Impedance Surfaces

    Directory of Open Access Journals (Sweden)

    A. Godard


    Full Text Available The conception of a novel Ultra-Wideband (UWB antenna array, designed especially for transient radar applications through the frequency band (300 MHz–3 GHz, is proposed in this paper. For these applications, the elementary antenna must be compact and nondispersive, and the array must be able to steer in two dimensions. The geometry of the elementary antenna and its radiation characteristics are presented. The array beam steering is analyzed and a technique making the increase of the transient front-to-back ratio possible is described.

  5. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    Boron is thought to be capable of blocking active sites at the edges of graphene layer. There are three important charac- teristic effects of substitutional boron: graphitization enhance- ment, formation of boron oxide layer and redistribution of π-electrons in the graphene layer, lowering the Fermi level of carbon and inhibiting ...

  6. Surfaces of Building Practice


    Surynková, Petra


    My diploma thesis Surfaces of Building Practice deals with the basic properties of surfaces, their mathematical description, categorization, and application in technical practice. Each studied surface is defined and its process of construction and parametrical description is listed. The thesis studies selected types of surfaces in details - these surfaces include surfaces of revolution, ruled surfaces, screw surfaces, and translational surfaces. An application of each studied surfaces is show...

  7. The simple complex numbers


    Zalesny, Jaroslaw


    A new simple geometrical interpretation of complex numbers is presented. It differs from their usual interpretation as points in the complex plane. From the new point of view the complex numbers are rather operations on vectors than points. Moreover, in this approach the real, imaginary and complex numbers have similar interpretation. They are simply some operations on vectors. The presented interpretation is simpler, more natural, and better adjusted to possible applications in geometry and ...

  8. The Visibility Complex

    NARCIS (Netherlands)

    Pocchiola, Michel; Vegter, Gert


    We introduce the visibility complex of a collection O of n pairwise disjoint convex objects in the plane. This 2–dimensional cell complex may be considered as a generalization of the tangent visibility graph of O. Its space complexity k is proportional to the size of the tangent visibility graph. We

  9. Complex fuzzy soft multisets (United States)

    Alkouri, Abd Ulazeez M.; Salleh, Abdul Razak


    In this paper we combine two definitions, namely fuzzy soft multiset and complex fuzzy set to construct the definition of a complex fuzzy soft multiset and study its properties. In other words, we study the extension of a fuzzy soft multiset from real numbers to complex numbers. We also introduce its basic operations, namely complement, union and intersection. Some examples are given.

  10. Surface waves on metal-dielectric metamaterials

    DEFF Research Database (Denmark)

    Takayama, Osamu; Shkondin, Evgeniy; Panah, Mohammad Esmail Aryaee


    of surface waves and, therefore, can serve as a platform allowing many applications for surface photonics. Most of these surface waves are directional and their propagation direction is sensitive to permittivities of the media forming the interface. Hence, their propagation can be effectively controlled...... by changing a wavelength or material parameters. We discover that two new types of surface waves with complex dispersion exist for a uniaxial medium with both negative ordinary and extraordinary permittivities. Such new surface wave solutions originate from the anisotropic permittivities of the uniaxial media...

  11. Geometry of surfaces a practical guide for mechanical engineers

    CERN Document Server

    Radzevich, Stephen P


    Presents an in-depth analysis of geometry of part surfaces and provides the tools for solving complex engineering problems Geometry of Surfaces: A Practical Guide for Mechanical Engineers is a comprehensive guide to applied geometry of surfaces with focus on practical applications in various areas of mechanical engineering. The book is divided into three parts on Part Surfaces, Geometry of Contact of Part Surfaces and Mapping of the Contacting Part Surfaces. Geometry of Surfaces: A Practical Guide for Mechanical Engineers combines differential geometry and gearing theory and presents new developments in the elementary theory of enveloping surfaces. Written by a leading expert of the field, this book also provides the reader with the tools for solving complex engineering problems in the field of mechanical engineering. Presents an in-depth analysis of geometry of part surfaces Provides tools for solving complex engineering problems in the field of mechanical engineering Combines differential geometry an...

  12. Rough surface

    International Nuclear Information System (INIS)

    Hudina, M.


    For the determination of the thermal-hydraulic performances of rough surfaces, the method of evaluation is particularly important. In order to increase confidence in the results, a new evaluation procedure was introduced. This procedure is based on the transformation of simple channel experimental results to equal boundary conditions, and on the suitable application and confirmation of these transformed values in more complicated flow channel geometries. Existing methods, applied to the results obtained in an annular channel, do not fulfil all the transformation requirements. Thus a new, more complete transformation method, which uses the turbulent eddy diffusivity model, was developed. To check the quality of this transformation, within the scope of the new evaluation procedure, the results of experimental investigation in annular channels and in a bundle of hexagonal geometry were used together with the predictions of benchmark calculations. The success of the new method was confirmed by extensive comparisons, with the results of different presently-acknowledged transformations being considered as well. Based on these comparisons an assessment of the individual transformations is given. (Auth.)

  13. Complex variables I essentials

    CERN Document Server

    Solomon, Alan D


    REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Complex Variables I includes functions of a complex variable, elementary complex functions, integrals of complex functions in the complex plane, sequences and series, and poles and r

  14. Robust topology design of periodic grating surfaces

    DEFF Research Database (Denmark)

    Friis, Kasper Storgaard; Sigmund, Ole


    Modern nanoscale manufacturing techniques allow for a high degree of flexibility in designing surface microstructures and nanostructures. Injection molding of nanosized features allows for mass production of plastic components with a tailored nanostructure producing specific optical effects...... depending on the purpose. This work details the use of topology optimization for designing periodic polymer grating surfaces with complex optical properties. A method based on robust topology optimization is formulated for designing the nanostructure of plastic surfaces with extreme reflection...

  15. Cell surface engineering to control cellular interactions


    Custódio, Catarina A.; Mano, João F.


    Cell surface composition determines all interactions of the cell with its environment, thus cell functions such as adhesion, migration and cell–cell interactions can potentially be controlled by engineering and manipulating the cell membrane. Cell membranes present a rich repertoire of molecules, therefore a versatile ground for modification. However the complex and dynamic nature of the cell surface is also a major challenge for cell surface engineering that should also involve strategies co...

  16. Surface Modification and Surface - Subsurface Exchange Processes on Europa (United States)

    Phillips, C. B.; Molaro, J.; Hand, K. P.


    The surface of Jupiter's moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa's leading-trailing hemisphere brightness asymmetry. Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted "chaos-type" terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features. In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa's surface area. Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age ( 50myr) of Europa. Quantifying the timescale

  17. Iron oxide surfaces (United States)

    Parkinson, Gareth S.


    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  18. Undergraduate Laboratory for Surface Science (United States)

    Okumura, Mitchio; Beauchamp, Jesse L.; Dickert, Jeffrey M.; Essy, Blair R.; Claypool, Christopher L.


    Surface science has developed into a multidisciplinary field of research with applications ranging from heterogeneous catalysis to semiconductor etching (1). Aspects of surface chemistry are now included in physical chemistry textbooks (2) and undergraduate curricula (3), but the perceived cost and complexity of equipment has deterred the introduction of surface science methods in undergraduate laboratories (4). Efforts to expose chemistry undergraduates to state-of-the-art surface instrumentation have just begun (5). To provide our undergraduates with hands-on experience in using standard techniques for characterizing surface morphology, adsorbates, kinetics, and reaction mechanisms, we have developed a set of surface science experiments for our physical chemistry laboratory sequence. The centerpiece of the laboratory is an ultrahigh vacuum (UHV) chamber for studies of single crystal surfaces. This instrument, shown in the figure, has surface analysis capabilities including low energy electron diffraction (LEED), Auger spectroscopy, and temperature-programmed desorption (TPD). The laboratory exercises involve experiments on the well-studied Pt(111) surface. Students prepare a previously mounted single crystal sample by sputtering it with an argon ion gun and heating it under O2. Electron diffraction patterns from the cleaned surface are then obtained with a reverse view LEED apparatus (Princeton Instruments). Images are captured by a charge-coupled device (CCD) camera interfaced to a personal computer for easy downloading and subsequent analysis. Although the LEED images from a Pt(111) surface can be readily interpreted using simple diffraction arguments, this lab provides an excellent context for introducing Miller indices and reciprocal lattices (6). The surface chemical composition can be investigated by Auger spectroscopy, using the LEED apparatus as a simple energy analyzer. The temperature programmed desorption experiment, which is nearly complete, will be

  19. Complex networks from multivariate time series

    Czech Academy of Sciences Publication Activity Database

    Paluš, Milan; Hartman, David; Vejmelka, Martin


    Roč. 12, - (2010), A-14382 ISSN 1607-7962. [General Asembly of the European Geophysical Society . 02.05.2010-07.05.2010, Vienna] R&D Projects: GA AV ČR IAA300420805 Institutional research plan: CEZ:AV0Z10300504 Keywords : complex network * surface air temperature * reanalysis data * global change Subject RIV: BB - Applied Statistics, Operational Research

  20. Condensation in complex geometries

    International Nuclear Information System (INIS)

    Lauro, F.


    A mathematical evaluation of the condensation exchange coefficient can only succeds for well specified cases: small upright or inclined plates, horizontal tubes, small height vertical tubes. Among the main hypotheses accounted for this mathematical development in the case of the condensate, a laminar flow and uniform surface temperature are always considered. In practice certain shapes of surfaces significantly increase the heat transfer during the vapor condensation on a surface wet by the condensate. Such surfaces are rough surfaces such as the condensate is submitted to surface tension effects, negligeable for plane or large curvature surfaces, and the nature of the material may play an important role (temperature gradients). Results from tests on tubes with special shapes, performed in France or out of France, are given [fr