The impact of surface chemistry on the performance of localized solar-driven evaporation system

PubMed Central

Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-01-01

This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation. PMID:26337561

The impact of surface chemistry on the performance of localized solar-driven evaporation system.

PubMed

Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-09-04

This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

Static Chemistry in Disks or Clouds

NASA Astrophysics Data System (ADS)

Semenov, D.; Wiebe, D.

2006-11-01

This FORTRAN77 code can be used to model static, time-dependent chemistry in ISM and circumstellar disks. Current version is based on the OSU'06 gas-grain astrochemical network with all updates to the reaction rates, and includes surface chemistry from Hasegawa & Herbst (1993) and Hasegawa, Herbst, and Leung (1992). Surface chemistry can be modeled either with the standard rate equation approach or modified rate equation approach (useful in disks). Gas-grain interactions include sticking of neutral molecules to grains, dissociative recombination of ions on grains as well as thermal, UV, X-ray, and CRP-induced desorption of frozen species. An advanced X-ray chemistry and 3 grain sizes with power-law size distribution are also included. An deuterium extension to this chemical model is available.

Recycling microcavity optical biosensors.

PubMed

Hunt, Heather K; Armani, Andrea M

2011-04-01

Optical biosensors have tremendous potential for commercial applications in medical diagnostics, environmental monitoring, and food safety evaluation. In these applications, sensor reuse is desirable to reduce costs. To achieve this, harsh, wet chemistry treatments are required to remove surface chemistry from the sensor, typically resulting in reduced sensor performance and increased noise due to recognition moiety and optical transducer degradation. In the present work, we suggest an alternative, dry-chemistry method, based on O₂ plasma treatment. This approach is compatible with typical fabrication of substrate-based optical transducers. This treatment completely removes the recognition moiety, allowing the transducer surface to be refreshed with new recognition elements and thus enabling the sensor to be recycled.

The behavior of MC3T3-E1 cells on chitosan/poly-L-lysine composite films: effect of nanotopography, surface chemistry, and wettability.

PubMed

Zheng, Zhenhuan; Zhang, Ling; Kong, Lijun; Wang, Aijun; Gong, Yandao; Zhang, Xiufang

2009-05-01

In the present work, a series of composite films were produced from chitosan/poly-L-lysine blend solutions. The surface topography, chemistry, and wettability of composite films were characterized by atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and contact angle assay, respectively. For all composite films, blending with poly-L-lysine induced changes in surface chemistry and wettability. Interestingly, it was also found that increasing poly-L-lysine weight fraction in blend solutions could result in different nanoscaled surface topographic features, which displayed particle-, granule-, or fiber-dominant morphologies. MC3T3-E1 osteoblast-like cells were cultured on all composite films to evaluate the effects of surface nanotopography, chemistry, and wettability on cell behavior. The observations indicated that MC3T3-E1 cell behavior was affected by surface topography, chemistry, and wettability simultaneously and that cells showed strong responses to surface topography. On fiber-dominant surface, cells fully spread with obvious cytoskeleton organization and exhibited significantly higher level of adhesion and proliferation compared with particle- or granule-dominant surfaces. Furthermore, fiber-dominant surface also induced greater expression of mature osteogenic marker osteocalcin and higher mineralization based on RT-PCR and von Kossa staining. The results suggest that topographic modification of chitosan substratum at the nanoscale may be exploited in regulating cell behavior for its applications in tissue engineering.

Molecular-level chemistry of model single-crystal oxide surfaces with model halogenated compounds

NASA Astrophysics Data System (ADS)

Adib, Kaveh

Synchrotron-based X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD) and low energy electron diffraction (LEED) have been used to investigate, at a molecular level, the chemistry of different terminations of single crystal iron-oxide surfaces with probe molecules (CCl4 and D2O). Comparisons of the reactivity of these surfaces towards CCl4, indicate that the presence of an uncapped surface Fe cation (strong Lewis acid site) and an adjacent oxygen site capped by that cation can effect the C-Cl bond cleavage in CCl4, resulting in dissociatively adsorbed Cl-adatoms and carbon-containing fragments. If in addition to these sites, an uncapped surface oxygen (Lewis base) site is also available, the carbon-containing moiety can then move that site, coordinate itself with that uncapped oxygen, and stabilize itself. At a later step, the carbon-containing fragment may form a strong covalent bond with the uncapped oxygen and may even abstract that surface oxygen. On the other hand, if an uncapped oxygen is not available to stabilize the carbon-containing fragment, the surface coordination will not occur and upon the subsequent thermal annealing of the surface the Cl-adatoms and the carbon-containing fragments will recombine and desorb as CCl4. Finally, the presence of surface deuteroxyls blocking the strong Lewis acid and base sites of the reactive surface, passivates this surface. Such a deuteroxylated surface will be unreactive towards CCl 4. Such a molecular level understanding of the surface chemistry of metal-oxides will have applications in the areas of selective catalysis, including environmental catalysis, and chemical sensor technology.

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

Modification of heterogeneous chemistry by complex substrate morphology

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

Henson, B.F.; Buelow, S.J.; Robinson, J.M.

1998-12-31

This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous reaction with a surface. Typically the surface exists as a dispersion or matrix of particulate matter or pores, and a determination of the heterogeneous chemistry of the system must address the extent to which the complexity of the environmental surface affects the reaction rates. Reactions that are of current interest are the series of chlorine nitrate reactions important in polar ozone depletion. The authors have applied surfacemore » spectroscopic techniques developed at LANL to address the chemistry of chlorine nitrate reactions on porous nitric and sulfuric acid ice surfaces as a model study of the measurement of complex, heterogeneous reaction rates. The result of the study is an experimental determination of the surface coverage of one adsorbed reagent and a mechanism of reactivity based on the dependence of this coverage on temperature and vapor pressure. The resulting mechanism allows the first comprehensive modeling of chlorine nitrate reaction probability data from several laboratories.« less

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

NASA Astrophysics Data System (ADS)

Williams, Mackenzie G.; Teplyakov, Andrew V.

2018-07-01

Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

Constitutional Dynamics of Metal-Organic Motifs on a Au(111) Surface.

PubMed

Kong, Huihui; Zhang, Chi; Xie, Lei; Wang, Likun; Xu, Wei

2016-06-13

Constitutional dynamic chemistry (CDC), including both dynamic covalent chemistry and dynamic noncovalent chemistry, relies on reversible formation and breakage of bonds to achieve continuous changes in constitution by reorganization of components. In this regard, CDC is considered to be an efficient and appealing strategy for selective fabrication of surface nanostructures by virtue of dynamic diversity. Although constitutional dynamics of monolayered structures has been recently demonstrated at liquid/solid interfaces, most of molecular reorganization/reaction processes were thought to be irreversible under ultrahigh vacuum (UHV) conditions where CDC is therefore a challenge to be achieved. Here, we have successfully constructed a system that presents constitutional dynamics on a solid surface based on dynamic coordination chemistry, in which selective formation of metal-organic motifs is achieved under UHV conditions. The key to making this reversible switching successful is the molecule-substrate interaction as revealed by DFT calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Aromatic, Alphatic, Enigmatic: The Chemistry of Titan

NASA Astrophysics Data System (ADS)

Horst, Sarah

2017-10-01

The extraordinary complexity of Titan’s atmospheric chemistry far surpasses that of any other solar system atmosphere. With its thick N2 atmosphere and stable bodies of liquid on its surface, Titan also possesses many physical processes that are similar to those that occur on Earth. The connection between Titan’s surface and atmosphere is unique in our solar system; atmospheric chemistry produces materials that are deposited on the surface and subsequently altered by surface-atmosphere interactions such as aeolian and fluvial processes resulting in the formation of extensive dune fields and expansive lakes and seas. Titan’s atmosphere is favorable for organic haze formation, which combined with the presence of some oxygen-bearing molecules indicates that Titan’s atmosphere may produce molecules of prebiotic interest. The combination of organics and liquid, in the form of water in a subsurface ocean and methane/ethane in the surface lakes and seas, means that Titan may be the ideal place in the solar system to test ideas about habitability, prebiotic chemistry, and the ubiquity and diversity of life in the universe. I will review our current understanding of chemistry on Titan forged from the powerful combination of Earth-based observations, remote sensing and in situ spacecraft measurements, laboratory experiments, and models. I will conclude with some of the questions that remain after Cassini-Huygens.

Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

NASA Astrophysics Data System (ADS)

Yonata, B.; Nasrudin, H.

2018-01-01

A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

Why surface chemistry matters for QD–QD resonance energy transfer

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

Hoffman, Jacob B.; Alam, Rabeka; Kamat, Prashant V.

Resonance energy transfer (RET) has been shown to occur in films of semiconductor quantum dots (QDs) with variation in QD composition and size. When coupled with charge carrier transfer, RET could provide a complementary strategy for light harvesting in QD based solid state photovoltaic devices. Due to a direct dependence on the optical properties of the donor and acceptor, QD surface chemistry plays a drastic role in determining the efficiency of RET. Here, the impact of QD surface chemistry on RET in QD films was investigated using a pair of different sized CdSe QDs spin-cast onto a glass substrate. Themore » effects of QD surface passivation on RET were studied by removing surface ligands through QD washing and adding an insulating ZnS shell. In addition, QD films were subjected to solid state ligand exchanges with thiolated ligands in order to mimic a layer-by-layer deposition method commonly used in the construction of QD photovoltaics. These solid state ligand exchanges exhibit drastic quenching of RET in the films. As a result, these experiments highlight the importance of understanding surface chemistry when designing photovoltaics that utilize RET.« less

Why surface chemistry matters for QD–QD resonance energy transfer

DOE PAGES

Hoffman, Jacob B.; Alam, Rabeka; Kamat, Prashant V.

2017-01-12

Resonance energy transfer (RET) has been shown to occur in films of semiconductor quantum dots (QDs) with variation in QD composition and size. When coupled with charge carrier transfer, RET could provide a complementary strategy for light harvesting in QD based solid state photovoltaic devices. Due to a direct dependence on the optical properties of the donor and acceptor, QD surface chemistry plays a drastic role in determining the efficiency of RET. Here, the impact of QD surface chemistry on RET in QD films was investigated using a pair of different sized CdSe QDs spin-cast onto a glass substrate. Themore » effects of QD surface passivation on RET were studied by removing surface ligands through QD washing and adding an insulating ZnS shell. In addition, QD films were subjected to solid state ligand exchanges with thiolated ligands in order to mimic a layer-by-layer deposition method commonly used in the construction of QD photovoltaics. These solid state ligand exchanges exhibit drastic quenching of RET in the films. As a result, these experiments highlight the importance of understanding surface chemistry when designing photovoltaics that utilize RET.« less

Dragonfly: In Situ Exploration of Titan's Organic Chemistry and Habitability

NASA Astrophysics Data System (ADS)

Turtle, E. P.; Barnes, J. W.; Trainer, M. G.; Lorenz, R. D.

2017-12-01

Titan's abundant complex carbon-rich chemistry, interior ocean, and past presence of liquid water on the surface make it an ideal destination to study prebiotic chemical processes and document the habitability of an extraterrestrial environment. Titan exploration is a high science priority due to the level of organic synthesis that it supports. Moreover, opportunities for organics to have interacted with liquid water at the surface (e.g., in impact melt sheets) increase the potential for chemical processes to progress further, providing an unparalleled opportunity to investigate prebiotic chemistry, as well as to search for signatures of potential water-based or even hydrocarbon-based life. The diversity of Titan's surface materials and environments drives the scientific need to be able to sample a variety of locations, thus mobility is key for in situ measurements. Titan's atmosphere is 4 times denser than Earth's reducing the wing/rotor area required to generate a given amount of lift, and the low gravity reduces the required magnitude of lift, making heavier-than-air mobility highly efficient. Dragonfly is a rotorcraft lander mission proposed to NASA's New Frontiers Program to take advantage of Titan's unique natural laboratory to understand how far chemistry can progress in environments that provide key ingredients for life. Measuring the compositions of materials in different environments will reveal how far organic chemistry has progressed. Surface material can be sampled into a mass spectrometer to identify the chemical components available and processes at work to produce biologically relevant compounds. Bulk elemental surface composition can be determined by a neutron-activated gamma-ray spectrometer. Meteorology measurements can characterize Titan's atmosphere and diurnal and spatial variations therein. Geologic features can be characterized via remote-sensing observations, which also provide context for samples. Seismic sensing can probe subsurface structure and activity. In addition to surface investigations, Dragonfly can perform measurements during flight, including atmospheric profiles and aerial observations of surface geology, which also provide sampling context and scouting for landing sites.

Particle self-assembly at ionic liquid-based interfaces.

PubMed

Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

2014-04-01

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. © 2013.

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

NASA Astrophysics Data System (ADS)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

2017-02-01

The Huisgen cycloaddition reaction (;click; chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

Selectivity in analytical chemistry: two interpretations for univariate methods.

PubMed

Dorkó, Zsanett; Verbić, Tatjana; Horvai, George

2015-01-01

Selectivity is extremely important in analytical chemistry but its definition is elusive despite continued efforts by professional organizations and individual scientists. This paper shows that the existing selectivity concepts for univariate analytical methods broadly fall in two classes: selectivity concepts based on measurement error and concepts based on response surfaces (the response surface being the 3D plot of the univariate signal as a function of analyte and interferent concentration, respectively). The strengths and weaknesses of the different definitions are analyzed and contradictions between them unveiled. The error based selectivity is very general and very safe but its application to a range of samples (as opposed to a single sample) requires the knowledge of some constraint about the possible sample compositions. The selectivity concepts based on the response surface are easily applied to linear response surfaces but may lead to difficulties and counterintuitive results when applied to nonlinear response surfaces. A particular advantage of this class of selectivity is that with linear response surfaces it can provide a concentration independent measure of selectivity. In contrast, the error based selectivity concept allows only yes/no type decision about selectivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Dragonfly: Exploring Titan's Surface with a New Frontiers Relocatable Lander

NASA Astrophysics Data System (ADS)

Barnes, Jason W.; Turtle, Elizabeth P.; Trainer, Melissa G.; Lorenz, Ralph

2017-10-01

We proposed to the NASA New Frontiers 4 mission call a lander to assess Titan's prebiotic chemistry, evaluate its habitability, and search for biosignatures on its surface. Titan as an Ocean World is ideal for the study of prebiotic chemical processes and the habitability of an extraterrestrial environment due to its abundant complex carbon-rich chemistry and because both liquid water and liquid hydrocarbons can occur on its surface. Transient liquid water surface environments can be created by both impacts and cryovolcanic processes. In both cases, the water could mix with surface organics to form a primordial soup. The mission would sample both organic sediments and water ice to measure surface composition, achieving surface mobility by using rotors to take off, fly, and land at new sites. The Dragonfly rotorcraft lander can thus convey a single capable instrument suite to multiple locations providing the capability to explore diverse locations 10s to 100s of kilometers apart to characterize the habitability of Titan's environment, investigate how far prebiotic chemistry has progressed, and search for chemical signatures indicative of water- and/or hydrocarbon-based life.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

PubMed

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

2016-03-14

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

PubMed Central

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

2016-01-01

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

Design, development and applications of novel techniques for studying surface mechanical properties

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa

1989-01-01

Research is reviewed for the adhesion, friction, and micromechanical properties of materials and examples of the results presented. The ceramic and metallic materials studied include silicon carbide, aluminum oxide, and iron-base amorphous alloys. The design and operation of a torsion balance adapted for study of adhesion from the Cavendish balance are discussed first. The pull-off force (adhesion) and shear force (friction) required to break the interfacial junctions between contacting surfaces of the materials were examined at various temperatures in a vacuum. The surface chemistry of the materials was analyzed by X-ray photoelectron spectroscopy. Properties and environmental conditions of the surface regions which affect adhesion and friction-such as surface segregation, composition, crystal structure, surface chemistry, and temperature were also studied.

Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

PubMed

Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

2013-12-17

This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (<4 mg/L of dissolved organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

NASA Astrophysics Data System (ADS)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

The tunable wettability in multistimuli-responsive smart graphene surfaces

NASA Astrophysics Data System (ADS)

Wan, Shanhong; Pu, Jibin; Zhang, Xiaoqian; Wang, Liping; Xue, Qunji

2013-01-01

The tunable wettability of smart graphene films onto stainless steel substrates with a multi-response to different environmental stimuli has been investigated including light irradiation, pH, electric field, and annealing temperature. Conductive graphene film exhibited the controllable transition from water-repellent to water-loving characteristic in response to different environment fields, which primarily resulted from the morpho-chemically synergistic effect as well as the restoration of electronic stucture. Based on the fundamental theories of wettability, mechanisms in switching from hydrophobicity to hydrophilicity for smart graphene surface including thermal chemistry, electrostatic, photo-induced surface chemistry, solvent, and pH methods were presented.

DNA-Mediated Electrochemistry

PubMed Central

Gorodetsky, Alon A.; Buzzeo, Marisa C.

2009-01-01

The base pair stack of DNA has been demonstrated as a medium for long range charge transport chemistry both in solution and at DNA-modified surfaces. This chemistry is exquisitely sensitive to structural perturbations in the base pair stack as occur with lesions, single base mismatches, and protein binding. We have exploited this sensitivity for the development of reliable electrochemical assays based on DNA charge transport at self-assembled DNA monolayers. Here we discuss the characteristic features, applications, and advantages of DNA-mediated electrochemistry. PMID:18980370

Development of a Detailed Surface Chemistry Framework in DSMC

NASA Technical Reports Server (NTRS)

Swaminathan-Gopalan, K.; Borner, A.; Stephani, K. A.

2017-01-01

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Chemistry of the surface and lower atmosphere of Venus

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Treiman, A.

1992-01-01

A comprehensive overview of the chemical interactions between the atmosphere and surface of Venus is presented. Earth-based, earth-orbital, and spacecraft data on the composition of the atmosphere and surface of Venus are presented and applied to quantitative evaluations of the chemical interactions between carbon, hydrogen, sulfur, chlorine, fluorine, and nitrogen-containing gases and possible minerals on the Venus surface. The calculation results are used to predict stable minerals and mineral assemblages on the Venus surface to determine which, if any, atmospheric gases are buffered by mineral assemblages on the surface, and to critically review and assess prior work on atmosphere-surface chemistry on Venus. It is concluded that the CO2 pressure on Venus is comparable to the CO2 equilibrium partial pressure developed by the calcite + wollastonite + quartz assemblage at the mean Venus surface temperature of 740 K.

Chemical state evolution in ferroelectric films during tip-induced polarization and electroresistive switching

DOE PAGES

Ievlev, Anton V.; Maksymovych, Petro; Trassin, Morgan; ...

2016-10-11

Domain formation and ferroelectric switching is fundamentally inseparable from polarization screening, which on free surfaces can be realized via band bending and ionic adsorption. In the latter case, polarization switching is intrinsically coupled to the surface electrochemical phenomena, and the electrochemical stage can control kinetics and induce long-range interactions. However, despite extensive evidence towards the critical role of surface electrochemistry, little is known about the nature of the associated processes. Here we combine SPM tip induce polarization switching and secondary ion mass spectrometry to explore the evolution of chemical state of ferroelectric during switching. Surprisingly, we find that even pristinemore » surfaces contain ions (e.g. Cl -) that are not anticipated based on chemistry of the system and processing. In the ferroelectric switching regime, we find surprising changes in surface chemistry, including redistribution of base cations. Finally, at higher voltages in the electroforming regime significant surface deformation was observed and associated with a strong ion intermixing.« less

Relationship of wood surface energy to surface composition

Treesearch

Feipeng P. Liu; Timothy G. Rials; John Simonsen

1998-01-01

The wood cell wall is composed of cellulose, lignin, hemicelluloses, and extractives. Thus, the surface energy of the wood material must be some combination of the surface energies of these components. The influence of extractives on wood surface chemistry can be important in diverse industrial applications, such as coating, pulping, and wood-based composites. In this...

Spectroscopic and electrochemical characterization of interfacial biomimetic assemblies on electrochemically generated gold oxide surfaces.

PubMed

Krysiński, Paweł; Blanchard, G J

2005-04-01

We report on the formation of a gold oxide layer and the reaction of this oxide with an acid chloride to form a stable, relatively complete monolayer bound through an ester-like bond to the gold oxide surface. We have used cyclic voltammetry, FTIR and optical ellipsometry to characterize this novel monolayer structure. The exposed functional groups of this monolayer can participate in subsequent surface reactions, opening the door to the use of oxide-based surface attachment chemistry on metallic substrates. This chemistry will allow for the formation of films tailored to contain both hydrophobic and hydrophilic regions, stacked at predetermined distances from the substrate that may serve as biomembrane mimetic assemblies.

Role of Surface Chemistry on Catalyst/Ionomer Interactions for Transition Metal–Nitrogen–Carbon Electrocatalysts

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

Artyushkova, Kateryna; Workman, Michael J.; Matanovic, Ivana

The role of the interaction between doped carbon-based materials and ionic conductors is essential in multiple technologies, from fuel cells and energy storage devices to conductive polymer composites. In this paper, we report how the surface chemistry of transition metal–nitrogen–carbon (MNC) electrocatalysts affects catalyst–ionomer interaction and the resulting structure of cathodes. The cathode structure resulting from these interactions is directly related to the performance in membrane electrode assembly (MEA) fuel cells. To advance the development of platinum group metal (PGM)-free electrodes for the oxygen reduction reaction it is necessary to understand the structure of the catalyst layers with focus onmore » chemistry and distribution of active sites and ionomer morphology. To assess catalyst interaction with an ionomer, X-ray photoelectron spectroscopy is applied to study the chemistry of catalyst layers while density functional theory (DFT) is used to calculate adsorption energies of the ionomer side chain on different nitrogen species. We report that a high surface concentration of hydrogenated nitrogen at the surface of MNC catalysts causes inefficient ionomer morphology, while an abundance of surface oxides promotes both an efficient distribution of active sites and an optimal ionomer–catalyst interface. The critical role of protonation of nitrogen within catalytic layers in inhibiting proton transport during fuel cell operation is also suggested. As a result, this is the first report of the effect the surface chemistry of MNC catalysts, in the presence of the ionomer, has on the structure and performance of MEA electrodes.« less

Role of Surface Chemistry on Catalyst/Ionomer Interactions for Transition Metal–Nitrogen–Carbon Electrocatalysts

DOE PAGES

Artyushkova, Kateryna; Workman, Michael J.; Matanovic, Ivana; ...

2017-12-18

The role of the interaction between doped carbon-based materials and ionic conductors is essential in multiple technologies, from fuel cells and energy storage devices to conductive polymer composites. In this paper, we report how the surface chemistry of transition metal–nitrogen–carbon (MNC) electrocatalysts affects catalyst–ionomer interaction and the resulting structure of cathodes. The cathode structure resulting from these interactions is directly related to the performance in membrane electrode assembly (MEA) fuel cells. To advance the development of platinum group metal (PGM)-free electrodes for the oxygen reduction reaction it is necessary to understand the structure of the catalyst layers with focus onmore » chemistry and distribution of active sites and ionomer morphology. To assess catalyst interaction with an ionomer, X-ray photoelectron spectroscopy is applied to study the chemistry of catalyst layers while density functional theory (DFT) is used to calculate adsorption energies of the ionomer side chain on different nitrogen species. We report that a high surface concentration of hydrogenated nitrogen at the surface of MNC catalysts causes inefficient ionomer morphology, while an abundance of surface oxides promotes both an efficient distribution of active sites and an optimal ionomer–catalyst interface. The critical role of protonation of nitrogen within catalytic layers in inhibiting proton transport during fuel cell operation is also suggested. As a result, this is the first report of the effect the surface chemistry of MNC catalysts, in the presence of the ionomer, has on the structure and performance of MEA electrodes.« less

Defining an optimal surface chemistry for pluripotent stem cell culture in 2D and 3D

NASA Astrophysics Data System (ADS)

Zonca, Michael R., Jr.

Surface chemistry is critical for growing pluripotent stem cells in an undifferentiated state. There is great potential to engineer the surface chemistry at the nanoscale level to regulate stem cell adhesion. However, the challenge is to identify the optimal surface chemistry of the substrata for ES cell attachment and maintenance. Using a high-throughput polymerization and screening platform, a chemically defined, synthetic polymer grafted coating that supports strong attachment and high expansion capacity of pluripotent stem cells has been discovered using mouse embryonic stem (ES) cells as a model system. This optimal substrate, N-[3-(Dimethylamino)propyl] methacrylamide (DMAPMA) that is grafted on 2D synthetic poly(ether sulfone) (PES) membrane, sustains the self-renewal of ES cells (up to 7 passages). DMAPMA supports cell attachment of ES cells through integrin beta1 in a RGD-independent manner and is similar to another recently reported polymer surface. Next, DMAPMA has been able to be transferred to 3D by grafting to synthetic, polymeric, PES fibrous matrices through both photo-induced and plasma-induced polymerization. These 3D modified fibers exhibited higher cell proliferation and greater expression of pluripotency markers of mouse ES cells than 2D PES membranes. Our results indicated that desirable surfaces in 2D can be scaled to 3D and that both surface chemistry and structural dimension strongly influence the growth and differentiation of pluripotent stem cells. Lastly, the feasibility of incorporating DMAPMA into a widely used natural polymer, alginate, has been tested. Novel adhesive alginate hydrogels have been successfully synthesized by either direct polymerization of DMAPMA and methacrylic acid blended with alginate, or photo-induced DMAPMA polymerization on alginate nanofibrous hydrogels. In particular, DMAPMA-coated alginate hydrogels support strong ES cell attachment, exhibiting a concentration dependency of DMAPMA. This research provides a new avenue for stem cell culture and maintenance using an optimal organic-based chemistry.

Surface chemistry, microstructure and friction properties of some ferrous-base metallic glasses at temperatures to 750 C

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analysis, transmission electron microscopy, diffraction studies, and sliding friction experiments were conducted with ferrous-base metallic glasses in sliding contact with aluminum oxide at temperatures from room to 750 C in a vacuum of 30 nPa. The results indicate that there is a significant temperature influence on the friction properties, surface chemistry, and microstructure of metallic glasses. The relative concentrations of the various constituents at the surface of the sputtered specimens were very different from the normal bulk compositions. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and silicon oxide at 350 C and boron nitride above 500 C. The coefficient of friction increased with increasing temperature to 350 C. Above 500 C the coefficient of friction decreased rapidly. The segregation of contaminants may be responsible for the friction behavior.

Direct conversion of hydride- to siloxane-terminated silicon quantum dots

DOE PAGES

Anderson, Ryan T.; Zang, Xiaoning; Fernando, Roshan; ...

2016-10-20

Here, peripheral surface functionalization of hydride-terminated silicon quantum dots (SiQD) is necessary in order to minimize their oxidation/aggregation and allow for solution processability. Historically thermal hydrosilylation addition of alkenes and alkynes across the Si-H surface to form Si-C bonds has been the primary method to achieve this. Here we demonstrate a mild alternative approach to functionalize hydride-terminated SiQDs using bulky silanols in the presence of free-radical initiators to form stable siloxane (~Si-O-SiR 3) surfaces with hydrogen gas as a byproduct. This offers an alternative to existing methods of forming siloxane surfaces that require corrosive Si-Cl based chemistry with HCl byproducts.more » A 52 nm blue shift in the photoluminescent spectra of siloxane versus alkyl-functionalized SiQDs is observed that we explain using computational theory. Model compound synthesis of silane and silsesquioxane analogues is used to optimize surface chemistry and elucidate reaction mechanisms. Thorough characterization on the extent of siloxane surface coverage is provided using FTIR and XPS. As a result, TEM is used to demonstrate SiQD size and integrity after surface chemistry and product isolation.« less

Interaction between carbon fibers and polymer sizing: Influence of fiber surface chemistry and sizing reactivity

NASA Astrophysics Data System (ADS)

Moosburger-Will, Judith; Bauer, Matthias; Laukmanis, Eva; Horny, Robert; Wetjen, Denise; Manske, Tamara; Schmidt-Stein, Felix; Töpker, Jochen; Horn, Siegfried

2018-05-01

Different aspects of the interaction of carbon fibers and epoxy-based polymer sizings are investigated, e.g. the wetting behavior, the strength of adhesion between fiber and sizing, and the thermal stability of the sizing layer. The influence of carbon fiber surface chemistry and sizing reactivity is investigated using fibers of different degree of anodic oxidation and sizings with different number of reactive epoxy groups per molecule. Wetting of the carbon fibers by the sizing dispersion is found to be specified by both, the degree of fiber activation and the sizing reactivity. In contrast, adhesion strength between fibers and sizing is dominated by the surface chemistry of the carbon fibers. Here, the number of surface oxygen groups seems to be the limiting factor. We also find that the sizing and the additional functionalities induced by anodic oxidation are removed by thermal treatment at 600 °C, leaving the carbon fiber in its original state after carbonization.

Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

NASA Astrophysics Data System (ADS)

Sodeau, J.; Oriordan, B.

2003-04-01

CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

Quantitative analysis of osteoblast behavior on microgrooved hydroxyapatite and titanium substrata.

PubMed

Lu, Xiong; Leng, Yang

2003-09-01

The effects of implant surface topography and chemistry on osteoblast behavior have been a research focus because of their potential importance in orthopedic and dental applications. This work focused on the topographic effects of hydroxyapatite (HA) and titanium (Ti) surface that had identical micropatterns to determine whether there was synergistic interaction between surface chemistry and surface topography. Surface microgrooves with six different groove widths (4, 8, 16, 24, 30, and 38 microm) and three different groove depths (2, 4, and 10 microm) were made on single crystalline silicon wafers using microfabrication techniques. Ti and HA thin films were coated on the microgrooves by radio-frequency magnetron sputtering. After that, human osteoblast-like cells were seeded and cultured on the microgrooved surfaces for up to 7 days. The cells' behavior was examined using scanning electron microscopy after cells were fixed and dehydrated. Statistical analysis was based on quantitative data of orientation angle, evaluating the contact guidance, and form index, describing cell shape or cell morphology changes. The contact guidance and cell shape changes were observed on the HA and Ti microgrooves. No difference in orientation angle between HA and Ti microgrooves was found. This might suggest that surface chemistry was not a significant influence on cell guidance. However, the form index analysis indicated an interaction between topographic effects and surface chemistry. Thus, conclusions about surface topographic effects on cell behavior drawn from one type of material cannot simply be applied to another type of material. Copyright 2003 Wiley Periodicals, Inc. J Biomed Mater Res 66A: 677-687, 2003

Supramolecular chemistry at interfaces: host-guest interactions for fabricating multifunctional biointerfaces.

PubMed

Yang, Hui; Yuan, Bin; Zhang, Xi; Scherman, Oren A

2014-07-15

CONSPECTUS: Host-guest chemistry can greatly improve the selectivity of biomolecule-ligand binding on account of recognition-directed interactions. In addition, functional structures and the actuation of supramolecular assemblies in molecular systems can be controlled efficiently through various host-guest chemistry. Together, these highly selective, strong yet dynamic interactions can be exploited as an alternative methodology for applications in the field of programmable and controllable engineering of supramolecular soft materials through the reversible binding between complementary components. Many processes in living systems such as biotransformation, transportation of matter, and energy transduction begin with interfacial molecular recognition, which is greatly influenced by various external stimuli at biointerfaces. Detailed investigations about the molecular recognition at interfaces can result in a better understanding of life science, and further guide us in developing new biomaterials and medicines. In order to mimic complicated molecular-recognition systems observed in nature that adapt to changes in their environment, combining host-guest chemistry and surface science is critical for fabricating the next generation of multifunctional biointerfaces with efficient stimuli-responsiveness and good biocompatibility. In this Account, we will summarize some recent progress on multifunctional stimuli-responsive biointerfaces and biosurfaces fabricated by cyclodextrin- or cucurbituril-based host-guest chemistry and highlight their potential applications including drug delivery, bioelectrocatalysis, and reversible adsorption and resistance of peptides, proteins, and cells. In addition, these biointerfaces and biosurfaces demonstrate efficient response toward various external stimuli, such as UV light, pH, redox chemistry, and competitive guests. All of these external stimuli can aid in mimicking the biological stimuli evident in complex biological environments. We begin by reviewing the current state of stimuli-responsive supramolecular assemblies formed by host-guest interactions, discussing how to transfer host-guest chemistry from solution onto surfaces required for fabricating multifunctional biosurfaces and biointerfaces. Then, we present different stimuli-responsive biosurfaces and biointerfaces, which have been prepared through a combination of cyclodextrin- or cucurbituril-based host-guest chemistry and various surface technologies such as self-assembled monolayers or layer-by-layer assembly. Moreover, we discuss the applications of these biointerfaces and biosurfaces in the fields of drug release, reversible adsorption and release of some organic molecules, peptides, proteins, and cells, and photoswitchable bioelectrocatalysis. In addition, we summarize the merits and current limitations of these methods for fabricating multifunctional stimuli-responsive biointerfaces in a dynamic noncovalent manner. Finally, we present possible strategies for future designs of stimuli-responsive multifunctional biointerfaces and biosurfaces by combining host-guest chemistry with surface science, which will lead to further critical development of supramolecular chemistry at interfaces.

Modeling, Measurements, and Fundamental Database Development for Nonequilibrium Hypersonic Aerothermodynamics

NASA Technical Reports Server (NTRS)

Bose, Deepak

2012-01-01

The design of entry vehicles requires predictions of aerothermal environment during the hypersonic phase of their flight trajectories. These predictions are made using computational fluid dynamics (CFD) codes that often rely on physics and chemistry models of nonequilibrium processes. The primary processes of interest are gas phase chemistry, internal energy relaxation, electronic excitation, nonequilibrium emission and absorption of radiation, and gas-surface interaction leading to surface recession and catalytic recombination. NASAs Hypersonics Project is advancing the state-of-the-art in modeling of nonequilibrium phenomena by making detailed spectroscopic measurements in shock tube and arcjets, using ab-initio quantum mechanical techniques develop fundamental chemistry and spectroscopic databases, making fundamental measurements of finite-rate gas surface interactions, implementing of detailed mechanisms in the state-of-the-art CFD codes, The development of new models is based on validation with relevant experiments. We will present the latest developments and a roadmap for the technical areas mentioned above

Nanoporous Gold as a Neural Interface Coating: Effects of Topography, Surface Chemistry, and Feature Size

DOE PAGES

Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; ...

2015-02-23

We report that designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron–electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au’s interactionmore » with cortical neuron–glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. In conclusion, our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron–electrode coupling through nanostructure-mediated suppression of scar tissue formation.« less

Effects of Chemistry on Blunt-Body Wake Structure

NASA Technical Reports Server (NTRS)

Dogra, Virendra K.; Moss, James N.; Wilmoth, Richard G.; Taylor, Jeff C.; Hassan, H. A.

1995-01-01

Results of a numerical study are presented for hypersonic low-density flow about a 70-deg blunt cone using direct simulation Monte Carlo (DSMC) and Navier-Stokes calculations. Particular emphasis is given to the effects of chemistry on the near-wake structure and on the surface quantities and the comparison of the DSMC results with the Navier-Stokes calculations. The flow conditions simulated are those experienced by a space vehicle at an altitude of 85 km and a velocity of 7 km/s during Earth entry. A steady vortex forms in the near wake for these freestream conditions for both chemically reactive and nonreactive air gas models. The size (axial length) of the vortex for the reactive air calculations is 25% larger than that of the nonreactive air calculations. The forebody surface quantities are less sensitive to the chemistry than the base surface quantities. The presence of the afterbody has no effect on the forebody flow structure or the surface quantities. The comparisons of DSMC and Navier-Stokes calculations show good agreement for the wake structure and the forebody surface quantities.

Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

NASA Astrophysics Data System (ADS)

Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

2014-06-01

Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding. Electronic supplementary information (ESI) is available: Fluorescence spectra, ITC, CD spectra and other data as described in the text. See DOI: 10.1039/c4nr01544d

How High Pressure Unifies Solvation Processes in Liquid Chromatography.

PubMed

Bocian, Szymon; Škrinjar, Tea; Bolanca, Tomislav; Buszewski, Bogusław

2017-11-01

A series of core-shell-based stationary phases of varying surface chemistry were subjected to solvent adsorption investigation under ultra-HPLC conditions. Acetonitrile and water excess isotherms were measured using a minor disturbance method. It was observed that adsorption of organic solvent is unified under high pressure. Preferential solvation due to specific interactions between the stationary phases and solvent molecules was limited. The obtained results showed that the solvation process is almost independent of surface chemistry, in contrast to HPLC conditions in which specific interactions differentiate solvation processes.

Biodegradable polyester-based microcarriers with modified surface tailored for tissue engineering.

PubMed

Privalova, A; Markvicheva, E; Sevrin, Ch; Drozdova, M; Kottgen, C; Gilbert, B; Ortiz, M; Grandfils, Ch

2015-03-01

Microcarriers have been proposed in tissue engineering, namely for bone, cartilage, skin, vascular, and central nervous system. Although polyester-based microcarriers have been already used for this purpose, their surface properties should be improved to provide better cell growth. The goal of this study was to prepare microbeads based on poly(D,L-lactide) acid, poly(L-lactide) acid, and to study cell behavior (adhesion, spreading, growth, and proliferation) in function of microbead topography and surface chemistry. To improve L-929 fibroblasts adhesion, microbead surface has been modified with three polycations: chitosan, poly(2-dimethylamino ethylmethacrylate) (PDMAEMA), or chitosan-g-oligolactide copolymer (chit-g-OLA). Although modification of the microbead surface with chitosan and PDMAEMA was performed through physical adsorption on the previously prepared microbeads, chit-g-OLA copolymer was introduced directly during microbead processing. This simple approach (1) bypass the use of an emulsifier (polyvinyl alcohol, PVA); (2) avoid surface "contamination" with PVA molecules limiting a control of the surface characteristics. In vitro study of the growth of mouse fibroblasts on the microbeads showed that both surface topography and chemistry affected cell attachment, spreading, and proliferation. Cultivation of L-929 fibroblasts for 7 days resulted in the formation of a 3D cell-scaffold network. © 2014 Wiley Periodicals, Inc.

Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

DTIC Science & Technology

2015-12-21

SECURITY CLASSIFICATION OF: The overall goal of this project is to determine how electrode surface chemistry can be rationally designed to decrease...2015 Approved for Public Release; Distribution Unlimited Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for...ABSTRACT Final Report: Rational Design of Anode Surface Chemistry in Microbial Fuel Cells for Improved Exoelectrogen Attachment and Electron Transfer

Versatile multi-functionalization of protein nanofibrils for biosensor applications

NASA Astrophysics Data System (ADS)

Sasso, L.; Suei, S.; Domigan, L.; Healy, J.; Nock, V.; Williams, M. A. K.; Gerrard, J. A.

2014-01-01

Protein nanofibrils offer advantages over other nanostructures due to the ease in their self-assembly and the versatility of surface chemistry available. Yet, an efficient and general methodology for their post-assembly functionalization remains a significant challenge. We introduce a generic approach, based on biotinylation and thiolation, for the multi-functionalization of protein nanofibrils self-assembled from whey proteins. Biochemical characterization shows the effects of the functionalization onto the nanofibrils' surface, giving insights into the changes in surface chemistry of the nanostructures. We show how these methods can be used to decorate whey protein nanofibrils with several components such as fluorescent quantum dots, enzymes, and metal nanoparticles. A multi-functionalization approach is used, as a proof of principle, for the development of a glucose biosensor platform, where the protein nanofibrils act as nanoscaffolds for glucose oxidase. Biotinylation is used for enzyme attachment and thiolation for nanoscaffold anchoring onto a gold electrode surface. Characterization via cyclic voltammetry shows an increase in glucose-oxidase mediated current response due to thiol-metal interactions with the gold electrode. The presented approach for protein nanofibril multi-functionalization is novel and has the potential of being applied to other protein nanostructures with similar surface chemistry.Protein nanofibrils offer advantages over other nanostructures due to the ease in their self-assembly and the versatility of surface chemistry available. Yet, an efficient and general methodology for their post-assembly functionalization remains a significant challenge. We introduce a generic approach, based on biotinylation and thiolation, for the multi-functionalization of protein nanofibrils self-assembled from whey proteins. Biochemical characterization shows the effects of the functionalization onto the nanofibrils' surface, giving insights into the changes in surface chemistry of the nanostructures. We show how these methods can be used to decorate whey protein nanofibrils with several components such as fluorescent quantum dots, enzymes, and metal nanoparticles. A multi-functionalization approach is used, as a proof of principle, for the development of a glucose biosensor platform, where the protein nanofibrils act as nanoscaffolds for glucose oxidase. Biotinylation is used for enzyme attachment and thiolation for nanoscaffold anchoring onto a gold electrode surface. Characterization via cyclic voltammetry shows an increase in glucose-oxidase mediated current response due to thiol-metal interactions with the gold electrode. The presented approach for protein nanofibril multi-functionalization is novel and has the potential of being applied to other protein nanostructures with similar surface chemistry. Electronic supplementary information (ESI) available: Cyclic voltammetry characterization of biosensor platforms including bare Au electrodes (Fig. S1), biosensor response to various glucose concentrations (Fig. S2), and AFM roughness measurements due to WPNF modifications (Fig. S3). See DOI: 10.1039/c3nr05752f

Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

PubMed

Law, Cheryl Suwen; Sylvia, Georgina M; Nemati, Madieh; Yu, Jingxian; Losic, Dusan; Abell, Andrew D; Santos, Abel

2017-03-15

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au 3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.

The spectroscopy and chemical dynamics of microparticles explored using an ultrasonic trap.

PubMed

Mason, N J; Drage, E A; Webb, S M; Dawes, A; McPheat, R; Hayes, G

2008-01-01

Microsized particles play an important role in many diverse areas of science and technology, for example, surface reactions of micron-sized particles play a key role in astrochemistry, plasma reactors and atmospheric chemistry. To date much of our knowledge of such surface chemistry is derived from 'traditional' surface science-based research. However, the large surface area and morphology of surface material commonly used in such surface science techniques may not necessarily mimic that on the surface of micron/nano scale particles. Hence, a new generation of experiments in which the spectroscopy (e.g., albedo) and chemical reactivity of micron-sized particles can be studied directly must be developed. One, as yet underexploited, non-invasive technique is the use of ultrasonic levitation. In this article, we describe the operation of an 'ultrasonic trap' to store and study the physical and chemical properties of microparticles.

Operando chemistry of catalyst surfaces during catalysis.

PubMed

Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

2017-04-03

Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

Advances on Aryldiazonium Salt Chemistry Based Interfacial Fabrication for Sensing Applications.

PubMed

Cao, Chaomin; Zhang, Yin; Jiang, Cheng; Qi, Meng; Liu, Guozhen

2017-02-15

Aryldiazonium salts as coupling agents for surface chemistry have evidenced their wide applications for the development of sensors. Combined with advances in nanomaterials, current trends in sensor science and a variety of particular advantages of aryldiazonium salt chemistry in sensing have driven the aryldiazonium salt-based sensing strategies to grow at an astonishing pace. This review focuses on the advances in the use of aryldiazonium salts for modifying interfaces in sensors and biosensors during the past decade. It will first summarize the current methods for modification of interfaces with aryldiazonium salts, and then discuss the sensing applications of aryldiazonium salts modified on different transducers (bulky solid electrodes, nanomaterials modified bulky solid electrodes, and nanoparticles). Finally, the challenges and perspectives that aryldiazonium salt chemistry is facing in sensing applications are critically discussed.

Mechanisms of Hydrocarbon Based Polymer Etch

NASA Astrophysics Data System (ADS)

Lane, Barton; Ventzek, Peter; Matsukuma, Masaaki; Suzuki, Ayuta; Koshiishi, Akira

2015-09-01

Dry etch of hydrocarbon based polymers is important for semiconductor device manufacturing. The etch mechanisms for oxygen rich plasma etch of hydrocarbon based polymers has been studied but the mechanism for lean chemistries has received little attention. We report on an experimental and analytic study of the mechanism for etching of a hydrocarbon based polymer using an Ar/O2 chemistry in a single frequency 13.56 MHz test bed. The experimental study employs an analysis of transients from sequential oxidation and Ar sputtering steps using OES and surface analytics to constrain conceptual models for the etch mechanism. The conceptual model is consistent with observations from MD studies and surface analysis performed by Vegh et al. and Oehrlein et al. and other similar studies. Parameters of the model are fit using published data and the experimentally observed time scales.

Composites Based on Polytetrafluoroethylene and Detonation Nanodiamonds: Filler-Matrix Chemical Interaction and Its Effect on a Composite's Properties

NASA Astrophysics Data System (ADS)

Koshcheev, A. P.; Perov, A. A.; Gorokhov, P. V.; Zaripov, N. V.; Tereshenkov, A. V.; Khatipov, S. A.

2018-06-01

Specific properties of PTFE composites filled with ultradisperse detonation diamonds (UDDs) with different surface chemistries are studied. It is found for the first time that filler in the form of UDDs affects not only the rate of PTFE thermal decomposition in vacuum pyrolysis, but also the chemical composition of the products of degradation. The wear resistance of UDD/PTFE composites is shown to depend strongly on the UDD surface chemistry. The presence of UDDs in a PTFE composite is found to result in perfluorocarbon telomeres, released as a readily condensable fraction upon composite pyrolysis. The chemical interaction between PTFE and UDDs, characterized by an increase in the rate of gas evolution and a change in the desorbed gas's composition, is found to occur at temperature as low as 380°C. It is shown that the intensity of this interaction depends on the concentration of oxygen-containing surface groups, the efficiency of UDDs in terms of the composite's wear resistance being reduced due to the presence of these groups. Based on the experimental data, a conclusion is reached about the chemical interaction between UDDs and a PTFE matrix, its dependence on the nanodiamond surface chemistry, and its effect on a composite's tribology.

Submicron Surface-Patterned Fibers and Textiles

DTIC Science & Technology

2016-11-04

These authors contributed equally Keywords: grating, fiber, polymer , patterning, textile Distribution A: approved for public release...requirements. Second, textile materials are primarily polymer -based, while most surface-patterning techniques have been developed for silicon...Alternative substrates, especially flexible polymers , remain challenging to pattern [25,26] due to the highly specific surface chemistry of different

Toxicity Evaluation of Engineered Nanomaterials (Phase 1 Studies)

DTIC Science & Technology

2012-01-01

Surface Chemistry on Cellular Response ...................................................................................................... 48...Gold Nanomaterial Solution Purity and Surface Chemistry Toxicity ................................................................. 18 Figure 7...Solution Purity and Surface Chemistry Control Although several studies have shown that both MPS and PEG are biocompatible, in order to ensure that

Characterization of low thermal conductivity PAN-based carbon fibers

NASA Technical Reports Server (NTRS)

Katzman, Howard A.; Adams, P. M.; Le, T. D.; Hemminger, Carl S.

1992-01-01

The microstructure and surface chemistry of eight low thermal conductivity (LTC) PAN-based carbon fibers were determined and compared with PAN-based fibers heat treated to higher temperatures. Based on wide-angle x ray diffraction, the LTC PAN fibers all appear to have a similar turbostratic structure with large 002 d-spacings, small crystallite sizes, and moderate preferred orientation. Limited small-angle x ray scattering (SAXS) results indicate that, with the exception of LTC fibers made by BASF, the LTC fibers do not have well developed pores. Transmission electron microscopy shows that the texture of the two LTC PAN-based fibers studied (Amoco T350/23X and /25X) consists of multiple sets of parallel, wavy, bent layers that interweave with each other forming a complex three dimensional network oriented randomly around the fiber axis. X ray photoelectron spectroscopy (XPS) analysis finds correlations between heat treated temperatures and the surface composition chemistry of the carbon fiber samples.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

PubMed

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels

PubMed Central

Syverud, Kristin

2014-01-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. PMID:24713295

Regulating Biocompatibility of Carbon Spheres via Defined Nanoscale Chemistry and a Careful Selection of Surface Functionalities

NASA Astrophysics Data System (ADS)

Misra, Santosh K.; Chang, Huei-Huei; Mukherjee, Prabuddha; Tiwari, Saumya; Ohoka, Ayako; Pan, Dipanjan

2015-10-01

A plethora of nanoarchitectures have been evaluated preclincially for applications in early detection and treatment of diseases at molecular and cellular levels resulted in limited success of their clinical translation. It is important to identify the factors that directly or indirectly affect their use in human. We bring a fundamental understanding of how to adjust the biocompatibility of carbon based spherical nanoparticles (CNPs) through defined chemistry and a vigilant choice of surface functionalities. CNPs of various size are designed by tweaking size (2-250 nm), surface chemistries (positive, or negatively charged), molecular chemistries (linear, dendritic, hyperbranched) and the molecular weight of the coating agents (MW 400-20 kDa). A combination of in vitro assays as tools were performed to determine the critical parameters that may trigger toxicity. Results indicated that hydrodynamic sizes are potentially not a risk factor for triggering cellular and systemic toxicity, whereas the presence of a highly positive surface charge and increasing molecular weight enhance the chance of inducing complement activation. Bare and carboxyl-terminated CNPs did present some toxicity at the cellular level which, however, is not comparable to those caused by positively charged CNPs. Similarly, negatively charged CNPs with hydroxyl and carboxylic functionalities did not cause any hemolysis.

Acetonitrile cluster solvation in a cryogenic ethane-methane-propane liquid: Implications for Titan lake chemistry.

PubMed

Corrales, L René; Yi, Thomas D; Trumbo, Samantha K; Shalloway, David; Lunine, Jonathan I; Usher, David A

2017-03-14

The atmosphere of Titan, Saturn's largest moon, exhibits interesting UV- and radiation-driven chemistry between nitrogen and methane, resulting in dipolar, nitrile-containing molecules. The assembly and subsequent solvation of such molecules in the alkane lakes and seas found on the moon's surface are of particular interest for investigating the possibility of prebiotic chemistry in Titan's hydrophobic seas. Here we characterize the solvation of acetonitrile, a product of Titan's atmospheric radiation chemistry tentatively detected on Titan's surface [H. B. Niemann et al., Nature 438, 779-784 (2005)], in an alkane mixture estimated to match a postulated composition of the smaller lakes during cycles of active drying and rewetting. Molecular dynamics simulations are employed to determine the potential of mean force of acetonitrile (CH 3 CN) clusters moving from the alkane vapor into the bulk liquid. We find that the clusters prefer the alkane liquid to the vapor and do not dissociate in the bulk liquid. This opens up the possibility that acetonitrile-based microscopic polar chemistry may be possible in the otherwise nonpolar Titan lakes.

Nano interface potential influences in CdTe quantum dots and biolabeling

NASA Astrophysics Data System (ADS)

Kanagasubbulakshmi, S.; Kadirvelu, K.

2018-05-01

Nano interface influences in physiochemical properties of quantum dots (QDs) are the challenging approach to tailor its surface functionalities. In this study, a set of polar and non-polar solvents were selected to analyze the influences in solvent-based dynamic radius and surface potential of QDs. From the nano interface chemistry of polar and non-polar solvents, an appropriate mechanism of precipitation and hydrophobic ligand exchange strategy were elucidated by correlating Henry's equation. Further, the in vitro cytotoxic potential and antimicrobial activity of QDs were assessed to perform biolabeling. From the observations, an appropriate dosage of QDs was fixed to label the animal ((RAW 264.7 cell lines) and bacterial cells (Escherichia coli) for effective cell attachment. Biolabeling was achieved by tailoring nano interface chemistry of QDs without additional support of biomolecules. Bacterial cell wall-based interaction of QDs was evaluated using SEM and EDAX analysis. Thus, provided clear insights into the nano interface chemistry in the development of highly photostable QDs will be helpful in biomedical applications.

Ethanol surface chemistry on MBE-grown GaN(0001), GaOx/GaN(0001), and Ga2O3(2 \\xAF 01 )

NASA Astrophysics Data System (ADS)

Kollmannsberger, Sebastian L.; Walenta, Constantin A.; Winnerl, Andrea; Knoller, Fabian; Pereira, Rui N.; Tschurl, Martin; Stutzmann, Martin; Heiz, Ueli

2017-09-01

In this work, ethanol is used as a chemical probe to study the passivation of molecular beam epitaxy-grown GaN(0001) by surface oxidation. With a high degree of oxidation, no reaction from ethanol to acetaldehyde in temperature-programmed desorption experiments is observed. The acetaldehyde formation is attributed to a mechanism based on α -H abstraction from the dissociatively bound alcohol molecule. The reactivity is related to negatively charged surface states, which are removed upon oxidation of the GaN(0001) surface. This is compared with the Ga2O3(2 ¯ 01 ) single crystal surface, which is found to be inert for the acetaldehyde production. These results offer a toolbox to explore the surface chemistry of nitrides and oxynitrides on an atomic scale and relate their intrinsic activity to systems under ambient atmosphere.

Specific and selective target detection of supra-genome 21 Mers Salmonella via silicon nanowires biosensor

NASA Astrophysics Data System (ADS)

Mustafa, Mohammad Razif Bin; Dhahi, Th S.; Ehfaed, Nuri. A. K. H.; Adam, Tijjani; Hashim, U.; Azizah, N.; Mohammed, Mohammed; Noriman, N. Z.

2017-09-01

The nano structure based on silicon can be surface modified to be used as label-free biosensors that allow real-time measurements. The silicon nanowire surface was functionalized using 3-aminopropyltrimethoxysilane (APTES), which functions as a facilitator to immobilize biomolecules on the silicon nanowire surface. The process is simple, economical; this will pave the way for point-of-care applications. However, the surface modification and subsequent detection mechanism still not clear. Thus, study proposed step by step process of silicon nano surface modification and its possible in specific and selective target detection of Supra-genome 21 Mers Salmonella. The device captured the molecule with precisely; the approach took the advantages of strong binding chemistry created between APTES and biomolecule. The results indicated how modifications of the nanowires provide sensing capability with strong surface chemistries that can lead to specific and selective target detection.

Ethanol surface chemistry on MBE-grown GaN(0001), GaOx/GaN(0001), and Ga2O3(2¯01).

PubMed

Kollmannsberger, Sebastian L; Walenta, Constantin A; Winnerl, Andrea; Knoller, Fabian; Pereira, Rui N; Tschurl, Martin; Stutzmann, Martin; Heiz, Ueli

2017-09-28

In this work, ethanol is used as a chemical probe to study the passivation of molecular beam epitaxy-grown GaN(0001) by surface oxidation. With a high degree of oxidation, no reaction from ethanol to acetaldehyde in temperature-programmed desorption experiments is observed. The acetaldehyde formation is attributed to a mechanism based on α-H abstraction from the dissociatively bound alcohol molecule. The reactivity is related to negatively charged surface states, which are removed upon oxidation of the GaN(0001) surface. This is compared with the Ga 2 O 3 (2¯01) single crystal surface, which is found to be inert for the acetaldehyde production. These results offer a toolbox to explore the surface chemistry of nitrides and oxynitrides on an atomic scale and relate their intrinsic activity to systems under ambient atmosphere.

Organic Chemistry in Two Dimensions: Surface-Functionalized Polymers and Self-Assembled Monolayer Films

DTIC Science & Technology

1988-09-01

surfaces as components of materials . In particular, we hope to develop the ability to rationalize and predict the macroscooic properties of surfaces...of much of the current research in areas such as materials science, condensed matter and device physics, and polymer physical chemistry. Surface...6 Underlying our program in surface chemistry is a broad interest in the prop- erties of organic surfaces as components of materials . In particular

CONTROL OF CHELATOR-BASED UPSETS IN SURFACE FINISHING SHOP WASTE WATER TREATMENT SYSTEMS

EPA Science Inventory

Actual surface finishing shop examples are used to illustrate the use of process chemistry understanding and analyses to identify immediate, interim and permanent response options for industrial waste water treatment plant (IWTP) upset problems caused by chelating agents. There i...

Low earth orbit durability evaluation of Haynes 188 solar receiver material

NASA Technical Reports Server (NTRS)

De Groh, Kim K.; Rutledge, Sharon K.; Burke, Christopher A.; Dever, Therese M.; Olle, Raymond M.; Terlep, Judith A.

1992-01-01

The effects of elevated-temperature vacuum and elevated-temperature atomic oxygen exposure on the mass, surface chemistry, surface morphology, and optical properties of Haynes 188, a possible heat receiver material for space-based solar dynamic power systems, have been studied. Pristine and surface modified Haynes 188 were exposed to vacuum less than or equal to 10 exp -6 torr at 820 C for 5215.5 h, and to atomic oxygen in an air plasma asher at 34 and 827 C for fluences up to 5.6 x 10 exp 21 atoms/sq cm. Results obtained indicate that vacuum heat treatment caused surface morphology and chemistry changes with corresponding optical property changes. Atomic oxygen exposure caused optical property changes which diminished with time. Mass changes are considered to be negligible for both exposures.

Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

PubMed

Pegalajar-Jurado, Adoracion; Easton, Christopher D; Crawford, Russell J; McArthur, Sally L

2015-03-26

Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

Investigation of molybdenum-crosslinker interfaces for affinity based electrochemical biosensing applications

NASA Astrophysics Data System (ADS)

Kamakoti, Vikramshankar; Shanmugam, Nandhinee Radha; Tanak, Ambalika Sanjeev; Jagannath, Badrinath; Prasad, Shalini

2018-04-01

Molybdenum (Mo) has been investigated for implementation as an electrode material for affinity based biosensing towards devloping flexibe electronic biosensors. Treatment of the native oxide of molybdenum was investigated through two surface treatment strategies namely thiol and carbodiimide crosslinking methods. The binding interaction between cross-linker molecules and Mo electrode surface has been characterized using Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and optical microscopy. The efficacy of treatment of Mo with its native oxide using carbodiimide cross linking methodology was established. The carbodiimide cross-linking chemistry was found to possess better surface coverage and binding affinity with Molybdenum electrode surface when compared to thiol cross-linking chemistry.Electrochemical characterization of Mo electrode using Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltametry (CV) techniques was performed to evaluate the effect of ionic properties of solution buffer on the Mo electrode's performance. Affinity based biosensing of C-Reactive Protein (CRP) has been demonstrated on a flexible nanoporous polymeric substrate with detection threshold of 100 pg/ml in synthetic urine buffer medium. The biosensor has been evaluated to be developed as a dipstick based point of care device for detection of biomarkers in urine.

Modulation of Protein Fouling and Interfacial Properties at Carbon Surfaces via Immobilization of Glycans Using Aryldiazonium Chemistry

PubMed Central

Zen, Federico; Angione, M. Daniela; Behan, James A.; Cullen, Ronan J.; Duff, Thomas; Vasconcelos, Joana M.; Scanlan, Eoin M.; Colavita, Paula E.

2016-01-01

Carbon materials and nanomaterials are of great interest for biological applications such as implantable devices and nanoparticle vectors, however, to realize their potential it is critical to control formation and composition of the protein corona in biological media. In this work, protein adsorption studies were carried out at carbon surfaces functionalized with aryldiazonium layers bearing mono- and di-saccharide glycosides. Surface IR reflectance absorption spectroscopy and quartz crystal microbalance were used to study adsorption of albumin, lysozyme and fibrinogen. Protein adsorption was found to decrease by 30–90% with respect to bare carbon surfaces; notably, enhanced rejection was observed in the case of the tested di-saccharide vs. simple mono-saccharides for near-physiological protein concentration values. ζ-potential measurements revealed that aryldiazonium chemistry results in the immobilization of phenylglycosides without a change in surface charge density, which is known to be important for protein adsorption. Multisolvent contact angle measurements were used to calculate surface free energy and acid-base polar components of bare and modified surfaces based on the van Oss-Chaudhury-Good model: results indicate that protein resistance in these phenylglycoside layers correlates positively with wetting behavior and Lewis basicity. PMID:27108562

Modulation of Protein Fouling and Interfacial Properties at Carbon Surfaces via Immobilization of Glycans Using Aryldiazonium Chemistry

NASA Astrophysics Data System (ADS)

Zen, Federico; Angione, M. Daniela; Behan, James A.; Cullen, Ronan J.; Duff, Thomas; Vasconcelos, Joana M.; Scanlan, Eoin M.; Colavita, Paula E.

2016-04-01

Carbon materials and nanomaterials are of great interest for biological applications such as implantable devices and nanoparticle vectors, however, to realize their potential it is critical to control formation and composition of the protein corona in biological media. In this work, protein adsorption studies were carried out at carbon surfaces functionalized with aryldiazonium layers bearing mono- and di-saccharide glycosides. Surface IR reflectance absorption spectroscopy and quartz crystal microbalance were used to study adsorption of albumin, lysozyme and fibrinogen. Protein adsorption was found to decrease by 30-90% with respect to bare carbon surfaces; notably, enhanced rejection was observed in the case of the tested di-saccharide vs. simple mono-saccharides for near-physiological protein concentration values. ζ-potential measurements revealed that aryldiazonium chemistry results in the immobilization of phenylglycosides without a change in surface charge density, which is known to be important for protein adsorption. Multisolvent contact angle measurements were used to calculate surface free energy and acid-base polar components of bare and modified surfaces based on the van Oss-Chaudhury-Good model: results indicate that protein resistance in these phenylglycoside layers correlates positively with wetting behavior and Lewis basicity.

OSCAR4: a flexible architecture for chemical text-mining.

PubMed

Jessop, David M; Adams, Sam E; Willighagen, Egon L; Hawizy, Lezan; Murray-Rust, Peter

2011-10-14

The Open-Source Chemistry Analysis Routines (OSCAR) software, a toolkit for the recognition of named entities and data in chemistry publications, has been developed since 2002. Recent work has resulted in the separation of the core OSCAR functionality and its release as the OSCAR4 library. This library features a modular API (based on reduction of surface coupling) that permits client programmers to easily incorporate it into external applications. OSCAR4 offers a domain-independent architecture upon which chemistry specific text-mining tools can be built, and its development and usage are discussed.

Response of surface water chemistry to reduced levels of acid precipitation: Comparison of trends in two regions of New York, USA

USGS Publications Warehouse

Burns, Douglas A.; McHale, M.R.; Driscoll, C.T.; Roy, K.M.

2006-01-01

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984-2001 and 1992-2001) and surface water chemistry (1992-2001) were determined in two of the most acid-sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO42-), nitrate (NO3-), and base cation (CB) concentrations and increasing pH during 1984-2001, but few significant trends during 1992-2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO42- concentrations at all sites, and decreasing trends in NO3-, CB, and H+ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid-neutralizing capacity (ANC increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO42- trends, but it caused several significant non-flow-corrected trends in NO3- and ANC to become non-significant, suggesting that trend results for flow-sensitive constituents are affected by flow-related climate variation. SO42- concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation-surface water comparisons, reflecting a strong link between S emissions, precipitation SO42- concentrations, and the processes that affect S cycling within these regions. NO3- and H+ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation-surface water comparisons, indicating that variation in local-scale processes driven by factors such as climate are affecting trends in acid-base chemistry in these two regions. Copyright ?? 2005 John Wiley & Sons, Ltd.

Aqueous aerosol SOA formation: impact on aerosol physical properties.

PubMed

Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

2013-01-01

Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions.

Advances in understanding the surface chemistry of lignocellulosic biomass via time-of-flight secondary ion mass spectrometry

DOE PAGES

Tolbert, Allison K.; Ragauskas, Arthur J.

2016-12-12

Overcoming the natural recalcitrance of lignocellulosic biomass is necessary in order to efficiently convert biomass into biofuels or biomaterials and many times this requires some type of chemical pretreatment and/or biological treatment. While bulk chemical analysis is the traditional method of determining the impact a treatment has on biomass, the chemistry on the surface of the sample can differ from the bulk chemistry. Specifically, enzymes and microorganisms bind to the surface of the biomass and their efficiency could be greatly impacted by the chemistry of the surface. Therefore, it is important to study and understand the chemistry of the biomassmore » at the surface. Time-of- flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool that can spectrally and spatially analyze the surface chemistry of a sample. This review discusses the advances in understanding lignocellulosic biomass surface chemistry using the ToF-SIMS by addressing the instrument parameters, biomass sample preparation, and characteristic lignocellulosic ion fragmentation peaks along with their typical location in the plant cell wall. Furthermore, the use of the ToF-SIMS in detecting chemical changes due to chemical pretreatments, microbial treatments, and physical or genetic modifications is discussed along with possible future applications of the instrument in lignocellulosic biomass studies.« less

Advances in understanding the surface chemistry of lignocellulosic biomass via time-of-flight secondary ion mass spectrometry

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

Tolbert, Allison K.; Ragauskas, Arthur J.

Overcoming the natural recalcitrance of lignocellulosic biomass is necessary in order to efficiently convert biomass into biofuels or biomaterials and many times this requires some type of chemical pretreatment and/or biological treatment. While bulk chemical analysis is the traditional method of determining the impact a treatment has on biomass, the chemistry on the surface of the sample can differ from the bulk chemistry. Specifically, enzymes and microorganisms bind to the surface of the biomass and their efficiency could be greatly impacted by the chemistry of the surface. Therefore, it is important to study and understand the chemistry of the biomassmore » at the surface. Time-of- flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool that can spectrally and spatially analyze the surface chemistry of a sample. This review discusses the advances in understanding lignocellulosic biomass surface chemistry using the ToF-SIMS by addressing the instrument parameters, biomass sample preparation, and characteristic lignocellulosic ion fragmentation peaks along with their typical location in the plant cell wall. Furthermore, the use of the ToF-SIMS in detecting chemical changes due to chemical pretreatments, microbial treatments, and physical or genetic modifications is discussed along with possible future applications of the instrument in lignocellulosic biomass studies.« less

Modeling the acid-base surface chemistry of montmorillonite.

PubMed

Bourg, Ian C; Sposito, Garrison; Bourg, Alain C M

2007-08-15

Proton uptake on montmorillonite edge surfaces can control pore water pH, solute adsorption, dissolution kinetics and clay colloid behavior in engineered clay barriers and natural weathering environments. Knowledge of proton uptake reactions, however, is currently limited by strong discrepancies between reported montmorillonite titration data sets and by conflicting estimates of edge structure, reactivity and electrostatics. In the present study, we show that the apparent discrepancy between titration data sets results in large part from the widespread use of an erroneous assumption of zero specific net proton surface charge at the onset of titration. Using a novel simulation scheme involving a surface chemistry model to simulate both pretreatment and titration, we find that montmorillonite edge surface chemistry models that account for the "spillover" of electrostatic potential from basal onto edge surfaces and for the stabilization of deprotonated Al-Si bridging sites through bond-length relaxation at the edge surface can reproduce key features of the best available experimental titration data (the influence of pretreatment conditions on experimental results, the absence of a point of zero salt effect, buffer capacity in the acidic pH range). However, no combination of current models of edge surface structure, reactivity and electrostatics can quantitatively predict, without fitted parameters, the experimental titration data over the entire range of pH (4.5 to 9) and ionic strength (0.001 to 0.5 mol dm(-3)) covered by available data.

Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases.

PubMed

De Roo, Jonathan; Van den Broeck, Freya; De Keukeleere, Katrien; Martins, José C; Van Driessche, Isabel; Hens, Zeger

2014-07-09

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.

Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

PubMed

Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

2007-07-19

The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

Role of Integrin Subunits in Mesenchymal Stem Cell Differentiation and Osteoblast Maturation on Graphitic Carbon-coated Microstructured Surfaces

PubMed Central

Olivares-Navarrete, Rene; Rodil, Sandra E.; Hyzy, Sharon L.; Dunn, Ginger R.; Almaguer-Flores, Argelia; Schwartz, Zvi; Boyan, Barbara D.

2015-01-01

Surface roughness, topography, chemistry, and energy promote osteoblast differentiation and increase osteogenic local factor production in vitro and bone-to-implant contact in vivo, but the mechanisms involved are not well understood. Knockdown of integrin heterodimer alpha2beta1 (α2β1) blocks the osteogenic effects of the surface, suggesting signaling by this integrin homodimer is required. The purpose of the present study was to separate effects of surface chemistry and surface structure on integrin expression by coating smooth or rough titanium (Ti) substrates with graphitic carbon, retaining surface morphology but altering surface chemistry. Ti surfaces (smooth [Ra<0.4μm], rough [Ra≥3.4μm]) were sputter-coated using a magnetron sputtering system with an ultrapure graphite target, producing a graphitic carbon thin film. Human mesenchymal stem cells and MG63 osteoblast-like cells had higher mRNA for integrin subunits α1, α2, αv, and β1 on rough surfaces in comparison to smooth, and integrin αv on graphitic-carbon-coated rough surfaces in comparison to Ti. Osteogenic differentiation was greater on rough surfaces in comparison to smooth, regardless of chemistry. Silencing integrins β1, α1, or α2 decreased osteoblast maturation on rough surfaces independent of surface chemistry. Silencing integrin αv decreased maturation only on graphitic carbon-coated surfaces, not on Ti. These results suggest a major role of the integrin β1 subunit in roughness recognition, and that integrin alpha subunits play a major role in surface chemistry recognition. PMID:25770999

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

Choi, Hyekyoung; Kim, Sungwoo; Luther, Joseph M.

Silver dimetal chalcogenide (Ag-V-VI 2) ternary quantum dots (QDs) are emerging lead-free materials for optoelectronic devices due to their NIR band gaps, large absorption coefficients, and superior electronic properties. However, thin film-based devices of the ternary QDs still lag behind due to the lack of understanding of the surface chemistry, compared to that of lead chalcogenide QDs even with the same crystal structure. Here in this paper, the surface ligand interactions of AgSbS 2 QDs, synthesized with 1-dodecanethiol used as a stabilizer, are studied. For nonpolar (1 0 0) surfaces, it is suggested that the thiolate ligands are associated withmore » the crystal lattices, thus preventing surface oxidation by protecting sulfur after air-exposure, as confirmed through optical and surface chemical analysis. Otherwise, silver rich (1 1 1) surfaces are passivated by thiolate ligands, allowing ligand exchange processes for the conductive films. This in-depth investigation of the surface chemistry of ternary QDs will prompt the performance enhancement of their optoelectronic devices.« less

Effects of surface chemistry on the optical properties and cellular interaction of lanthanide-based nanoparticles

NASA Astrophysics Data System (ADS)

Pedraza, Francisco J.; Avalos, Julio C.; Mimun, Lawrence C.; Yust, Brian G.; Tsin, Andrew; Sardar, Dhiraj K.

2015-03-01

Fluorescent nanoparticles (NPs) such as KYb2F7:Tm3+ potential in biomedical applications due to their ability to absorb and emit within the biological window, where near infrared light is less attenuated by soft tissue. This results in less tissue damage and deeper tissue penetration making it a viable candidate in biological imaging. Another big factor in determining their ability to perform in a biological setting is the surface chemistry. Biocompatible coatings, including polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), pluronic and folic acid are commonly used because they pose several advantages such as ease of functionalization, better dispersion, and higher cellular uptake. To study the effects of the NP surface chemistry, KYb2F7:Tm3+ a solvothermal method using PEG, PVP, pluronic acid, and folic acid as a capping agent, followed by thorough optical characterizations. Optical changes were thoroughly studied and compared using absorption, emission, and quantum yield data. Cell viability was obtained by treating Rhesus Monkey Retinal Endothelial cells (RhREC) with KYb2F7:Tm3+ and counting viable cells following a 24 hour uptake period. The work presented will compare the optical properties and toxicity dependency on the surface chemistry on KYb2F7:Tm3+. The results will also indicate that KYb2F7:Tm3+ nanoparticles are viable candidates for various biomedical applications.

JPRS Report, Science & Technology, USSR: Chemistry

DTIC Science & Technology

1990-11-08

desorption cycle. The photochemical activity of the oxides was determined by irradiating them with UV light at 353 K during the oxidation reactions of...No 1, Jan 90] 8 Acid-Base Properties Photochemically Active Titanium Oxide Surfaces [N D. Konovalova, V. I. Stepanenko, etal; UKRAINSKIY...Figures 4; references 13: 10 Russian, 3 Western. UDC 541.183 Acid-Base Properties Photochemically Active Titanium Oxide Surfaces 907M0149B Kiev

Schottky-barrier-free contacts with two-dimensional semiconductors by surface-engineered MXenes

DOE PAGES

Liu, Yuanyue; Xiao, Hai; Goddard, III, William A.

2016-11-22

Two-dimensional (2D) metal carbides and nitrides, called MXenes, have attracted great interest for applications such as energy storage. Here we demonstrate their potential as Schottky-barrier-free metal contacts to 2D semiconductors, providing a solution to the contact-resistance problem in 2D electronics. Based on first principles calculations, we find that the surface chemistry strongly affects the Fermi level of MXenes: O termination always increases the work function with respect to that of bare surface, OH always decreases it, while F exhibits either trend depending on the specific material. This phenomenon originates from the effect of surface dipoles, which together with the weakmore » Fermi level pinning, enable Schottky-barrier-free hole (or electron) injection into 2D semiconductors through van der Waals junctions with some of the O-terminated (or all the OH-terminated) MXenes. Furthermore, we suggest synthetic routes to control the surface terminations based on the calculated formation energies. Finally, this study enhances the understanding of the correlation between surface chemistry and electronic/transport properties of 2D materials, and also gives practical predictions for improving 2D electronics.« less

Nanoporous Anodic Alumina Platforms: Engineered Surface Chemistry and Structure for Optical Sensing Applications

PubMed Central

Kumeria, Tushar; Santos, Abel; Losic, Dusan

2014-01-01

Electrochemical anodization of pure aluminum enables the growth of highly ordered nanoporous anodic alumina (NAA) structures. This has made NAA one of the most popular nanomaterials with applications including molecular separation, catalysis, photonics, optoelectronics, sensing, drug delivery, and template synthesis. Over the past decades, the ability to engineer the structure and surface chemistry of NAA and its optical properties has led to the establishment of distinctive photonic structures that can be explored for developing low-cost, portable, rapid-response and highly sensitive sensing devices in combination with surface plasmon resonance (SPR) and reflective interference spectroscopy (RIfS) techniques. This review article highlights the recent advances on fabrication, surface modification and structural engineering of NAA and its application and performance as a platform for SPR- and RIfS-based sensing and biosensing devices. PMID:25004150

Surface functionalization of thin-film diamond for highly stable and selective biological interfaces

PubMed Central

Stavis, Courtney; Clare, Tami Lasseter; Butler, James E.; Radadia, Adarsh D.; Carr, Rogan; Zeng, Hongjun; King, William P.; Carlisle, John A.; Aksimentiev, Aleksei; Bashir, Rashid; Hamers, Robert J.

2011-01-01

Carbon is an extremely versatile family of materials with a wide range of mechanical, optical, and mechanical properties, but many similarities in surface chemistry. As one of the most chemically stable materials known, carbon provides an outstanding platform for the development of highly tunable molecular and biomolecular interfaces. Photochemical grafting of alkenes has emerged as an attractive method for functionalizing surfaces of diamond, but many aspects of the surface chemistry and impact on biological recognition processes remain unexplored. Here we report investigations of the interaction of functionalized diamond surfaces with proteins and biological cells using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and fluorescence methods. XPS data show that functionalization of diamond with short ethylene glycol oligomers reduces the nonspecific binding of fibrinogen below the detection limit of XPS, estimated as > 97% reduction over H-terminated diamond. Measurements of different forms of diamond with different roughness are used to explore the influence of roughness on nonspecific binding onto H-terminated and ethylene glycol (EG)-terminated surfaces. Finally, we use XPS to characterize the chemical stability of Escherichia coli K12 antibodies on the surfaces of diamond and amine-functionalized glass. Our results show that antibody-modified diamond surfaces exhibit increased stability in XPS and that this is accompanied by retention of biological activity in cell-capture measurements. Our results demonstrate that surface chemistry on diamond and other carbon-based materials provides an excellent platform for biomolecular interfaces with high stability and high selectivity. PMID:20884854

General Dialdehyde Click Chemistry for Amine Bioconjugation.

PubMed

Elahipanah, Sina; O'Brien, Paul J; Rogozhnikov, Dmitry; Yousaf, Muhammad N

2017-05-17

The development of methods for conjugating a range of molecules to primary amine functional groups has revolutionized the fields of chemistry, biology, and material science. The primary amine is a key functional group and one of the most important nucleophiles and bases used in all of synthetic chemistry. Therefore, tremendous interest in the synthesis of molecules containing primary amines and strategies to devise chemical reactions to react with primary amines has been at the core of chemical research. In particular, primary amines are a ubiquitous functional group found in biological systems as free amino acids, as key side chain lysines in proteins, and in signaling molecules and metabolites and are also present in many natural product classes. Due to its abundance, the primary amine is the most convenient functional group handle in molecules for ligation to other molecules for a broad range of applications that impact all scientific fields. Because of the primary amine's central importance in synthetic chemistry, acid-base chemistry, redox chemistry, and biology, many methods have been developed to efficiently react with primary amines, including activated carboxylic acids, isothiocyanates, Michael addition type systems, and reaction with ketones or aldehydes followed by in situ reductive amination. Herein, we introduce a new traceless, high-yield, fast click-chemistry method based on the rapid and efficient trapping of amine groups via a functionalized dialdehyde group. The click reaction occurs in mild conditions in organic solvents or aqueous media and proceeds in high yield, and the starting dialdehyde reagent and resulting dialdehyde click conjugates are stable. Moreover, no catalyst or dialdehyde-activating group is required, and the only byproduct is water. The initial dialdehyde and the resulting conjugate are both straightforward to characterize, and the reaction proceeds with high atom economy. To demonstrate the broad scope of this new click-conjugation strategy, we designed a straightforward scheme to synthesize a suite of dialdehyde reagents. The dialdehyde molecules were used for applications in cell-surface engineering and for tailoring surfaces for material science applications. We anticipate the broad utility of the general dialdehyde click chemistry to primary amines in all areas of chemical research, ranging from polymers and bioconjugation to material science and nanoscience.

Impact of managed moorland burning on peat nutrient and base cation status

NASA Astrophysics Data System (ADS)

Palmer, Sheila; Gilpin, Martin; Wearing, Catherine; Johnston, Kerrylyn; Holden, Joseph; Brown, Lee

2013-04-01

Controlled 'patch' burning of moorland vegetation has been used for decades in the UK to stimulate growth of heather (Calluna vulgaris) for game bird habitat and livestock grazing. Typically small patches (300-900 m2) are burned in rotations of 8-25 years. However, our understanding of the short-to-medium term environmental impacts of the practice on these sensitive upland areas has so far been limited by a lack of scientific data. In particular the effect of burning on concentrations of base cations and acid-base status of these highly organic soils has implications both for ecosystem nutrient status and for buffering of acidic waters. As part of the EMBER project peat chemistry data were collected in ten upland blanket peat catchments in the UK. Five catchments were subject to a history of prescribed rotational patch burning. The other five catchments acted as controls which were not subject to burning, nor confounded by other detrimental activities such as drainage or forestry. Soil solution chemistry was also monitored at two intensively studied sites (one regularly burned and one control). Fifty-centimetre soil cores, sectioned into 5-cm intervals, were collected from triplicate patches of four burn ages at each burned site, and from twelve locations at similar hillslope positions at each control site. At the two intensively monitored sites, soil solution chemistry was monitored at four depths in each patch. Across all sites, burned plots had significantly smaller cation exchange capacities, lower concentrations of exchangeable base cations and increased concentrations of exchangeable H+ and Al3+ in near-surface soil. C/N ratios were also lower in burned compared to unburned surface soils. There was no consistent trend between burn age and peat chemistry across all burned sites, possibly reflecting local controls on post-burn recovery rates or external influences on burn management decisions. At the intensively monitored site, plots burned less than two years prior to sampling had significantly smaller exchange capacities and lower concentrations of soil base cations in surface soils relative to plots burned 15-25 years previously. In contrast, surface soil solutions in recently burned plots were enriched in base cations relative to older plots and relative to the control site, possibly due to enhanced leaching at bare soil surfaces. The results offer evidence for an impact of burning on peat nutrient and acid-base status, but suggest that soils recover given time with no further burning.

Anion Solvation in Carbonate-Based Electrolytes

DOE PAGES

von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; ...

2015-11-16

The correlation between Li + solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li +, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li + solvation studies, this work focuses on the interactions between carbonate-based solvents andmore » two anions (hexafluorophosphate, PF 6–, and tetrafluoroborate, BF 4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.« less

Materials Chemistry and Performance of Silicone-Based Replicating Compounds.

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

Brumbach, Michael T.; Mirabal, Alex James; Kalan, Michael

Replicating compounds are used to cast reproductions of surface features on a variety of materials. Replicas allow for quantitative measurements and recordkeeping on parts that may otherwise be difficult to measure or maintain. In this study, the chemistry and replicating capability of several replicating compounds was investigated. Additionally, the residue remaining on material surfaces upon removal of replicas was quantified. Cleaning practices were tested for several different replicating compounds. For all replicating compounds investigated, a thin silicone residue was left by the replica. For some compounds, additional inorganic species could be identified in the residue. Simple solvent cleaning could removemore » some residue.« less

Preparation of water-soluble magnetic nanocrystals using aryl diazonium salt chemistry.

PubMed

Griffete, Nébéwia; Herbst, Frédéric; Pinson, Jean; Ammar, Souad; Mangeney, Claire

2011-02-16

A novel and facile methodology for the in situ surface functionalization of Fe(3)O(4) nanoparticles is proposed, based on the use of aryl diazonium salts chemistry. The grafting reaction involves the formation of diazoates in a basic medium. These species are unstable and dediazonize along a homolytic pathway to give aryl radicals which further react with the Fe(3)O(4) NPs during their formation and stop their growth. Advantages of the present approach rely not only on the simplicity, rapidity, and efficiency of the procedure but also on the formation of strong Fe(3)O(4)-aryl surface bonds, highly suitable for further applications.

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

NASA Astrophysics Data System (ADS)

Hoppe, E. W.; Seifert, A.; Aalseth, C. E.; Bachelor, P. P.; Day, A. R.; Edwards, D. J.; Hossbach, T. W.; Litke, K. E.; McIntyre, J. I.; Miley, H. S.; Schulte, S. M.; Smart, J. E.; Warren, G. A.

2007-08-01

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu +/Cu 2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified.

OSCAR4: a flexible architecture for chemical text-mining

PubMed Central

2011-01-01

The Open-Source Chemistry Analysis Routines (OSCAR) software, a toolkit for the recognition of named entities and data in chemistry publications, has been developed since 2002. Recent work has resulted in the separation of the core OSCAR functionality and its release as the OSCAR4 library. This library features a modular API (based on reduction of surface coupling) that permits client programmers to easily incorporate it into external applications. OSCAR4 offers a domain-independent architecture upon which chemistry specific text-mining tools can be built, and its development and usage are discussed. PMID:21999457

The selectivity of protein-imprinted gels and its relation to protein properties: A computer simulation study.

PubMed

Yankelov, Rami; Yungerman, Irena; Srebnik, Simcha

2017-07-01

Polymer-based protein recognition systems have enormous potential within clinical and diagnostic fields due to their reusability, biocompatibility, ease of manufacturing, and potential specificity. Imprinted polymer matrices have been extensively studied and applied as a simple technique for creating artificial polymer-based recognition gels for a target molecule. Although this technique has been proven effective when targeting small molecules (such as drugs), imprinting of proteins have so far resulted in materials with limited selectivity due to the large molecular size of the protein and aqueous environment. Using coarse-grained molecular simulation, we investigate the relation between protein makeup, polymer properties, and the selectivity of imprinted gels. Nonspecific binding that results in poor selectivity is shown to be strongly dependent on surface chemistry of the template and competitor proteins as well as on polymer chemistry. Residence time distributions of proteins diffusing within the gels provide a transparent picture of the relation between polymer constitution, protein properties, and the nonspecific interactions with the imprinted gel. The pronounced effect of protein surface chemistry on imprinted gel specificity is demonstrated. Copyright © 2017 John Wiley & Sons, Ltd.

Endothelial cell behaviour on gas-plasma-treated PLA surfaces: the roles of surface chemistry and roughness.

PubMed

Shah, Amita; Shah, Sarita; Mani, Gopinath; Wenke, Joseph; Agrawal, Mauli

2011-04-01

Glow-discharge gas-plasma (GP) treatment has been shown to induce surface modifications such that cell adhesion and growth are enhanced. However, it is not known which gas used in GP treatment is optimal for endothelial cell function. Polylactic acid (PLA) films treated oxygen, argon, or nitrogen GP were characterized using contact angles, scanning electron microscopy, atomic force microscopy, optical profilometry, and x-ray photoelectron spectroscopy. All three GP treatments decreased the carbon atomic concentration and surface roughness and increased the oxygen atomic concentration. Human umbilical vein endothelial cells were cultured on the PLA films for up to 7 days. Based on proliferation and live/dead assays, surface chemistry was shown to have the greatest effect on the attachment, proliferation, and viability of these cells, while roughness did not have a significant influence. Of the different gases, endothelial cell viability, attachment and proliferation were most significantly increased on PLA surfaces treated with oxygen and argon gas plasma. Copyright © 2010 John Wiley & Sons, Ltd.

A Bioanalytical Chemistry Experiment for Undergraduate Students: Biosensors Based on Metal Nanoparticles

ERIC Educational Resources Information Center

Niagi, John; Warner, John; Andreesco, Silvana

2007-01-01

The study describes the development of new biosensors based on metal nanoparticles because of its high surface area and large binding ability. The adopted procedure is extremely simple and versatile and can be used in various applications of electrochemistry.

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

DOE PAGES

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.; ...

2017-12-06

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

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

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

Tunable Luminescent Carbon Nanospheres with Well-Defined Nanoscale Chemistry for Synchronized Imaging and Therapy.

PubMed

Mukherjee, Prabuddha; Misra, Santosh K; Gryka, Mark C; Chang, Huei-Huei; Tiwari, Saumya; Wilson, William L; Scott, John W; Bhargava, Rohit; Pan, Dipanjan

2015-09-01

In this work, we demonstrate the significance of defined surface chemistry in synthesizing luminescent carbon nanomaterials (LCN) with the capability to perform dual functions (i.e., diagnostic imaging and therapy). The surface chemistry of LCN has been tailored to achieve two different varieties: one that has a thermoresponsive polymer and aids in the controlled delivery of drugs, and the other that has fluorescence emission both in the visible and near-infrared (NIR) region and can be explored for advanced diagnostic modes. Although these particles are synthesized using simple, yet scalable hydrothermal methods, they exhibit remarkable stability, photoluminescence and biocompatibility. The photoluminescence properties of these materials are tunable through careful choice of surface-passivating agents and can be exploited for both visible and NIR imaging. Here the synthetic strategy demonstrates the possibility to incorporate a potent antimetastatic agent for inhibiting melanomas in vitro. Since both particles are Raman active, their dispersion on skin surface is reported with Raman imaging and utilizing photoluminescence, their depth penetration is analysed using fluorescence 3D imaging. Our results indicate a new generation of tunable carbon-based probes for diagnosis, therapy or both. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

WATER CHEMISTRY ASSESSMENT METHODS

EPA Science Inventory

This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

Surface chemistry: Key to control and advance myriad technologies

PubMed Central

Yates, John T.; Campbell, Charles T.

2011-01-01

This special issue on surface chemistry is introduced with a brief history of the field, a summary of the importance of surface chemistry in technological applications, a brief overview of some of the most important recent developments in this field, and a look forward to some of its most exciting future directions. This collection of invited articles is intended to provide a snapshot of current developments in the field, exemplify the state of the art in fundamental research in surface chemistry, and highlight some possibilities in the future. Here, we show how those articles fit together in the bigger picture of this field. PMID:21245359

Reaction of methyl formate with VC(1 0 0) and TiC(1 0 0) surfaces

NASA Astrophysics Data System (ADS)

Frantz, Peter; Kim, Hyun I.; Didziulis, Stephen V.; Li, Shuang; Chen, Zhiying; Perry, Scott S.

2005-12-01

The chemistry of the (1 0 0) surface of the tribologically important materials vanadium carbide (VC) and titanium carbide (TiC) with methyl formate (CH 3OCHO) has been studied with X-ray photoelectron spectroscopy (XPS), high resolution electron energy loss spectroscopy (HREELS), and temperature programmed desorption (TPD). The molecule reacts with each surface at temperatures below 150 K, although the extent of reaction is greater on the TiC surface. XPS and HREELS results indicate that the first step in this chemistry is the cleavage of the CH 3O-CHO bond, generating surface methoxy groups (CH 3O-) and either carbon monoxide on VC or a formyl (CHO) group on TiC. The methoxy group reacts further on both surfaces via pathways expected based on previous methanol adsorption studies, primarily decomposing through a formyl intermediate on VC to generate formaldehyde and evolving methanol on TiC. The formyl group formed directly from methyl formate on TiC enables the production and evolution of formaldehyde, and also appears to break down further to the elements. These results indicate a propensity for these carbides to react with esters, leading potentially to the beneficial formation of friction lowering surface films or the deleterious degradation of ester-based lubricants.

In the Footsteps of Irving Langmuir: Physical Chemistry in Service of Society

NASA Astrophysics Data System (ADS)

Carter, Emily

The approach that Irving Langmuir took during his scientific career in industry at General Electric exemplifies the best that we chemical physicists/physical chemists can offer the world. His name is associated with very fundamental concepts and phenomena (e.g., the Langmuir isotherm, Langmuir-Blodgett films) along with practical inventions (e.g., the Langmuir probe, Langmuir trough). He worked at the interface of physics, chemistry, and engineering, with much of his important work devoted to understanding surface and interface phenomena. I have - unintentionally - followed in his footsteps, trained as a physical chemist who now leads the engineering school at Princeton. In this talk, I will give examples from my research as to how fundamental physical chemistry techniques and concepts - based largely on quantum mechanics - can be harnessed to help the world transition to a sustainable energy future. In the footsteps of Irving, surface and interfacial phenomena will figure prominently in the examples chosen.

Bioactivating Silicon (100) Surfaces with Novel UV Grafting of Cyclopropylamine for Promotion of Cell Adhesion

PubMed Central

Ching, Jing Yuan

2018-01-01

In this report, utraviolent (UV) photoionization of cyclopropylamine on silicon (100) hydride was employed to examine interfacing with three different epithelial cell types (MDA-MB 231, AGS and HEC1A). The cellular viability using this novel methodology had been quantified to evaluate the bioactivating potential of this ring-opening chemistry when compared to standardized controls (aminopropyltriethoxylamine, collagen and poly-L lysine). X-ray photospectroscopy (XPS) and atomic force microscopy (AFM) were used to characterize surface chemistry composition, while cell viability and confocal microscopy after 24 h of incubation were performed. Based on the results acquired from this novel ring-opening metastasis process, the promotion of cell adhesion and viability was found to be higher using this chemistry when compared to other conventional control groups, even for the collagen coating, without any observable issues of cytotoxicity. PMID:29724039

Tuning the Reversibility of Mg Anodes via Controlled Surface Passivation by H 2O/Cl – in Organic Electrolytes

DOE PAGES

Connell, Justin G.; Genorio, Bostjan; Lopes, Pietro Papa; ...

2016-10-17

Developing a new generation of battery chemistries is a critical challenge to moving beyond current Li-ion technologies. In this work, we introduce a surface-science-based approach for understanding the complex phenomena controlling the reversibility of Mg anodes for Mg-ion batteries. In addition, we identify the profound impact of trace levels of H 2O (≤3 ppm) on the kinetics of Mg deposition and determine that passive films of MgO and Mg(OH) 2 are formed only after Mg deposition ceases, rather than continuously during Mg reduction. We also find that Cl – inhibits passivation through the formation of adsorbed Cl – (Mg–Cl(ad)) and/ormore » MgCl 2 on the surface, as well as through a dynamic competition with H 2O in the double layer. In conclusion, this surface-science-based approach goes well beyond Mg anodes, highlighting the need for more in-depth understanding of electrolyte chemistries before a new generation of efficient and reversible battery technologies can be realized.« less

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

2017-05-02

In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

A Study on Advanced Lithium-Based Battery Cell Chemistries to Enhance Lunar Exploration Missions

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Bennett, William R.

2010-01-01

NASAs Exploration Technology Development Program (ETDP) Energy Storage Project conducted an advanced lithium-based battery chemistry feasibility study to determine the best advanced chemistry to develop for the Altair Lunar Lander and the Extravehicular Activities (EVA) advanced Lunar surface spacesuit. These customers require safe, reliable batteries with extremely high specific energy as compared to state-of-the-art. The specific energy goals for the development project are 220 watt-hours per kilogram (Wh/kg) delivered at the battery-level at 0 degrees Celsius ( C) at a C/10 discharge rate. Continuous discharge rates between C/5 and C/2, operation between 0 and 30 C and 200 cycles are targeted. Electrode materials that were considered include layered metal oxides, spinel oxides, and olivine-type cathode materials, and lithium metal, lithium alloy, and silicon-based composite anode materials. Advanced cell chemistry options were evaluated with respect to multiple quantitative and qualitative attributes while considering their projected performance at the end of the available development timeframe. Following a rigorous ranking process, a chemistry that combines a lithiated nickel manganese cobalt oxide Li(LiNMC)O2 cathode with a silicon-based composite anode was selected as the technology that can potentially offer the best combination of safety, specific energy, energy density, and likelihood of success.

Molecular Studies of Complex Soil Organic Matter Interactions with Metal Ions and Mineral Surfaces using Classical Molecular Dynamics and Quantum Chemistry Methods

NASA Astrophysics Data System (ADS)

Andersen, A.; Govind, N.; Laskin, A.

2017-12-01

Mineral surfaces have been implicated as potential protectors of soil organic matter (SOM) against decomposition and ultimate mineralization to small molecules which can provide nutrients for plants and soil microbes and can also contribute to the Earth's elemental cycles. SOM is a complex mixture of organic molecules of biological origin at varying degrees of decomposition and can, itself, self-assemble in such a way as to expose some biomolecule types to biotic and abiotic attack while protecting other biomolecule types. The organization of SOM and SOM with mineral surfaces and solvated metal ions is driven by an interplay of van der Waals and electrostatic interactions leading to partitioning of hydrophilic (e.g. sugars) and hydrophobic (e.g., lipids) SOM components that can be bridged with amphiphilic molecules (e.g., proteins). Classical molecular dynamics simulations can shed light on assemblies of organic molecules alone or complexation with mineral surfaces. The role of chemical reactions is also an important consideration in potential chemical changes of the organic species such as oxidation/reduction, degradation, chemisorption to mineral surfaces, and complexation with solvated metal ions to form organometallic systems. For the study of chemical reactivity, quantum chemistry methods can be employed and combined with structural insight provided by classical MD simulations. Moreover, quantum chemistry can also simulate spectroscopic signatures based on chemical structure and is a valuable tool in interpreting spectra from, notably, x-ray absorption spectroscopy (XAS). In this presentation, we will discuss our classical MD and quantum chemistry findings on a model SOM system interacting with mineral surfaces and solvated metal ions.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

Transmission electron microscopy and diffraction are powerful tools for solving complex structural problems. They complement other analytical techniques, such as x-ray diffraction, elucidating problems which cannot be solved by other techniques. One area where they are of particularly great value is in the determination of surface structures. The research presented herein uses electron microscopy and diffraction as the primary experimental techniques in the development of a chemistry of surface structures. High-resolution electron microscopy revealed that the La4Cu 3MoO12 structure has turbostratic disorder and a lower symmetry space group (Pm) than was previously found. The refinement of the x-ray data was significantly improved by using a disordered model and the Pm space group. A bond valence analysis confirmed that the disordered structure is the superior model. Strontium titanate, SrTiO3, single crystal surfaces were examined principally via transmission electron diffraction. A homologous series with intergrowths was discovered on the (110) surface of strontium titanate, marking the first time that these important concepts of solid state chemistry have been found at the surface. Atmospheric adsorbates, such as H2O and CO2, were found to help to stabilize undercoordinated surface structures on the (100) surface. It was shown that chemical bonding, bond valence, atomic coordination, and stoichiometry greatly influence the development of surface structures. Additionally, such chemistry based analysis was demonstrated to be able to predict surface structure stability and reactivity. Application of a modified Wulff construction to the observed shape of strontium titanate nanocuboids revealed that the surface structure and particle stoichiometry are interlinked, with control over one allowing equally precise control over the other. Platinum nanoparticles on the strontium titanate nanocuboids were shown via high resolution electron microscopy to have cube-on-cube epitaxy, with the shape of the platinum nanoparticles governed by the Winterbottom construction. Precise modification of the support surface will therefore allow engineering of supported metal particles with precise control over which facets are exposed. These results suggest that control over the support surface chemistry can be used to engineer thermodynamically stable, face selective catalysts.

Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

PubMed

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

Chemistry of surface nanostructures in lead precursor-rich PbZr0.52Ti0.48O3 sol-gel films

NASA Astrophysics Data System (ADS)

Gueye, I.; Le Rhun, G.; Gergaud, P.; Renault, O.; Defay, E.; Barrett, N.

2016-02-01

We present a study of the chemistry of the nanostructured phase at the surface of lead zirconium titanate PbZr0.52Ti0.48O3 (PZT) films synthesized by sol-gel method. In sol-gel synthesis, excess lead precursor is used to maintain the target stoichiometry. Surface nanostructures appear at 10% excess whereas 30% excess inhibits their formation. Using the surface-sensitive, quantitative X-ray photoelectron spectroscopy and glancing angle X-ray diffraction we have shown that the chemical composition of the nanostructures is ZrO1.82-1.89 rather than pyrochlore often described in the literature. The presence of a possibly discontinuous layer of wide band gap ZrO1.82-1.89 could be of importance in determining the electrical properties of PZT-based metal-insulator-metal heterostructures.

Chemistry and Materials Science, 1990--1991. [Second annual report

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

Sugihara, T.T.; Bruner, J.M.; McElroy, L.A.

1991-12-31

This 2-year (FY 1990-91) contains 49 technical articles in ten sections: research sampler, metals and alloys, energetic materials, chemistry and physics of advanced materials, bonding and reactions at surfaces and interfaces, superconductivity, energy R and D, waste processing and management, characterization and analysis, and facilities and instrumentation. Two more sections list department personnel, their publications etc., consultants, and summary of department budgets. The articles are processed separately for the data base. (DLC)

Organic chemistry on solid surfaces

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zaera, Francisco

2006-07-01

Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed.

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

PubMed

Barry, Seán T; Teplyakov, Andrew V; Zaera, Francisco

2018-03-20

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be viewed from the point of view of the metalorganic complexes used as precursors: they are bulky and rigid, can provide multiple binding sites for a single reaction, and can promote unique bonding modes, especially on metals, which have delocalized electronic structures. The differences between the molecular and surface chemistry of CVD and ALD precursors can result in significant variations in their reactivity, ultimately leading to unpredictable properties in the newly grown films. In this Account, we discuss some of the main similarities and differences in chemistry that CVD/ALD precursors follow on surfaces when contrasted against their known behavior in solution, with emphasis on our own work but also referencing other key contributions. Our approach is unique in that it combines expertise from the inorganic, surface science, and quantum-mechanics fields to better understand the mechanistic details of the chemistry of CVD and ALD processes and to identify new criteria to consider when designing CVD/ALD precursors.

Study of the Effect of Grafting Method on Surface Polarity of Tempo-Oxidized Nanocellulose Using Polycaprolactone as the Modifying Compound: Esterification versus Click-Chemistry

PubMed Central

Benkaddour, Abdelhaq; Jradi, Khalil; Robert, Sylvain; Daneault, Claude

2013-01-01

Esterification and click-chemistry were evaluated as surface modification treatments for TEMPO-oxidized nanocelluloses (TONC) using Polycaprolactone-diol (PCL) as modifying compound in order to improve the dispersion of nanofibers in organic media. These two grafting strategies were analyzed and compared. The first consists of grafting directly the PCL onto TONC, and was carried out by esterification between hydroxyl groups of PCL and carboxyl groups of TONC. The second strategy known as click-chemistry is based on the 1,3-dipolar cycloaddition reaction between azides and alkyne terminated moieties to form the triazole ring between PCL and TONC. The grafted samples were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Thermogravimetry analysis (TGA). Further, the effects of the two treatments on the surface hydrophobization of TONC were investigated by contact angle measurements. The results show that both methods confirm the success of such a modification and the click reaction was significantly more effective than esterification. PMID:28348357

Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques.

PubMed

Somorjai, Gabor A; Frei, Heinz; Park, Jeong Y

2009-11-25

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

Friction and surface chemistry of some ferrous-base metallic glasses

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

Marrying the mussel inspired chemistry and Kabachnik-Fields reaction for preparation of SiO2 polymer composites and enhancement removal of methylene blue

NASA Astrophysics Data System (ADS)

Huang, Qiang; Liu, Meiying; Chen, Junyu; Wan, Qing; Tian, Jianwen; Huang, Long; Jiang, Ruming; Deng, Fengjie; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-11-01

The removal of organic dyes using functionalization SiO2 composites (denoted as SiO2-PDA-CSH) were prepared via a facile method that combined with mussel inspired chemistry and Kabachnik-Fields (KF) reaction. The size and surface morphology, chemical structure, thermal stability, surface charging property, and elemental composition were evaluated by means of transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), zeta potential, and X-ray photoelectron spectroscopy (XPS), respectively. The results demonstrated that the organic functional groups can be successfully introduced onto the surface of SiO2 microspheres through the combination of mussel inspired chemistry and KF reaction. The removal of cationic dye methylene blue (MB) by the raw SiO2 and SiO2-PDA-CSH composites was examined and compared using a series of batch adsorption experiments. The results suggested that SiO2-PDA-CSH composites had a 3-fold increase in the adsorption capacity towards MB than that of pure SiO2 microspheres and the adsorption process was dependent on the solution pH. According to the adsorption kinetics, the adsorption of MB onto SiO2-PDA-CSH composites was well described by pseudo-second-order kinetic model. The equilibrium data were fitted with Langmuir and Freundlich isotherm models with R2 = 0.9981 and R2 = 0.9982, respectively. The maximum adsorption capacity from Langmuir isotherm was found to be 688.85 mg/g. The adsorption thermodynamics was also investigated in detailed. The parameters revealed that the adsorption process was spontaneous and endothermic in nature. The adsorption mechanism might be the synergistic action of physical adsorption of SiO2-PDA-CSH particles and electrostatic interaction between the MB and functional groups on the surface of SiO2-PDA-CSH composites, including sulfydryl, amino, aromatic moieties, and phosphate groups. Taken together, we developed a novel and facile strategy for the surface modification of SiO2 to achieve high adsorption towards MB based on the mussel inspired chemistry and multicomponent KF reaction. More importantly, this strategy could be easily extended for fabrication of many other high efficient adsorbents due to the universality of mussel inspired chemistry and various multicomponent reactions based on amino groups. Therefore, this work will open a new avenue and direction for the environmental applications of mussel inspired chemistry.

Droplet Deformation in an Extensional Flow: The Role of Surfactant Physical Chemistry

NASA Technical Reports Server (NTRS)

Stebe, Kathleen J.

1996-01-01

Surfactant-induced Marangoni effects strongly alter the stresses exerted along fluid particle interfaces. In low gravity processes, these stresses can dictate the system behavior. The dependence of Marangoni effects on surfactant physical chemistry is not understood, severely impacting our ability to predict and control fluid particle flows. A droplet in an extensional flow allows the controlled study of stretching and deforming interfaces. The deformations of the drop allow both Marangoni stresses, which resist tangential shear, and Marangoni elasticities, which resist surface dilatation, to develop. This flow presents an ideal model system for studying these effects. Prior surfactant-related work in this flow considered a linear dependence of the surface tension on the surface concentration, valid only at dilute surface concentrations, or a non-linear framework at concentrations sufficiently dilute that the linear approximation was valid. The linear framework becomes inadequate for several reasons. The finite dimensions of surfactant molecules must be taken into account with a model that includes surfaces saturation. Nonideal interactions between adsorbed surfactant molecules alter the partitioning of surfactant between the bulk and the interface, the dynamics of surfactant adsorptive/desorptive exchange, and the sensitivity of the surface tension to adsorbed surfactant. For example, cohesion between hydrocarbon chains favors strong adsorption. Cohesion also slows the rate of desorption from interfaces, and decreases the sensitivity of the surface tension to adsorbed surfactant. Strong cohesive interactions result in first order surface phase changes with a plateau in the surface tension vs surface concentration. Within this surface concentration range, the surface tension is decoupled from surface concentration gradients. We are engaged in the study of the role of surfactant physical chemistry in determining the Marangoni stresses on a drop in an extensional flow in a numerical and experimental program. Using surfactants whose dynamics and equilibrium behavior have been characterized in our laboratory, drop deformation will be studied in ground-based experiment. In an accompanying numerical study, predictive drop deformations will be determined based on the isotherm and equation of state determined in our laboratory. This work will improve our abilities to predict and control all fluid particle flows.

An investigation into the effectiveness of problem-based learning in a physical chemistry laboratory course

NASA Astrophysics Data System (ADS)

Gürses, Ahmet; Açıkyıldız, Metin; Doğar, Çetin; Sözbilir, Mustafa

2007-04-01

The aim of this study was to investigate the effectiveness of a problem-based learning (PBL) approach in a physical chemistry laboratory course. The parameters investigated were students’ attitudes towards a chemistry laboratory course, scientific process skills of students and their academic achievement. The design of the study was one group pre-test post-test. Four experiments, covering the topics adsorption, viscosity, surface tension and conductivity were performed using a PBL approach in the fall semester of the 2003/04 academic year at Kazim Karabekir Education Faculty of Atatürk University. Each experiment was done over a three week period. A total of 40 students, 18 male and 22 female, participated in the study. Students took the Physical Chemistry Laboratory Concept Test (PCLCT), Attitudes towards Chemistry Laboratory (ATCL) questionnaire and Science Process Skills Test (SPST) as pre and post-tests. In addition, the effectiveness of the PBL approach was also determined through four different scales; Scales Specific to Students’ Views of PBL. A statistically significant difference between the students’ academic achievement and scientific process skills at p

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

Spatially controlled immobilisation of biomolecules: A complete approach in green chemistry

NASA Astrophysics Data System (ADS)

Grinenval, Eva; Nonglaton, Guillaume; Vinet, Françoise

2014-01-01

The development of 'green' sensors is a challenging task in the field of biomolecule sensing, for example in the detection of cardiac troponin-I (cTnI). In the present work a complete approach in green chemistry was developed to create chemically active patterns for the immobilisation of biological probes. This key technology is discussed on the basis of the twelve green chemistry principles, and is a combination of surface patterning by spotting and surface chemistries modified by molecular vapour deposition. The (1H,1H,2H,2H)-perfluorodecyltrichlorosilane (FDTS) was used as a novel anti-adsorption layer while the 3,4-epoxybutyltrimethoxysilane (EBTMOS) was used to immobilise probes. Oligonucleotides and the anti-cTnI antibody were studied. The spatially controlled immobilisation of probes was characterised by fluorescence. The demonstrated surface modification has broad applications in areas such as diagnostics and bio-chemical sensing. Moreover, the environmental impacts of surface patterning and surface chemistry were discussed from a 'greenness' point of view.

Facet-Specific Ligand Interactions on Ternary AgSbS 2 Colloidal Quantum Dots

DOE PAGES

Choi, Hyekyoung; Kim, Sungwoo; Luther, Joseph M.; ...

2017-11-07

Silver dimetal chalcogenide (Ag-V-VI 2) ternary quantum dots (QDs) are emerging lead-free materials for optoelectronic devices due to their NIR band gaps, large absorption coefficients, and superior electronic properties. However, thin film-based devices of the ternary QDs still lag behind due to the lack of understanding of the surface chemistry, compared to that of lead chalcogenide QDs even with the same crystal structure. Here in this paper, the surface ligand interactions of AgSbS 2 QDs, synthesized with 1-dodecanethiol used as a stabilizer, are studied. For nonpolar (1 0 0) surfaces, it is suggested that the thiolate ligands are associated withmore » the crystal lattices, thus preventing surface oxidation by protecting sulfur after air-exposure, as confirmed through optical and surface chemical analysis. Otherwise, silver rich (1 1 1) surfaces are passivated by thiolate ligands, allowing ligand exchange processes for the conductive films. This in-depth investigation of the surface chemistry of ternary QDs will prompt the performance enhancement of their optoelectronic devices.« less

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

PubMed

Nady, Norhan

2016-04-18

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

PubMed Central

Nady, Norhan

2016-01-01

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)—is presented. PMID:27096873

Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

PubMed

Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

2016-10-01

Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Engineered microtopographies and surface chemistries direct cell attachment and function

NASA Astrophysics Data System (ADS)

Magin, Chelsea Marie

Harrison, in 1914, first recognized that cells respond to physicochemical cues such as substratum topography when he observed that fibroblasts elongated while cultured on spider silk. Recently, techniques developed in the micro-electronics industry have been used to create molds for producing microscaled topographies with various shapes and spatial arrangements. Although these patterning techniques are well-established, very little is known about the mechanisms underlying cell sensing and response to microtopographies. In this work cellular micro-environments with varying surface topographies and chemistries were evaluated with marine organisms and mammalian cells to investigate cellular sensing and response. Biofouling---the accumulation of micro-organisms, plants, and animals on submerged surfaces---is an environmental and economic concern. Engineered topographies, replicated in polydimethylsiloxane elastomer (PDMSe) and functionalized poly(ethylene glycol)-dimethacrylate (PEGDMA) hydrogels, were evaluated for inhibition of marine fouling organism attachment. Microtopographies replicated in PDMSe inhibited attachment of the marine bacterium, Cobetia marina up to 99% versus smooth. The average normalized attachment densities of cells of C. marina and zoospores of the green algae Ulva on PDMSe topographies scaled inversely with the Engineered Roughness Index (ERIII), a representation of surface energy. Attachment densities of Ulva from four assays and C. marina from two growth phases to PDMSe surfaces scaled inversely with one equation: ERI II multiplied by the Reynolds number of the organism (Re) (R 2 = 0.77). The same microtopographies created in PDMSe reduced the initial attachment density and attachment strength of cells of the diatoms Navicula incerta and Seminavis robusta compared to smooth PDMSe. The average normalized attachment density of Navicula after exposure to shear stress (48 Pa) was correlated with the contact area between the diatom and a topographically modified surface (R2=0.82). Functionalized PEGDMA hydrogels significantly reduced attachment and attachment strength of Navicula and C. marina. These hydrogels also reduced attachment of zoospores of Ulva compared to PDMSe. Attachment of Ulva to microtopographies in PDMSe and PEGDMA-co-HEMA negatively correlated with ERIII*Re (R2 = 0.94 and R2 = 0.99, respectively). Incorporating a surface energy term into this equation created a correlation between the attachment densities of cells from two evolutionarily diverse groups on substrates of two surface chemistries with an equation that describes the various microtopographies and surface chemistries in terms of surface energy (R2 = 0.80). The current Attachment Model can now be used to design engineered antifouling surface microtopographies and chemistries that inhibit the attachment of organisms from three evoluntionarily diverse groups. Hydrogels based on PEGDMA were also chosen as a substratum material for mammalian cell culture. Capturing endothelial progenitor cells (EPCs) and inducing differentiation into the endothelial cell (EC) phenotype is the ideal way to re-endothelialize a small-diameter vascular graft. Substratum elasticity has been reported to direct stem cell differentiation into specific lineages. Functionalized PEGDMA hydrogels provided good compliance, high fidelity of topographic features and sites for surface modification with biomolecules. Fibronectin grafting and topography both increased EC attachment. This combination of adjustable elasticity, surface chemistry and topography has the potential to promote the capture and differentiation of EPCs into a confluent EC monolayer. Engineered microtopographies replicated in PDMSe directed elongation and alignment of human coronary artery endothelial cells (HCAECs) and human coronary artery smooth muscle cells (HCASMCs) compared to smooth surfaces. Engineered cellular micro-environments were created with specific surface energies defined by chemistry and topography to successfully direct cell attachment and function.

Sol-gel chemistry-based Ucon-coated columns for capillary electrophoresis.

PubMed

Hayes, J D; Malik, A

1997-07-18

A sol-gel chemistry-based novel approach for the preparation of a Ucon-coated fused-silica capillary column in capillary electrophoresis is presented. In this approach the sol-gel process is carried out inside 25 microm I.D. fused-silica capillaries. The sol solution contained appropriate quantities of an alkoxide-based sol-gel precursor, a polymeric coating material (Ucon), a crosslinking reagent, a surface derivatizing reagent, controlled amounts of water and a catalyst dissolved in a suitable solvent system. The coating procedure involves filling a capillary with the sol solution and allowing the sol-gel process to proceed for an optimum period. Hydrolysis of the alkoxide precursor and polycondensation of the hydrolyzed products with the surface silanol groups and the hydroxy-terminated Ucon molecules lead to the formation of a surface-bonded sol-gel coating on the inner walls of the capillary. The thickness of the coated film can be controlled by varying the reaction time, coating solution composition and experimental conditions. Commercial availability of high purity sol-gel precursors (e.g., TEOS 99.999%), the ease of coating, run-to-run and column-to-column reproducibility, and long column lifetimes make sol-gel coating chemistry very much suitable for being applied in analytical microseparations column technology. Test samples of basic proteins and nucleotides were used to evaluate the column performance. These results show that the sol-gel coating scheme has allowed for the generation of bio-compatible surfaces characterized by high separation efficiencies in CE. For different types of solutes, the sol-gel coated Ucon column consistently provided migration time R.S.D. values of the order of 0.5%.

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

2016-08-01

The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

Method of protecting the surface of a substrate. [by applying aluminide coating

NASA Technical Reports Server (NTRS)

Gedwill, M. A. (Inventor); Grisaffe, S. J.

1974-01-01

The surface of a metallic base system is initially coated with a metallic alloy layer that is ductile and oxidation resistant. An aluminide coating is then applied to the metallic alloy layer. The chemistry of the metallic alloy layer is such that the oxidation resistance of the subsequently aluminized outermost layer is not seriously degraded.

MURI Center for Materials Chemistry in the Space Environment

DTIC Science & Technology

2006-11-30

ionic species in relevant reaction environments, surface photochemistry expertise, synchrotron-based measurement and irradiation, synthesis of structural...and Ne+ ions with dodecanethiolate and semifluorinated dodecanethiolate self-assembled monolayers (SAM), polyhedral oligomeric silsesquioxane (POSS...POSS/Kapton models as gas phase species, and with alkane thiol self assembled monolayers on gold surfaces, and with liquid squalane. We have also

THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

EPA Science Inventory

In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

A Self Consistent RF Discharge, Plasma Chemistry and Surface Model for Plasma Enhanced Chemical Vapor Deposition

DTIC Science & Technology

1988-06-30

consists of three submodels for the electron kinetics, plasma chemistry , and surface deposition kinetics for a-Si:H deposited from radio frequency...properties. Plasma enhanced, Chemical vapor deposition, amorphous silicon, Modeling, Electron kinetics, Plasma chemistry , Deposition kinetics, Rf discharge, Silane, Film properties, Silicon.

Acetone Chemistry on Oxidized and Reduced TiO 2(110)

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

Henderson, Michael A

2004-12-09

The chemistry of acetone on the oxidized and reduced surfaces of TiO 2(110) was examined using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The reduced surface was prepared with about 7% oxygen vacancy sites by annealing in ultrahigh vacuum (UHV) at 850 K, and the oxidized surface was prepared by exposure of the reduced surface to molecular oxygen at 95 K followed by heating the surface to a variety of temperatures between 200 and 500 K. Acetone adsorbs molecularly on the reduced surface with no evidence for either decomposition or preferential binding at vacancy sites.more » Based on HREELS, the majority of acetone molecules adsorbed in an η¹ configuration at Ti⁴⁺ sites through interaction of lone pair electrons on the carbonyl oxygen atom. Repulsive acetone-acetone interactions shift the desorption peak from 345 K at low coverage to 175 K as the first layer saturates with a coverage of ~ 1 ML. In contrast, about 7% of the acetone adlayer decomposes when the surface is pretreated with molecular oxygen. Acetate is among the detected decomposition products, but only comprises about 1/3rd of the amount of acetone decomposed and its yield depends on the temperature at which the O₂ exposed surface was preheated to prior to acetone adsorption. Aside from the small level of irreversible decomposition, about 0.25 ML of acetone is stabilized to 375 K by coadsorbed oxygen. These acetone species exhibit an HREELS spectrum unlike that of η¹-acetone or of any other species proposed to exist from the interaction of acetone with TiO₂ powders. Based on the presence of extensive ¹⁶O/¹⁸O exchange between acetone and coadsorbed oxygen in the 375 K acetone TPD state, it is proposed that a polymeric form of acetone forms on the TiO₂(110) surface through nucleophilic attack of oxygen on the carbonyl carbon atom of acetone, and is propagated to neighboring η¹-acetone molecules. This process is initiated at temperatures as low as 135 K based on HREELS. Although the dominant thermal pathway of this surface species is to liberate acetone in UHV, it may be a key intermediate in acetone thermal and photolytic chemistry on TiO₂ surfaces.« less

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

2015-10-01

Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems. Electronic supplementary information (ESI) available: Experimental procedures, synthesis, and characterization of molecules 1, 2 and 3. Explanation of the electrochemical method for approximating nanopore diameter. Additional XPS spectra. See DOI: 10.1039/C5NR02939B

Chemical changes in DMP1-null murine bone & silica based pecvd coatings for titanium implant osseoapplications

NASA Astrophysics Data System (ADS)

Maginot, Megen

In order to improve clinical outcomes in bone-implant systems, a thorough understanding of both local bone chemistry and implant surface chemistry is necessary. This study consists, therefore, of two main parts: one focused on determining the nature of the changes in bone chemistry in a DMP1-null transgenic disease model and the other on the development of amorphous silica-based coatings for potential use as titanium bone implant coatings. For the study of bone mineral in the DMP1 transgenic model, which is known to have low serum phosphate levels, transgenic DMP1-null and wild type mice were fed a high phosphate diet, sacrificed, and had their long bone harvested. This bone was characterized using SEM, FTIR, microCT and XANES and compared to DMP1-null and wild type control groups to assess the therapeutic effect of high Pi levels on the phenotype and the role of DMP1 in mineralization in vivo. Findings suggest that though the high phosphate diet results in restoring serum phosphate levels, it does not completely rescue the bone mineral phenotype at an ultrastructural level and implicates DMP1 in phosphate nucleation. Since plasma enhanced chemical vapor deposition (PECVD) silica like coatings have not previously been fabricated for use in oessoapplications, the second part of this study initially focused on the characterization of novel SiOx chemistries fabricated via a chemical vapor deposition process that were designed specifically to act as bioactive coatings with a loose, hydrogenated structure. These coatings were then investigated for their potential initial stage response to bone tissue through immersion in a simulated body fluid and through the culture of MC3T3 cells on the coating surfaces. Coating surfaces were characterized by SEM, FTIR, contact angle measurements, and XANES. Coating dissolution and ionic release were also investigated by ICP-OES. Findings suggest that some SiOx chemistries may form a bioactive coating while more highly substituted chemistries may form a bioresorbable coating, similar to commercially available bioactive glasses.

2013 Chemical reactions at surfaces. Surfaces in Energy and the Environment. Gordon Research Conference and Gordon Research Seminar (April 28 - May 3, 2013 - Les Diablerets, Switzerland)

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

Stair, Peter C.

presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments.

The effects of atmospheric chemistry on radiation budget in the Community Earth Systems Model

NASA Astrophysics Data System (ADS)

Choi, Y.; Czader, B.; Diao, L.; Rodriguez, J.; Jeong, G.

2013-12-01

The Community Earth Systems Model (CESM)-Whole Atmosphere Community Climate Model (WACCM) simulations were performed to study the impact of atmospheric chemistry on the radiation budget over the surface within a weather prediction time scale. The secondary goal is to get a simplified and optimized chemistry module for the short time period. Three different chemistry modules were utilized to represent tropospheric and stratospheric chemistry, which differ in how their reactions and species are represented: (1) simplified tropospheric and stratospheric chemistry (approximately 30 species), (2) simplified tropospheric chemistry and comprehensive stratospheric chemistry from the Model of Ozone and Related Chemical Tracers, version 3 (MOZART-3, approximately 60 species), and (3) comprehensive tropospheric and stratospheric chemistry (MOZART-4, approximately 120 species). Our results indicate the different details in chemistry treatment from these model components affect the surface temperature and impact the radiation budget.

Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

ERIC Educational Resources Information Center

White, J. M.; Campbell, Charles T.

1980-01-01

Provides background data on surface chemistry as an emerging discipline. Highlights the important role which surfaces play in catalysis by focusing on the catalyzed oxidation of carbon monoxide. Provides a demonstration of how surfaces exert their influences in heterogeneous phenomena and illustrates how experimental problems in this field are…

Effect of chitosan and cationic starch on the surface chemistry properties of bagasse paper.

PubMed

Ashori, Alireza; Cordeiro, Nereida; Faria, Marisa; Hamzeh, Yahya

2013-07-01

The use of non-wood fibers in the paper industry has been an economical and environmental necessity. The application of dry-strength agents has been a successful method to enhance the strength properties of paper. The experimental results evidencing the potential of chitosan and cationic starch utilization in bagasse paper subjected to hot water pre-extraction has been presented in this paper. The research analyzes the surface properties alterations due to these dry-strength agents. Inverse gas chromatography was used to evaluate the properties of surface chemistry of the papers namely the surface energy, active sites, surface area as well as the acidic/basic character. The results of the study revealed that the handsheets process causes surface arrangement and orientation of chemical groups, which induce a more hydrophobic and basic surface. The acid-base surface characteristics after the addition of dry-strength agents were the same as the bagasse handsheets with and without hot water pre-extraction. The results showed that the dry-strength agent acts as a protecting film or glaze on the surfaces of bagasse paper handsheets. Copyright © 2013 Elsevier B.V. All rights reserved.

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

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

Hoppe, Eric W.; Seifert, Allen; Aalseth, Craig E.

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaningmore » of surfaces. The acidified hydrogen peroxide solution will generally target the Cu+/Cu2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified. © 2001 Elsevier Science. All rights reserved« less

Technique for etching monolayer and multilayer materials

DOEpatents

Bouet, Nathalie C. D.; Conley, Raymond P.; Divan, Ralu; Macrander, Albert

2015-10-06

A process is disclosed for sectioning by etching of monolayers and multilayers using an RIE technique with fluorine-based chemistry. In one embodiment, the process uses Reactive Ion Etching (RIE) alone or in combination with Inductively Coupled Plasma (ICP) using fluorine-based chemistry alone and using sufficient power to provide high ion energy to increase the etching rate and to obtain deeper anisotropic etching. In a second embodiment, a process is provided for sectioning of WSi.sub.2/Si multilayers using RIE in combination with ICP using a combination of fluorine-based and chlorine-based chemistries and using RF power and ICP power. According to the second embodiment, a high level of vertical anisotropy is achieved by a ratio of three gases; namely, CHF.sub.3, Cl.sub.2, and O.sub.2 with RF and ICP. Additionally, in conjunction with the second embodiment, a passivation layer can be formed on the surface of the multilayer which aids in anisotropic profile generation.

Biochip-based instruments development for space exploration: influence of the antibody immobilization process on the biochip resistance to freeze-drying, temperature shifts and cosmic radiations

NASA Astrophysics Data System (ADS)

Coussot, G.; Moreau, T.; Faye, C.; Vigier, F.; Baqué, M.; Le Postollec, A.; Incerti, S.; Dobrijevic, M.; Vandenabeele-Trambouze, O.

2017-04-01

Due to the diversity of antibody (Ab)-based biochips chemistries available and the little knowledge about biochips resistance to space constraints, immobilization of Abs on the surface of the biochips dedicated to Solar System exploration is challenging. In the present paper, we have developed ten different biochip models including covalent or affinity immobilization with full-length Abs or Ab fragments. Ab immobilizations were carried out in oriented/non-oriented manner using commercial activated surfaces with N-hydroxysuccinic ester (NHS-surfaces) or homemade surfaces using three generations of dendrimers (dendrigraft of poly L-lysine (DGL) surfaces). The performances of the Ab -based surfaces were cross-compared on the following criteria: (i) analytical performances (expressed by both the surface density of immobilized Abs and the amount of antigens initially captured by the surface) and (ii) resistance of surfaces to preparation procedure (freeze-drying, storage) or spatial constraints (irradiation and temperature shifts) encountered during a space mission. The latter results have been expressed as percentage of surface binding capacity losses (or percentage of remaining active Abs). The highest amount of captured antigen was achieved with Ab surfaces having full-length Abs and DGL-surfaces that have much higher surface densities than commercial NHS-surface. After freeze-drying process, thermal shift and storage sample exposition, we found that more than 80% of surface binding sites remained active in this case. In addition, the resistance of Ab surfaces to irradiation with particles such as electron, carbon ions or protons depends not only on the chemistries (covalent/affinity linkages) and strategies (oriented/non-oriented) used to construct the biochip, but also on the type, energy and fluence of incident particles. Our results clearly indicate that full-length Ab immobilization on NHS-surfaces and DGL-surfaces should be preferred for potential use in instruments for planetary exploration.

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

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

Alvarado, Samuel R.; Guo, Yijun; Ruberu, T. Purnima A.

2014-03-15

The optoelectronic and chemical properties of semiconductor nanocrystals heavily depend on their composition, size, shape and internal structure, surface functionality, etc. Available strategies to alter these properties through traditional colloidal syntheses and ligand exchange methods place a premium on specific reaction conditions and surfactant combinations. In this invited review, we apply a molecular-level understanding of chemical precursor reactivity to reliably control the morphology, composition and intimate architecture (core/shell vs. alloyed) of semiconductor nanocrystals. We also describe our work aimed at achieving highly selective, low-temperature photochemical methods for the synthesis of semiconductor–metal and semiconductor–metal oxide photocatalytic nanocomposites. In addition, we describemore » our work on surface modification of semiconductor nanocrystal quantum dots using new approaches and methods that bypass ligand exchange, retaining the nanocrystal's native ligands and original optical properties, as well as on spectroscopic methods of characterization useful in determining surface ligand organization and chemistry. Using recent examples from our group and collaborators, we demonstrate how these efforts have lead to faster, wider and more systematic application of semiconductor nanocrystal-based materials to biological imaging and tracking, and to photocatalysis of unconventional substrates. We believe techniques and methods borrowed from inorganic chemistry (including coordination, organometallic and solid state chemistry) have much to offer in reaching a better understanding of the synthesis, functionalization and real-life application of such exciting materials as semiconductor nanocrystals (quantum dots, rods, tetrapods, etc.).« less

How Reliable Are ATP Bioluminescence Meters in Assessing Decontamination of Environmental Surfaces in Healthcare Settings?

PubMed Central

Omidbakhsh, Navid; Ahmadpour, Faraz; Kenny, Nicole

2014-01-01

Background Meters based on adenosine triphosphate (ATP) bioluminescence measurements in relative light units (RLU) are often used to rapidly assess the level of cleanliness of environmental surfaces in healthcare and other settings. Can such ATP measurements be adversely affected by factors such as soil and cleaner-disinfectant chemistry? Objective This study tested a number of leading ATP meters for their sensitivity, linearity of the measurements, correlation of the readings to the actual microbial contamination, and the potential disinfectant chemicals’ interference in their readings. Methods First, solutions of pure ATP in various concentrations were used to construct a standard curve and determine linearity and sensitivity. Serial dilutions of a broth culture of Staphylococcus aureus, as a representative nosocomial pathogen, were then used to determine if a given meter’s ATP readings correlated with the actual CFUs. Next, various types of disinfectant chemistries were tested for their potential to interfere with the standard ATP readings. Results All four ATP meters tested herein demonstrated acceptable linearity and repeatability in their readings. However, there were significant differences in their sensitivity to detect the levels of viable microorganisms on experimentally contaminated surfaces. Further, most disinfectant chemistries tested here quenched the ATP readings variably in different ATP meters evaluated. Conclusions Apart from their limited sensitivity in detecting low levels of microbial contamination, the ATP meters tested were also prone to interference by different disinfectant chemistries. PMID:24940751

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan.

PubMed

Rahm, Martin; Lunine, Jonathan I; Usher, David A; Shalloway, David

2016-07-19

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini-Huygens mission measurements of the atmosphere and the surface of Saturn's moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable "natural laboratory" for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan's atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI's intermolecular and intramolecular =N-H(…)N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

F 2 excimer laser (157 nm) radiation modification and surface ablation of PHEMA hydrogels and the effects on bioactivity: Surface attachment and proliferation of human corneal epithelial cells

NASA Astrophysics Data System (ADS)

Zainuddin; Chirila, Traian V.; Barnard, Zeke; Watson, Gregory S.; Toh, Chiong; Blakey, Idriss; Whittaker, Andrew K.; Hill, David J. T.

2011-02-01

Physical and chemical changes at the surface of poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels modified by ablation with an F 2 excimer laser were investigated experimentally. An important observation was that only the outer exposed surface layers of the hydrogel were affected by the exposure to 157 nm radiation. The effect of the surface changes on the tendency of cells to adhere to the PHEMA was also investigated. A 0.5 cm 2 area of the hydrogel surfaces was exposed to laser irradiation at 157 nm to fluences of 0.8 and 4 J cm -2. The changes in surface topography were analysed by light microscopy and atomic force microscopy, while the surface chemistry was characterized by attenuated total reflection infrared and X-ray photoelectron spectroscopies. Cell-interfacial interactions were examined based on the proliferation of human corneal limbal epithelial (HLE) cells cultured on the laser-modified hydrogels, and on the unexposed hydrogels and tissue culture plastic for comparison. It was observed that the surface topography of laser-exposed hydrogels showed rippled patterns with a surface roughness increasing at the higher exposure dose. The changes in surface chemistry were affected not only by an indirect effect of hydrogen and hydroxyl radicals, formed by water photolysis, on the PHEMA, but also by the direct action of laser radiation on PHEMA if the surface layers of the gel become depleted of water. The laser treatment led to a change in the surface characteristics, with a lower concentration of ester side-chains and the formation of new oxygenated species at the surface. The surface also became more hydrophobic. Most importantly, the surface chemistry and the newly created surface topographical features were able to improve the attachment, spreading and growth of HLE cells.

Characterization of the surface properties of epoxy-type models used for multiphase flow studies in fractured media and creation of a new model

NASA Astrophysics Data System (ADS)

Bergslien, Elisa; Fountain, John; Giese, Rossman

2004-05-01

Epoxy models have been used as analogs for fractured rock surfaces in many laboratory investigations of multiphase flow processes. However, there is no agreement on how well or poorly such an analog replicates the surface chemistry of geologic materials, nor is there a satisfactory analysis of the surface properties of epoxy. This paper addresses the issue of accurately characterizing the surface chemistry of a typical epoxy used in laboratory multiphase flow studies and comparing that surface to a polystyrene surface and a radio frequency glow discharge treated polystyrene surface. Surface properties were determined using direct contact angle measurements of polar and apolar liquids on flat test samples. The epoxy was determined to have surface properties as follows: γ = 62.3, γLW = 39, γAB = 23.3, γ⊕ = 0, and γ? = 23.3 mJ/m2, where γ is the total surface tension of the solid, γLW is the Lifshitz-van der Waals (LW) surface tension component, γAB is the Lewis acid base (AB) surface tension component, γ? is the electron-donor (negative) parameter, and γ⊕ is the electron-acceptor (positive) parameter. Values of γ? < 27.9 mJ/m2 indicate a hydrophobic surface, which means that epoxy is not a good analog for most geologic materials. This study also explores the use of radio frequency glow discharge plasma to add hydroxyl functionality to polymer surfaces producing a material with alterable surface properties and the same optical and casting properties as epoxy. Using this method, the degree of alteration of the surface chemistry of polymer fracture models can be controlled, allowing the creation of models with a variety of different wettabilities. The resultant models were found to be durable, long lasting, and a potentially very useful alternative to the more typical epoxy models.

Use of soil-streamwater relationships to assess regional patterns of acidic deposition effects in the northeastern USA

USGS Publications Warehouse

Siemion, Jason; Lawrence, Gregory B.; Murdoch, Peter S.

2013-01-01

Declines of acidic deposition levels by as much as 50% since 1990 have led to partial recovery of surface waters in the northeastern USA but continued depletion of soil calcium through this same period suggests a disconnection between soil and surface water chemistry. To investigate the role of soil-surface water interactions in recovery from acidification, the first regional survey to directly relate soil chemistry to stream chemistry during high flow was implemented in a 4144-km2 area of the Catskill region of New York, where acidic deposition levels are among the highest in the East.More than 40% of 95 streams sampled in the southern Catskill Mountains were determined to be acidified and had inorganic monomeric aluminum concentrations that exceeded a threshold that is toxic to aquatic biota. More than 80% likely exceeded this threshold during the highest flows, but less than 10% of more than 100 streams sampled were acidified in the northwestern portion of the region. Median Oa horizon soil base saturation ranged from 50% to 80% at 200 sites across the region, but median base saturation in the upper 10 cm of the B horizon was less than 20% across the region and was only 2% in the southern area. Aluminum is likely to be interfering with root uptake of calcium in the mineral horizon in approximately half the sampled watersheds. Stream chemistry was highly variable over the Catskill region and, therefore, did not always reflect the calcium depletion of the B horizon that our sampling suggested was nearly ubiquitous throughout the region. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

Iron oxide magnetic nanoparticles with versatile surface functions based on dopamine anchors

NASA Astrophysics Data System (ADS)

Mazur, Mykola; Barras, Alexandre; Kuncser, Victor; Galatanu, Andrei; Zaitzev, Vladimir; Turcheniuk, Kostiantyn V.; Woisel, Patrice; Lyskawa, Joel; Laure, William; Siriwardena, Aloysius; Boukherroub, Rabah; Szunerits, Sabine

2013-03-01

The synthesis of multifunctional magnetic nanoparticles (MF-MPs) is one of the most active research areas in advanced materials as their multifunctional surfaces allow conjugation of biological and chemical molecules, thus making it possible to achieve target-specific diagnostic in parallel to therapeutics. We report here a simple strategy to integrate in a one-step reaction several reactive sites onto the particles. The preparation of MF-MPs is based on their simultaneous modification with differently functionalized dopamine derivatives using simple solution chemistry. The formed MF-MPs show comparable magnetic properties to those of naked nanoparticles with almost unaltered particle size of around 25 nm. The different termini, amine, azide and maleimide functions, enable further functionalization of MF-MPs by the grafting-on approach. Michael addition, Cu(i) catalyzed « click » chemistry and amidation reactions are performed on the MF-MPs integrating subsequently 6-(ferrocenyl)-hexanethiol, horseradish peroxidase (HRP) and mannose.

What's on the Surface? Physics and Chemistry of Delta-Doped Surfaces

NASA Technical Reports Server (NTRS)

Hoenk, Michael

2011-01-01

Outline of presentation: 1. Detector surfaces and the problem of stability 2. Delta-doped detectors 3. Physics of Delta-doped Silicon 4. Chemistry of the Si-SiO2 Interface 5. Physics and Chemistry of Delta-doped Surfaces a. Compensation b. Inversion c. Quantum exclusion. Conclusions: 1. Quantum confinement of electrons and holes dominates the behavior of delta-doped surfaces. 2. Stability of delta-doped detectors: Delta-layer creates an approx 1 eV tunnel barrier between bulk and surface. 3. At high surface charge densities, Tamm-Shockley states form at the surface. 4. Surface passivation by quantum exclusion: Near-surface delta-layer suppresses T-S trapping of minority carriers. 5. The Si-SiO2 interface compensates the surface 6. For delta-layers at intermediate depth, surface inversion layer forms 7. Density of Si-SiO2 interface charge can be extremely high (>10(exp 14)/sq cm)

Nanocellulose-Based Materials for Water Purification

PubMed Central

Voisin, Hugo; Bergström, Lennart; Liu, Peng; Mathew, Aji P.

2017-01-01

Nanocellulose is a renewable material that combines a high surface area with high strength, chemical inertness, and versatile surface chemistry. In this review, we will briefly describe how nanocellulose is produced, and present—in particular, how nanocellulose and its surface modified versions affects the adsorption behavior of important water pollutants, e.g., heavy metal species, dyes, microbes, and organic molecules. The processing of nanocellulose-based membranes and filters for water purification will be described in detail, and the uptake capacity, selectivity, and removal efficiency will also be discussed. The processing and performance of nanocellulose-based membranes, which combine a high removal efficiency with anti-fouling properties, will be highlighted. PMID:28336891

Mass Spectrometric Analysis of the Cell Surface N-Glycoproteome by Combining Metabolic Labeling and Click Chemistry

NASA Astrophysics Data System (ADS)

Smeekens, Johanna M.; Chen, Weixuan; Wu, Ronghu

2015-04-01

Cell surface N-glycoproteins play extraordinarily important roles in cell-cell communication, cell-matrix interactions, and cellular response to environmental cues. Global analysis is exceptionally challenging because many N-glycoproteins are present at low abundances and effective separation is difficult to achieve. Here, we have developed a novel strategy integrating metabolic labeling, copper-free click chemistry, and mass spectrometry (MS)-based proteomics methods to analyze cell surface N-glycoproteins comprehensively and site-specifically. A sugar analog containing an azido group, N-azidoacetylgalactosamine, was fed to cells to label glycoproteins. Glycoproteins with the functional group on the cell surface were then bound to dibenzocyclooctyne-sulfo-biotin via copper-free click chemistry under physiological conditions. After protein extraction and digestion, glycopeptides with the biotin tag were enriched by NeutrAvidin conjugated beads. Enriched glycopeptides were deglycosylated with peptide- N-glycosidase F in heavy-oxygen water, and in the process of glycan removal, asparagine was converted to aspartic acid and tagged with 18O for MS analysis. With this strategy, 144 unique N-glycopeptides containing 152 N-glycosylation sites were identified in 110 proteins in HEK293T cells. As expected, 95% of identified glycoproteins were membrane proteins, which were highly enriched. Many sites were located on important receptors, transporters, and cluster of differentiation proteins. The experimental results demonstrated that the current method is very effective for the comprehensive and site-specific identification of the cell surface N-glycoproteome and can be extensively applied to other cell surface protein studies.

Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

NASA Astrophysics Data System (ADS)

Petit, Camille

Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism involves dissolution of ammonia in water when moisture is present in the system. Even though this process increases the breakthrough capacity of a material, it provides rather weak retention forces since ammonia dissolved in water is easily desorbed from the adsorbent's surface.

Hydrogeology and Water Quality of the Pepacton Reservoir Watershed in Southeastern New York. Part 3. Responses of Stream Base-Flow Chemistry to Hydrogeologic Factors and Nonpoint-Sources of Contamination

USGS Publications Warehouse

Heisig, Paul M.; Phillips, Patrick J.

2004-01-01

The implications of this study are that seasonal and more frequent base-flow surveys of water chemistry from small stream basins can help refine the understanding of local hydrogeologic systems and define the effects of nonpointsource contamination on base-flow water quality. The concentration of most nonpoint sources in valley-bottom or lower-hillside areas helped indicate the relative contributions of water from hillside and valley-bottom areas at different times of year. The positive correlations between the intensity of nonpoint-source activities and nonpoint-source constituents in base flow underscores the link between land use (nonpoint sources), ground-water quality, and surface-water quality.

Manipulating the Surface Chemistry of Quantum Dots for Sensitive Ratiometric Fluorescence Detection of Sulfur Dioxide.

PubMed

Li, Huihui; Zhu, Houjuan; Sun, Mingtai; Yan, Yehan; Zhang, Kui; Huang, Dejian; Wang, Suhua

2015-08-11

Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.

Impacts of chemical modification on the toxicity of diverse nanocellulose materials to developing zebrafish

PubMed Central

Harper, Bryan J.; Clendaniel, Alicea; Sinche, Federico; Way, Daniel; Hughes, Michael; Schardt, Jenna; Simonsen, John; Stefaniak, Aleksandr B.

2016-01-01

Cellulose is an abundant and renewable resource currently being investigated for utility in nanomaterial form for various promising applications ranging from medical and pharmaceutical uses to mechanical reinforcement and biofuels. The utility of nanocellulose and wide implementation ensures increasing exposure to humans and the environment as nanocellulose-based technologies advance. Here, we investigate how differences in aspect ratio and changes to surface chemistry, as well as synthesis methods, influence the biocompatibility of nanocellulose materials using the embryonic zebrafish. Investigations into the toxicity of neutral, cationic and anionic surface functionalities revealed that surface chemistry had a minimal influence on the overall toxicity of nanocellulose materials. Higher aspect ratio cellulose nanofibers produced by mechanical homogenization were, in some cases, more toxic than other cellulose-based nanofibers or nanocrystals produced by chemical synthesis methods. Using fluorescently labeled nanocellulose we were able to show that nanocellulose uptake did occur in embryonic zebrafish during development. We conclude that the benign nature of nanocellulose materials makes them an ideal platform to systematically investigate the inherent surface features driving nanomaterial toxicity in order to create safer design principles for engineered nanoparticles. PMID:27468180

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores

DOE PAGES

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

2016-07-27

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

Polar boundary layer bromine explosion and ozone depletion events in the chemistry-climate model EMAC v2.52: implementation and evaluation of AirSnow algorithm

NASA Astrophysics Data System (ADS)

Falk, Stefanie; Sinnhuber, Björn-Martin

2018-03-01

Ozone depletion events (ODEs) in the polar boundary layer have been observed frequently during springtime. They are related to events of boundary layer enhancement of bromine. Consequently, increased amounts of boundary layer volume mixing ratio (VMR) and vertical column densities (VCDs) of BrO have been observed by in situ observation, ground-based as well as airborne remote sensing, and from satellites. These so-called bromine explosion (BE) events have been discussed serving as a source of tropospheric BrO at high latitudes, which has been underestimated in global models so far. We have implemented a treatment of bromine release and recycling on sea-ice- and snow-covered surfaces in the global chemistry-climate model EMAC (ECHAM/MESSy Atmospheric Chemistry) based on the scheme of Toyota et al. (2011). In this scheme, dry deposition fluxes of HBr, HOBr, and BrNO3 over ice- and snow-covered surfaces are recycled into Br2 fluxes. In addition, dry deposition of O3, dependent on temperature and sunlight, triggers a Br2 release from surfaces associated with first-year sea ice. Many aspects of observed bromine enhancements and associated episodes of near-complete depletion of boundary layer ozone, both in the Arctic and in the Antarctic, are reproduced by this relatively simple approach. We present first results from our global model studies extending over a full annual cycle, including comparisons with Global Ozone Monitoring Experiment (GOME) satellite BrO VCDs and surface ozone observations.

Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

NASA Technical Reports Server (NTRS)

Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

2009-01-01

Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Linking molecular level chemistry to macroscopic combustion behavior for nano-energetic materials with halogen containing oxides.

PubMed

Farley, Cory W; Pantoya, Michelle L; Losada, Martin; Chaudhuri, Santanu

2013-08-21

Coupling molecular scale reaction kinetics with macroscopic combustion behavior is critical to understanding the influences of intermediate chemistry on energy propagation, yet bridging this multi-scale gap is challenging. This study integrates ab initio quantum chemical calculations and condensed phase density functional theory to elucidate factors contributing to experimentally measured high flame speeds (i.e., >900 m∕s) associated with halogen based energetic composites, such as aluminum (Al) and iodine pentoxide (I2O5). Experiments show a direct correlation between apparent activation energy and flame speed suggesting that flame speed is directly influenced by chemical kinetics. Toward this end, the first principle simulations resolve key exothermic surface and intermediate chemistries contributing toward the kinetics that promote high flame speeds. Linking molecular level exothermicity to macroscopic experimental investigations provides insight into the unique role of the alumina oxide shell passivating aluminum particles. In the case of Al reacting with I2O5, the alumina shell promotes exothermic surface chemistries that reduce activation energy and increase flame speed. This finding is in contrast to Al reaction with metal oxides that show the alumina shell does not participate exothermically in the reaction.

Boosting the Supercapacitance of Nitrogen-Doped Carbon by Tuning Surface Functionalities.

PubMed

Biemolt, Jasper; Denekamp, Ilse M; Slot, Thierry K; Rothenberg, Gadi; Eisenberg, David

2017-10-23

The specific capacitance of a highly porous, nitrogen-doped carbon is nearly tripled by orthogonal optimization of the microstructure and surface chemistry. First, the carbons' hierarchical pore structure and specific surface area were tweaked by controlling the temperature and sequence of the thermal treatments. The best process (pyrolysis at 900 °C, washing, and subsequent annealing at 1000 °C) yielded a carbon with a specific capacitance of 117 F g -1 -nearly double that of a carbon made by a typical single-step synthesis at 700 °C. Following the structural optimization, the surface chemistry of the carbons was enriched by applying an oxidation routine based on a mixture of nitric and sulfuric acid in a 1:4 ratio at two different treatment temperatures (0 and 20 °C) and different treatment times. The optimal treatment times were 4 h at 0 °C and only 1 h at 20 °C. Overall, the specific capacitance nearly tripled relative to the original carbon, reaching 168 F g -1 . The inherent nitrogen doping of the carbon comes into interplay with the acid-induced surface functionalization, creating a mixture of oxygen- and nitrogen-oxygen functionalities. The evolution of the surface chemistry was carefully followed by X-ray photoelectron spectroscopy and by N 2 sorption porosimetry, revealing stepwise surface functionalization and simultaneous carbon etching. Overall, these processes are responsible for the peak-shaped capacitance trends in the carbons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of activated carbon surface chemistry and pore structure on the adsorption of trace organic contaminants from aqueous solution

NASA Astrophysics Data System (ADS)

Li, Lei

The objectives were (1) to identify activated pore structure and surface chemistry characteristics that assure the effective removal of trace organic contaminants from aqueous-solution, and (2) to develop a procedure to predict the adsorption capacity of activated carbons from fundamental adsorbent and adsorbate properties. A matrix of activated carbon fibers (ACFs) (with three activation levels and four surface chemistry levels) and three commercially available granular activated carbons (GACs) served as the adsorbents. BET surface area, pore size distribution, elemental composition, point of zero charge and infrared spectroscopy data were obtained to characterize the adsorbents. The adsorption of relative hydrophilic methyl tertiary-butyl ether (MTBE) and relative hydrophobic trichloroethene (TCE) were conducted in both ultrapure water and Sacramento-San Joaquin Delta water. The results showed that an effective adsorbent for the removal of micropollutants from water requires (1) a large volume of micropores with widths that are about 1.5 times larger than the kinetic diameter of the target adsorbate, (2) a micropore size distribution that extends to widths that are approximately twice the kinetic diameter of the target adsorbate to prevent pore blockage by NOM, and (3) a hydrophobic pore surface chemistry with the sum of oxygen and nitrogen contents less than 2 to 3 mmol/g. A procedure based on the Polanyi Potential Theory (PPT) was developed to predict the adsorption capacities of activated carbons from fundamental adsorbent and adsorbate properties. A correlation between the coalescing factor for water adsorption and adsorbent oxygen content was developed. Based on this correlation, the PPT yielded reasonable estimates of aqueous phase adsorption capacities for both relatively polar and non-polar adsorbates on both relatively hydrophobic and hydrophilic activated carbons. With the developed procedure, the adsorption capacities of organic compounds that are partially miscible in water can be predicted from (1) N2 and CO2 adsorption isotherms of a given adsorbent, (2) the adsorbent oxygen content, and (3) the molar volume and parachor of the target adsorbate.

Photothermal-enhanced catalysis in core-shell plasmonic hierarchical Cu7S4 microsphere@zeolitic imidazole framework-8.

PubMed

Wang, Feifan; Huang, Yanjie; Chai, Zhigang; Zeng, Min; Li, Qi; Wang, Yuan; Xu, Dongsheng

2016-12-01

Conventional semiconductor photocatalysis based on band-edge absorption remains inefficient due to the limited harvesting of solar irradiation and the complicated surface/interface chemistry. Herein, novel photothermal-enhanced catalysis was achieved in a core-shell hierarchical Cu 7 S 4 nano-heater@ZIF-8 heterostructures via near-infrared localized surface plasmon resonance. Our results demonstrated that both the high surface temperature of the photothermal Cu 7 S 4 core and the close-adjacency of catalytic ZIF-8 shell contributed to the extremely enhanced catalytic activity. Under laser irradiation (1450 nm, 500 mW), the cyclocondensation reaction rate increased 4.5-5.4 fold compared to that of the process at room temperature, in which the 1.6-1.8 fold enhancement was due to the localized heating effect. The simulated sunlight experiments showed a photothermal activation efficiency (PTAE) of 0.07%, further indicating the validity of photothermal catalysis based on the plasmonic semiconductor nanomaterials. More generally, this approach provides a platform to improve reaction activity with efficient utilization of solar energy, which can be readily extended to other green-chemistry processes.

Soil mineralogy and chemistry on Mars - Possible clues from salts and clays in SNC meteorites

NASA Technical Reports Server (NTRS)

Gooding, James L.

1992-01-01

If the shergottite, nakhlite, and chassignite (SNC) meteorites' parent planet is Mars, then the aqueous precipitates found in them imply that oxidizing, water-based solutions may have been chemically active on that planet over the past 200-1300 million yrs. It is suggested that the mixture of aqueous precipitates found in the SNCs furnish a self-consistent model for the bulk elemental composition of surface sediments at the Viking Lander sites. Further mineralogical and stable-isotope studies of the secondary minerals may establish the limits for biological activity over the last 1300 million years of Mars' water-based chemistry.

Effects of topographical and mechanical property alterations induced by oxygen plasma modification on stem cell behavior.

PubMed

Yang, Yong; Kulangara, Karina; Lam, Ruby T S; Dharmawan, Rena; Leong, Kam W

2012-10-23

Polymeric substrates intended for cell culture and tissue engineering are often surface-modified to facilitate cell attachment of most anchorage-dependent cell types. The modification alters the surface chemistry and possibly topography. However, scant attention has been paid to other surface property alterations. In studying oxygen plasma treatment of polydimethylsiloxane (PDMS), we show that oxygen plasma treatment alters the surface chemistry and, consequently, the topography and elasticity of PDMS at the nanoscale level. The elasticity factor has the predominant effect, compared with the chemical and topographical factors, on cell adhesions of human mesenchymal stem cells (hMSCs). The enhanced focal adhesions favor cell spreading and osteogenesis of hMSCs. Given the prevalent use of PDMS in biomedical device construction and cell culture experiments, this study highlights the importance of understanding how oxygen plasma treatment would impact subsequent cell-substrate interactions. It helps explain inconsistency in the literature and guides preparation of PDMS-based biomedical devices in the future.

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

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

Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assessmore » the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.« less

Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

PubMed

Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

2018-05-29

We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

Simulation studies of DNA at the nanoscale: Interactions with proteins, polycations, and surfaces

NASA Astrophysics Data System (ADS)

Elder, Robert M.

Understanding the nanoscale interactions of DNA, a multifunctional biopolymer with sequence-dependent properties, with other biological and synthetic substrates and molecules is essential to advancing these technologies. This doctoral thesis research is aimed at understanding the thermodynamics and molecular-level structure when DNA interacts with proteins, polycations, and functionalized surfaces. First, we investigate the ability of a DNA damage recognition protein (HMGB1a) to bind to anti-cancer drug-induced DNA damage, seeking to explain how HMGB1a differentiates between the drugs in vivo. Using atomistic molecular dynamics simulations, we show that the structure of the drug-DNA molecule exhibits drug- and base sequence-dependence that explains some of the experimentally observed differential recognition of the drugs in various sequence contexts. Then, we show how steric hindrance from the drug decreases the deformability of the drug-DNA molecule, which decreases recognition by the protein, a concept that can be applied to rational drug design. Second, we study how polycation architecture and chemistry affect polycation-DNA binding so as to design optimal polycations for high efficiency gene (DNA) delivery. Using a multiscale computational approach involving atomistic and coarse-grained simulations, we examine how rearranging polylysine from a linear to a grafted architecture, and several aspects of the grafted architecture, affect polycation-DNA binding and the structure of polycation-DNA complexes. Next, going beyond lysine we examine how oligopeptide chemistry and sequence in the grafted architecture affects polycation-DNA binding and find that strategic placement of hydrophobic peptides might be used to tailor binding strength. Third, we study the adsorption and conformations of single-stranded DNA (an amphiphilic biopolymer) on model hydrophilic and hydrophobic surfaces. Short ssDNA oligomers adsorb to both surfaces with similar strength, with the strength of adsorption to the hydrophobic surface depending on the composition of the DNA strands, i.e. purine or pyrimidine bases. Additionally, DNA-surface and DNA-water interactions near the surfaces govern the adsorption. For longer ssDNA oligomers, the effects of surface chemistry and temperature on ssDNA conformations are rather small, but either the hydrophilic surface or increased temperature favor slightly more compact conformations due to energetic and entropic effects, respectively.

Influence of matrix and filler fraction on biofilm formation on the surface of experimental resin-based composites.

PubMed

Ionescu, Andrei; Brambilla, Eugenio; Wastl, Daniel S; Giessibl, Franz J; Cazzaniga, Gloria; Schneider-Feyrer, Sibylle; Hahnel, Sebastian

2015-01-01

The aim of this study was to investigate the impact of resin matrix chemistry and filler fraction on biofilm formation on the surface of experimental resin-based composites (RBCs). Specimens were prepared from eight experimental RBC formulations differing in resin matrix blend (BisGMA/TEGDMA in a 7:3 wt% ratio or UDMA/aliphatic dimethacrylate in a 1:1 wt% ratio) and filler fraction (no fillers; 65 wt% dental glass with an average diameter of 7 or 0.7 µm or 65 wt% SiO2 with an average diameter of 20 nm). Surface roughness, surface free energy, and chemical surface composition were determined; surface topography was visualized using atomic force microscopy. Biofilm formation was simulated under continuous flow conditions for a 48 h period using a monospecies Streptococcus mutans and a multispecies biofilm model. In the monospecies biofilm model, the impact of the filler fraction overruled the influence of the resin matrix, indicating lowest biofilm formation on RBCs with nano-scaled filler particles and those manufactured from the neat resin blends. The multispecies model suggested a more pronounced effect of the resin matrix blend, as significantly higher biofilm formation was identified on RBCs with a UDMA/dimethacrylate matrix blend than on those including a BisGMA/TEGDMA matrix blend but analogous filler fractions. Although significant differences in surface properties between the various materials were identified, correlations between the surface properties and biofilm formation were poor, which highlights the relevance of surface topography and chemistry. These results may help to tailor novel RBC formulations which feature reduced biofilm formation on their surface.

Role of Viscous Dissipative Processes on the Wetting of Textured Surfaces

PubMed Central

Grewal, H. S.; Nam Kim, Hong; Cho, Il-Joo; Yoon, Eui-Sung

2015-01-01

We investigate the role of viscous forces on the wetting of hydrophobic, semi-hydrophobic, and hydrophilic textured surfaces as second-order effects. We show that during the initial contact, the transition from inertia- to viscous-dominant regime occurs regardless of their surface topography and chemistry. Furthermore, we demonstrate the effect of viscosity on the apparent contact angle under quasi-static conditions by modulating the ratio of a water/glycerol mixture and show the effect of viscosity, especially on the semi-hydrophobic and hydrophobic textured substrates. The reason why the viscous force does not affect the apparent contact angle of the hydrophilic surface is explained based on the relationship between the disjoining pressure and surface chemistry. We further propose a wetting model that can predict the apparent contact angle of a liquid drop on a textured substrate by incorporating a viscous force component in the force balance equation. This model can predict apparent contact angles on semi-hydrophobic and hydrophobic textured surfaces exhibiting Wenzel state more accurately than the Wenzel model, indicating the importance of viscous forces in determining the apparent contact angle. The modified model can be applied for estimating the wetting properties of arbitrary engineered surfaces. PMID:26390958

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Influence of EDC/NHS coupling chemistry on stability and cytotoxicity of ZnO nanoparticles modified with proteins

NASA Astrophysics Data System (ADS)

Keleştemur, Seda; Altunbek, Mine; Culha, Mustafa

2017-05-01

The toxicity of ZnO nanoparticles (NPs) is a growing concern due to its increasing use in several products including sunscreens, paints, pigments and ceramics for its antibacterial, antifungal, anti-corrosive and UV filtering properties. The toxicity of ZnO NPs is mostly attributed to the Zn2+ release causing an increase in the intracellular reactive oxygen species (ROS) level. The surface modification with a biocompatible ligand or a polymer can be a good strategy to reduce dissolution based toxicity. In two previous studies, the conflicting results with EDC/NHS coupling chemistry for ZnO NPs were reported. In this study, the same surface modification strategy with an emphasis on the stability of ZnO NPs is clarified. First, the density of -OH groups on the ZnO NPs is increased with hydrogen peroxide (H2O2) treatment, and then a silica coating on the ZnO NPs (Si-ZnO) surface is performed. Finally, a covalent attachment of bovine serum albumin (BSA) on three different concentrations of ZnO-Si is carried out by EDC/NHS coupling chemistry. ZnO NPs have a very high dissolution rate under acidic conditions of EDC/NHS coupling chemistry as determined from the ICP-MS analysis. In addition, the amount of ZnO NPs in coupling reaction has an important effect on the dissolution rate of Zn2+ and dependently BSA attached on the ZnO NP surfaces. Finally, the cytotoxicity of the BSA modified Si-ZnO NPs on human lung cancer (A549) and human skin fibroblast (HSF) is evaluated. Although an increased association of BSA modified ZnO NPs with cells was observed, the modification significantly decreased their cytotoxicity. This can be explained with the decreased active surface area of ZnO NPs with the surface modification. However, an increase in the mitochondrial depolarization and ROS production was observed depending on the amount of BSA coverage.

Phage as a Genetically Modifiable Supramacromolecule in Chemistry, Materials and Medicine.

PubMed

Cao, Binrui; Yang, Mingying; Mao, Chuanbin

2016-06-21

Filamentous bacteriophage (phage) is a genetically modifiable supramacromolecule. It can be pictured as a semiflexible nanofiber (∼900 nm long and ∼8 nm wide) made of a DNA core and a protein shell with the former genetically encoding the latter. Although phage bioengineering and phage display techniques were developed before the 1990s, these techniques have not been widely used for chemistry, materials, and biomedical research from the perspective of supramolecular chemistry until recently. Powered by our expertise in displaying a foreign peptide on its surface through engineering phage DNA, we have employed phage to identify target-specific peptides, construct novel organic-inorganic nanohybrids, develop biomaterials for disease treatment, and generate bioanalytical methods for disease diagnosis. Compared with conventional biomimetic chemistry, phage-based supramolecular chemistry represents a new frontier in chemistry, materials science, and medicine. In this Account, we introduce our recent successful efforts in phage-based supramolecular chemistry, by integrating the unique nanofiber-like phage structure and powerful peptide display techniques into the fields of chemistry, materials science, and medicine: (1) successfully synthesized and assembled silica, hydroxyapatite, and gold nanoparticles using phage templates to form novel functional materials; (2) chemically introduced azo units onto the phage to form photoresponsive functional azo-phage nanofibers via a diazotization reaction between aromatic amino groups and the tyrosine residues genetically displayed on phage surfaces; (3) assembled phage into 2D films for studying the effects of both biochemical (the peptide sequences displayed on the phages) and biophysical (the topographies of the phage films) cues on the proliferation and differentiation of mesenchymal stem cells (MSCs) and induced pluripotent stem cells (iPSCs) and identified peptides and topographies that can induce their osteogenic differentiation; (4) discovered that phage could induce angiogenesis and osteogenesis for MSC-based vascularized bone regeneration; (5) identified novel breast cancer cell-targeting and MSC-targeting peptides and used them to significantly improve the efficiency of targeted cancer therapy and MSC-based gene delivery, respectively; (6) employed engineered phage as a probe to achieve ultrasensitive detection of biomarkers from serum of human patients for disease diagnosis; and (7) constructed centimeter-scale 3D multilayered phage assemblies with the potential application as scaffolds for bone regeneration and functional device fabrication. Our findings demonstrated that phage is indeed a very powerful supramacromolecule suitable for not only developing novel nanostructures and biomaterials but also advancing important fields in biomedicine, including molecular targeting, cancer diagnosis and treatment, drug and gene delivery, stem cell fate direction, and tissue regeneration. Our successes in exploiting phage in chemistry, materials, and medicine suggest that phage itself is nontoxic at the cell level and can be safely used for detecting biomarkers in vitro. Moreover, although we have demonstrated successful in vivo tissue regeneration induced by phage, we believe future studies are needed to evaluate the in vivo biodistribution and potential risks of the phage-based biomaterials.

Phage as a Genetically Modifiable Supramacromolecule in Chemistry, Materials and Medicine

PubMed Central

Cao, Binrui; Yang, Mingying; Mao, Chuanbin

2016-01-01

CONSPECTUS Filamentous bacteriophage (phage) is a genetically modifiable supramacromolecule. It can be pictured as a semiflexible nanofiber (~900 nm long and ~8 nm wide) made of a DNA core and a protein shell with the former genetically encoding the latter. Although phage bioengineering and phage display techniques were developed before the 1990s, these techniques have not been widely used for chemistry, materials, and biomedical research from the perspective of supramolecular chemistry until recently. Powered by our expertise in displaying a foreign peptide on its surface through engineering phage DNA, we have employed phage to identify target-specific peptides, construct novel organic–inorganic nanohybrids, develop biomaterials for disease treatment, and generate bioanalytical methods for disease diagnosis. Compared with conventional biomimetic chemistry, phage-based supramolecular chemistry represents a new frontier in chemistry, materials science, and medicine. In this Account, we introduce our recent successful efforts in phage-based supramolecular chemistry, by integrating the unique nanofiber-like phage structure and powerful peptide display techniques into the fields of chemistry, materials science, and medicine: (1) successfully synthesized and assembled silica, hydroxyapatite, and gold nanoparticles using phage templates to form novel functional materials; (2) chemically introduced azo units onto the phage to form photoresponsive functional azo-phage nanofibers via a diazotization reaction between aromatic amino groups and the tyrosine residues genetically displayed on phage surfaces; (3) assembled phage into 2D films for studying the effects of both biochemical (the peptide sequences displayed on the phages) and biophysical (the topographies of the phage films) cues on the proliferation and differentiation of mesenchymal stem cells (MSCs) and induced pluripotent stem cells (iPSCs) and identified peptides and topographies that can induce their osteogenic differentiation; (4) discovered that phage could induce angiogenesis and osteogenesis for MSC-based vascularized bone regeneration; (5) identified novel breast cancer cell-targeting and MSC-targeting peptides and used them to significantly improve the efficiency of targeted cancer therapy and MSC-based gene delivery, respectively; (6) employed engineered phage as a probe to achieve ultrasensitive detection of biomarkers from serum of human patients for disease diagnosis; and (7) constructed centimeter-scale 3D multilayered phage assemblies with the potential application as scaffolds for bone regeneration and functional device fabrication. Our findings demonstrated that phage is indeed a very powerful supramacromolecule suitable for not only developing novel nanostructures and biomaterials but also advancing important fields in biomedicine, including molecular targeting, cancer diagnosis and treatment, drug and gene delivery, stem cell fate direction, and tissue regeneration. Our successes in exploiting phage in chemistry, materials, and medicine suggest that phage itself is nontoxic at the cell level and can be safely used for detecting biomarkers in vitro. Moreover, although we have demonstrated successful in vivo tissue regeneration induced by phage, we believe future studies are needed to evaluate the in vivo biodistribution and potential risks of the phage-based biomaterials. PMID:27153341

ATR-FTIR Spectroscopy in the Undergraduate Chemistry Laboratory: Part II--A Physical Chemistry Laboratory Experiment on Surface Adsorption

ERIC Educational Resources Information Center

Schuttlefield, Jennifer D.; Larsen, Sarah C.; Grassian, Vicki H.

2008-01-01

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy is a useful technique for measuring the infrared spectra of solids and liquids as well as probing adsorption on particle surfaces. The use of FTIR-ATR spectroscopy in organic and inorganic chemistry laboratory courses as well as in undergraduate research was presented…

Catalase coupled gold nanoparticles: Comparison between carbodiimide and biotin-streptavidin methods

PubMed Central

Chirra, Hariharasudhan D.; Sexton, Travis; Biswal, Dipti; Hersh, Louis B.; Hilt, J. Zach

2011-01-01

The use of proteins for therapeutic applications requires the protein to maintain sufficient activity for the period of in vivo treatment. Many proteins exhibit a short half-life in vivo and, thus, require delivery systems for them to be applied as therapeutics. The relative biocompatibility and the ability to form functionalized bioconjugates via simple chemistry make gold nanoparticles excellent candidates as protein delivery systems. Herein, two protocols for coupling proteins to gold nanoparticles were compared. In the first, the strong biomolecular binding between biotin and streptavidin was used to couple catalase to the surface of gold nanoparticles. In the second protocol, the formation of an amide bond between carboxylic acid coated gold nanoparticles and free surface amines of catalase using carbodiimide chemistry was performed. The stability and kinetics of the different steps involved in these protocols were studied using UV-Visible spectroscopy, dynamic light scattering, and transmission electron microscopy. The addition of mercaptoundecanoic acid in conjugation with (N-(6-(biotinamido)hexyl)-3′-(2′-pyridyldithio)-propionamide increased the stability of biotinylated gold nanoparticles. Although the carbodiimide chemistry based bioconjugation approach exhibited a decrease in catalase activity, the carbodiimide chemistry based bioconjugation approach resulted in more active catalase per gold nanoparticle compared to that of mercaptoundecanoic acid stabilized biotinylated gold nanoparticles. Both coupling protocols resulted in gold nanoparticles loaded with active catalase. Thus, these gold nanoparticle systems and coupling protocols represent promising methods for the application of gold nanoparticles for protein delivery. PMID:21232642

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

NASA Astrophysics Data System (ADS)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

Nitrogen Oxides in the Nocturnal Boundary Layer: Chemistry of Nitrous Acid (HONO) and the Nitrate Radical (N03)

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

Jochen Stutz

Summary Chemical processes occurring at night in the lowest part of the urban atmosphere, the so called nocturnal boundary layer (NBL), can influence the composition of the atmosphere during the night as well as the following day. They may impact the budgets of some of the most important pollutants, such as ozone and nitrogen oxides, as well as influence size and composition of particular matter. Few studies have thus far concentrated on the nocturnal chemistry of the urban NBL, most likely due to the strong influence of vertical transport and mixing, which requires the measurement of trace gas profiles insteadmore » of simple point observations. Motivated by our lack of observations and understanding of nocturnal chemistry, the focus of this project was the study of the vertical distribution of trace gases and the altitude dependence of nocturnal chemistry under polluted conditions through field observations and modeling studies. The analysis of three field experiments (TEXAQS, Houston, 2000; Phoenix Sunrise Ozone Experiment, 2001; NAPOX, Boston, 2002), two of which were performed in this project, showed that ozone concentrations typically increase with height in the lowest 150m, while NO2 typically decreases. NO3, the dominant nocturnal radical species, showed much higher concentrations in the upper part of the NBL, and was often not present at the ground. With the help of a one-dimensional chemical transport model, developed in this project, we found that the interaction of ground emissions of NOx and hydrocarbons, together with their vertical transport, is responsible for the vertical profiles. The dominant chemical reactions influencing ozone, NO2 and NO3 are the reaction of ozone and NO3 with freshly emitted NO. Sensitivity studies with our model showed that the magnitude of the trace gas gradients depend both on the emission rates and the vertical stability of the NBL. Observations and model analysis clearly show that nocturnal chemistry in urban areas is altitude dependent. Measurements at one altitude, for example at the ground, where most air quality monitoring stations are located, are not representative for the rest of the NBL. Our model also revealed that radical chemistry is, in general, altitude dependent at night. We distinguish three regions: an unreactive, NO rich, ground layer; an upper, O3 and NO3 dominated layer, and a reactive mixing layer, where RO2 radicals are mixed from aloft with NO from the ground. In this reactive layer an active radical chemistry and elevated OH radical levels can be found. The downward transport of N2O5 and HO2NO2, followed by their thermal decay, was also identified as a radical source in this layer. Our observations also gave insight into the formation of HONO in the NBL. Based on our field experiments we were able to show that the NO2 to HONO conversion was relative humidity dependent. While this fact was well known, we found that it is most likely the uptake of HONO onto surfaces which is R.H. dependent, rather than the NO2 to HONO conversion. This finding led to the proposal of a new NO2 to HONO conversion mechanism, which is based on solid physical chemical principles. Noteworthy is also the observation of enhanced NO2 to HONO conversion during a dust storm event in Phoenix. The final activity in our project investigated the influence of the urban canopy, i.e. building walls and surfaces, on nocturnal chemistry. For the first time the surface area of a city was determined based on a Geographical Information System database of the city of Santa Monica. The surface to volume areas found in this study showed that, in the 2 lower part of the NBL, buildings provide a much larger surface area than the aerosol. In addition, buildings take up a considerable amount of the volume near the ground. The expansion of our model and sensitivity studies based on the Santa Monica data revealed that the surface area of buildings considerably influences HONO levels in urban areas. The volume reduction leads to a decrease of O3 and an increase of NO2 near the ground due to the stronger impact of NO emissions. Our project shows that the urban canopy should be included in future air quality models to better represent nocturnal chemistry. This project has considerably advanced our understanding of the chemistry of the urban nocturnal boundary layer. The results of this project have implications for air quality studies in the urban nocturnal boundary layer. The study has also identified new questions on nocturnal processes, which we will continue to address through other projects.« less

Computer Series, 115.

ERIC Educational Resources Information Center

Birk, James P., Ed.

1990-01-01

Reviewed are six computer programs which may be useful in teaching college level chemistry. Topics include dynamic data storage in FORTRAN, "KC?DISCOVERER," pH of acids and bases, calculating percent boundary surfaces for orbitals, and laboratory interfacing with PT Nomograph for the Macintosh. (CW)

Effects of surface chemistry on hot corrosion life

NASA Technical Reports Server (NTRS)

Fryxell, R. E.; Gupta, B. K.

1984-01-01

Hot corrosion life prediction methodology based on a combination of laboratory test data and field service turbine components, which show evidence of hot corrosion, were examined. Components were evaluated by optical metallography, scanning electron microscopy (SEM), and electron micropulse (EMP) examination.

[60]Fullerene-based monolayers as neuroprotective biocompatible hybrid materials.

PubMed

Giust, Davide; Albasanz, José Luis; Martín, Mairena; Marega, Riccardo; Delforge, Arnaud; Bonifazi, Davide

2011-10-14

Here we report on the surface immobilization of redox-active [60]fullerene derivatives and the consequent neuroprotective effects toward l-glutamate induced excitotoxicity in human derived undifferentiated neuroblastoma cells. This journal is © The Royal Society of Chemistry 2011

Rapid in situ generation of two patterned chemoselective surface chemistries from a single hydroxy-terminated surface using controlled microfluidic oxidation.

PubMed

Pulsipher, Abigail; Westcott, Nathan P; Luo, Wei; Yousaf, Muhammad N

2009-06-10

In this work, we develop a new, rapid and inexpensive method to generate spatially controlled aldehyde and carboxylic acid surface groups by microfluidic oxidation of 11-hydroxyundecylphosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO) surfaces. SAMs are activated and patterned using a reversibly sealable, elastomeric polydimethylsiloxane cassette, fabricated with preformed micropatterns by soft lithography. By flowing the mild oxidant pyridinium chlorochromate through the microchannels, only selected areas of the SAM are chemically altered. This microfluidic oxidation strategy allows for ligand immobilization by two chemistries originating from a single SAM composition. ITO is robust, conductive, and transparent, making it an ideal platform for studying interfacial interactions. We display spatial control over the immobilization of a variety of ligands on ITO and characterize the resulting oxime and amide linkages by electrochemistry, X-ray photoelectron spectroscopy, contact angle, fluorescence microscopy, and atomic force microscopy. This general method may be used with many other materials to rapidly generate patterned and tailored surfaces for studies ranging from molecular electronics to biospecific cell-based assays and biomolecular microarrays.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of `polar ice' mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm `carbonyl' absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes.

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

NASA Astrophysics Data System (ADS)

Rahm, Martin; Lunine, Jonathan I.; Usher, David A.; Shalloway, David

2016-07-01

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini-Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N-H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

PubMed Central

Rahm, Martin; Lunine, Jonathan I.; Usher, David A.; Shalloway, David

2016-01-01

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini–Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N–H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan. PMID:27382167

Metal-composite adhesion based on diazonium chemistry.

PubMed

Oweis, Yara; Alageel, Omar; Kozak, Paige; Abdallah, Mohamed-Nur; Retrouvey, Jean-Marc; Cerruti, Marta; Tamimi, Faleh

2017-11-01

Composite resins do not adhere well to dental alloys. This weak bond can result in failure at the composite-metal interface in fixed dental prostheses and orthodontic brackets. The aim of this study was to develop a new adhesive, based on diazonium chemistry, to facilitate chemical bonding between dental alloys and composite resin. Samples of two types of dental alloys, stainless steel and cobalt chromium were primed with a diazonium layer in order to create a surface coating favorable for composite adhesion. Untreated metal samples served as controls. The surface chemical composition of the treated and untreated samples was analyzed by X-ray photoelectron spectroscopy (XPS) and the tensile strength of the bond with composite resin was measured. The diazonium adhesive was also tested for shear bond strength between stainless steel orthodontic brackets and teeth. XPS confirmed the presence of a diazonium coating on the treated metals. The coating significantly increased the tensile and shear bond strengths by three and four folds respectively between the treated alloys and composite resin. diazonium chemistry can be used to develop composite adhesives for dental alloys. Diazonium adhesion can effectively achieve a strong chemical bond between dental alloys and composite resin. This technology can be used for composite repair of fractured crowns, for crown cementation with resin based cements, and for bracket bonding. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

DOE PAGES

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; ...

2017-01-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

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

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

NASA Astrophysics Data System (ADS)

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; Berg, Larry K.; Fast, Jerome D.; Easter, Richard C.; Shrivastava, Manish; Thomas, Jennie L.

2017-10-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain-Fritsch + Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces.

PubMed

Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M D; Pike, Andrew R; Horrocks, Benjamin R; Fulton, David A; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A

2017-01-27

Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ∼ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces

NASA Astrophysics Data System (ADS)

Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M. D.; Pike, Andrew R.; Horrocks, Benjamin R.; Fulton, David A.; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A.

2017-01-01

Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ˜ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

Dragonfly: Investigating the Surface Composition of Titan

NASA Technical Reports Server (NTRS)

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

Impact of ship emissions on air pollution and AOD over North Atlantic and European Arctic

NASA Astrophysics Data System (ADS)

Kaminski, Jacek W.; Struzewska, Joanna; Jefimow, Maciej; Durka, Pawel

2016-04-01

The iAREA project is combined of experimental and theoretical research in order to contribute to the new knowledge on the impact of absorbing aerosols on the climate system in the European Arctic (http://www.igf.fuw.edu.pl/iAREA). A tropospheric chemistry model GEM-AQ (Global Environmental Multiscale Air Quality) was used as a computational tool. The core of the model is based on a weather prediction model with environmental processes (chemistry and aerosols) implanted on-line and are interactive (i.e. providing feedback of chemistry on radiation and dynamics). The numerical grid covered the Euro-Atlantic region with the resolution of 50 km. Emissions developed by NILU in the ECLIPSE project was used (Klimont et al., 2013). The model was run for two 1-year scenarios. 2014 was chosen as a base year for simulations and analysis. Scenarios include a base run with most up-to-date emissions and a run without maritime emissions. The analysis will focus on the contribution of maritime emissions on levels of particulate matter and gaseous pollutants over the European Arctic, North Atlantic and coastal areas. The annual variability will be assessed based on monthly mean near-surface concentration fields. Analysis of shipping transport on near-surface air pollution over the Euro-Atlantic region will be assessed for ozone, NO2, SO2, CO, PM10, PM2.5. Also, a contribution of ship emissions to AOD will be analysed.

Titan's atmosphere and climate

NASA Astrophysics Data System (ADS)

Hörst, S. M.

2017-03-01

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

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

PubMed

Szakal, Christopher; McCarthy, James A; Ugelow, Melissa S; Konicek, Andrew R; Louis, Kacie; Yezer, Benjamin; Herzing, Andrew A; Hamers, Robert J; Holbrook, R David

2012-07-01

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.

The influence of EI-21 redox ion-exchange resins on the secondary-coolant circuit water chemistry of vehicular nuclear power installations

NASA Astrophysics Data System (ADS)

Moskvin, L. N.; Rakov, V. T.

2015-06-01

The results obtained from testing the secondary-coolant circuit water chemistry of full-scale land-based prototype bench models of vehicular nuclear power installations equipped with water-cooled water-moderated and liquid-metal reactor plants are presented. The influence of copper-containing redox ionexchange resins intended for chemically deoxygenating steam condensate on the working fluid circulation loop's water chemistry is determined. The influence of redox ion-exchange resins on the water chemistry is evaluated by generalizing an array of data obtained in the course of extended monitoring using the methods relating to physicochemical analysis of the quality of condensate-feedwater path media and the methods relating to metallographic analysis of the state of a faulty steam generator's tube system surfaces. The deoxygenating effectiveness of the normal state turbine condensate vacuum deaeration system is experimentally determined. The refusal from applying redox ion-exchange resins in the condensate polishing ion-exchange filters is formulated based on the obtained data on the adverse effect of copper-containing redox ionexchange resins on the condensate-feedwater path water chemistry and based on the data testifying a sufficient effect from using the normal state turbine condensate vacuum deaeration system. Data on long-term operation of the prototype bench model of a vehicular nuclear power installation without subjecting the turbine condensate to chemical deoxygenation are presented.

Colloidal characterization of ultrafine silicon carbide and silicon nitride powders

NASA Technical Reports Server (NTRS)

Whitman, Pamela K.; Feke, Donald L.

1986-01-01

The effects of various powder treatment strategies on the colloid chemistry of aqueous dispersions of silicon carbide and silicon nitride are examined using a surface titration methodology. Pretreatments are used to differentiate between the true surface chemistry of the powders and artifacts resulting from exposure history. Silicon nitride powders require more extensive pretreatment to reveal consistent surface chemistry than do silicon carbide powders. As measured by titration, the degree of proton adsorption from the suspending fluid by pretreated silicon nitride and silicon carbide powders can both be made similar to that of silica.

On the use of SPM to probe the interplay between polymer surface chemistry and polymer surface mechanics

NASA Astrophysics Data System (ADS)

Brogly, Maurice; Noel, Olivier; Awada, Houssein; Castelein, Gilles

2007-03-01

Adhesive properties of a polymer surface results from the complex contribution of surface chemistry and activation of sliding and dissipating mechanisms within the polymer surface layer. The purpose of this study is to dissociate the different contributions (chemical and mechanical) included in an AFM force-distance curve in order to establish relationships between the surface viscoelastic properties of the polymer, the surface chemistry of functionalized polymer surfaces and the adhesive forces, as determined by C-AFM experiments. Indeed we are interested in the measurements of local attractive or adhesive forces in AFM contact mode, of controlled chemical and mechanical model substrates. In order to investigate the interplay between mechanical or viscoelastic mechanisms and surface chemistry during the tip - polymer contact, we achieved force measurements on model PDMS polymer networks, whose surfaces are chemically controlled with the same functional groups as before (silicon substrates). On the basis of AFM nano-indentation experiments, surface Young moduli have been determined. The results show that the viscoelastic contribution is dominating in the adhesion force measurement. We propose an original model, which express the local adhesion force to the energy dissipated within the contact and the surface properties of the material (thermodynamic work of adhesion). Moreover we show that the dissipation function is related to Mc, the mass between crosslinks of the network.

Space-Based Diagnosis of Surface Ozone Sensitivity to Anthropogenic Emissions

NASA Technical Reports Server (NTRS)

Martin, Randall V.; Fiore, Arlene M.; VanDonkelaar, Aaron

2004-01-01

We present a novel capability in satellite remote sensing with implications for air pollution control strategy. We show that the ratio of formaldehyde columns to tropospheric nitrogen dioxide columns is an indicator of the relative sensitivity of surface ozone to emissions of nitrogen oxides (NO(x) = NO + NO2) and volatile organic compounds (VOCs). The diagnosis from these space-based observations is highly consistent with current understanding of surface ozone chemistry based on in situ observations. The satellite-derived ratios indicate that surface ozone is more sensitive to emissions of NO(x) than of VOCs throughout most continental regions of the Northern Hemisphere during summer. Exceptions include Los Angeles and industrial areas of Germany. A seasonal transition occurs in the fall when surface ozone becomes less sensitive to NOx and more sensitive to VOCs.

Chemistry of atmosphere-surface interactions on Venus and Mars

NASA Astrophysics Data System (ADS)

Fegley, Bruce, Jr.; Treiman, Allan H.

Earth-based, earth-orbital, and spacecraft observational data are used in the present evaluation of Venus atmosphere-surface interactions to quantitatively characterize the reactions between C, H, S, Cl, F, and N gases and plausible surface minerals. Calculation results are used to predict stable minerals and mineral assemblages on the Venus surface, in order to ascertain which (if any) of the atmospheric gases are buffeted by mineral assemblages. Chemical equilibrium calculations using extant thermodynamic data on scapolite minerals predict that carbonate-bearing scapolite and sulfate meionite are unstable on the surface of Venus, while chloride-bearing scapolite is stable.

Surface chemistry driven actuation in nanoporous gold

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

Biener, J; Wittstock, A; Zepeda-Ruiz, L

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry driven actuation can be realized in high surface area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes in the order of a few tenths of a percent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into amore » mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.« less

Molecular Rotors

DTIC Science & Technology

2006-10-31

microwave signal processing components, and micro-fluidic devices. The projected involved the preparation, surface mounting, and characterization of...Guisinger, R. Basu, and M. C. Hersam, “Atomic-level characterization and control of free radical surface chemistry using scanning tunneling microscopy...Basu, and M. C. Hersam, “Atomic level characterization and control of organosilicon surface chemistry using scanning tunneling microscopy,” presented

Surface chemistry and moisture sorption properties of wood coated with multifunctional alkoxysilanes by sol-gel process

Treesearch

Mandla A. Tshabalala; Peter Kingshott; Mark R. VanLandingham; David Plackett

2003-01-01

Sol-gel surface deposition of a hydrophobic polysiloxane coating on wood was accomplished by using a mixture of a low molecular weight multifunctional alkoxysilane, methyltrimethoxysilane (MTMOS), and a high molecular weight multifunctional alkoxysilane, hexadecyltrimethoxysilane (HDTMOS). Investigation of the surface chemistry and morphology of the wood specimens by...

Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

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

Yoon, Yeohoon; Du, Yingge; Garcia, Juan C.

2015-02-02

Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absencemore » of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas. We also postulate that the entire nearest subsurface region could be voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.« less

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

PubMed

Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

2016-07-01

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Hydrofluoric Acid Etching Time on Titanium Topography, Chemistry, Wettability, and Cell Adhesion

PubMed Central

Zahran, R.; Rosales Leal, J. I.; Rodríguez Valverde, M. A.; Cabrerizo Vílchez, M. A.

2016-01-01

Titanium implant surface etching has proven an effective method to enhance cell attachment. Despite the frequent use of hydrofluoric (HF) acid, many questions remain unresolved, including the optimal etching time and its effect on surface and biological properties. The objective of this study was to investigate the effect of HF acid etching time on Ti topography, surface chemistry, wettability, and cell adhesion. These data are useful to design improved acid treatment and obtain an improved cell response. The surface topography, chemistry, dynamic wetting, and cell adhesiveness of polished Ti surfaces were evaluated after treatment with HF acid solution for 0, 2; 3, 5, 7, or 10 min, revealing a time-dependent effect of HF acid on their topography, chemistry, and wetting. Roughness and wetting increased with longer etching time except at 10 min, when roughness increased but wetness decreased. Skewness became negative after etching and kurtosis tended to 3 with longer etching time. Highest cell adhesion was achieved after 5–7 min of etching time. Wetting and cell adhesion were reduced on the highly rough surfaces obtained after 10-min etching time. PMID:27824875

Controlling nonspecific protein adsorption in a plug-based microfluidic system by controlling interfacial chemistry using fluorous-phase surfactants.

PubMed

Roach, L Spencer; Song, Helen; Ismagilov, Rustem F

2005-02-01

Control of surface chemistry and protein adsorption is important for using microfluidic devices for biochemical analysis and high-throughput screening assays. This paper describes the control of protein adsorption at the liquid-liquid interface in a plug-based microfluidic system. The microfluidic system uses multiphase flows of immiscible fluorous and aqueous fluids to form plugs, which are aqueous droplets that are completely surrounded by fluorocarbon oil and do not come into direct contact with the hydrophobic surface of the microchannel. Protein adsorption at the aqueous-fluorous interface was controlled by using surfactants that were soluble in fluorocarbon oil but insoluble in aqueous solutions. Three perfluorinated alkane surfactants capped with different functional groups were used: a carboxylic acid, an alcohol, and a triethylene glycol group that was synthesized from commercially available materials. Using complementary methods of analysis, adsorption was characterized for several proteins (bovine serum albumin (BSA) and fibrinogen), including enzymes (ribonuclease A (RNase A) and alkaline phosphatase). These complementary methods involved characterizing adsorption in microliter-sized droplets by drop tensiometry and in nanoliter plugs by fluorescence microscopy and kinetic measurements of enzyme catalysis. The oligoethylene glycol-capped surfactant prevented protein adsorption in all cases. Adsorption of proteins to the carboxylic acid-capped surfactant in nanoliter plugs could be described by using the Langmuir model and tensiometry results for microliter drops. The microfluidic system was fabricated using rapid prototyping in poly(dimethylsiloxane) (PDMS). Black PDMS microfluidic devices, fabricated by curing a suspension of charcoal in PDMS, were used to measure the changes in fluorescence intensity more sensitively. This system will be useful for microfluidic bioassays, enzymatic kinetics, and protein crystallization, because it does not require surface modification during fabrication to control surface chemistry and protein adsorption.

Surface Functionalization of Exosomes Using Click Chemistry

PubMed Central

2015-01-01

A method for conjugation of ligands to the surface of exosomes was developed using click chemistry. Copper-catalyzed azide alkyne cycloaddition (click chemistry) is ideal for biocojugation of small molecules and macromolecules to the surface of exosomes, due to fast reaction times, high specificity, and compatibility in aqueous buffers. Exosomes cross-linked with alkyne groups using carbodiimide chemistry were conjugated to a model azide, azide-fluor 545. Conjugation had no effect on the size of exosomes, nor was there any change in the extent of exosome adherence/internalization with recipient cells, suggesting the reaction conditions were mild on exosome structure and function. We further investigated the extent of exosomal protein modification with alkyne groups. Using liposomes with surface alkyne groups of a similar size and concentration to exosomes, we estimated that approximately 1.5 alkyne groups were present for every 150 kDa of exosomal protein. PMID:25220352

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Elementary photocatalytic chemistry on TiO2 surfaces.

PubMed

Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

2016-07-07

Photocatalytic hydrogen production and pollutant degradation provided both great opportunities and challenges in the field of sustainable energy and environmental science. Over the past few decades, we have witnessed fast growing interest and efforts in developing new photocatalysts, improving catalytic efficiency and exploring the reaction mechanism at the atomic and molecular levels. Owing to its relatively high efficiency, nontoxicity, low cost and high stability, TiO2 becomes one of the most extensively investigated metal oxides in semiconductor photocatalysis. Fundamental studies on well characterized single crystals using ultrahigh vacuum based surface science techniques could provide key microscopic insight into the underlying mechanism of photocatalysis. In this review, we have summarized recent progress in the photocatalytic chemistry of hydrogen, water, oxygen, carbon monoxide, alcohols, aldehydes, ketones and carboxylic acids on TiO2 surfaces. We focused this review mainly on the rutile TiO2(110) surface, but some results on the rutile TiO2(011), anatase TiO2(101) and (001) surfaces are also discussed. These studies provided fundamental insights into surface photocatalysis as well as stimulated new investigations in this exciting field. At the end of this review, we have discussed how these studies can help us to develop new photocatalysis models.

Low temperature surface chemistry and nanostructures

NASA Astrophysics Data System (ADS)

Sergeev, G. B.; Shabatina, T. I.

2002-03-01

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.

Emphasizing the role of surface chemistry on hydrophobicity and cell adhesion behavior of polydimethylsiloxane/TiO2 nanocomposite films.

PubMed

Yousefi, Seyedeh Zahra; Tabatabaei-Panah, Pardis-Sadat; Seyfi, Javad

2018-07-01

Improving the bioinertness of materials is of great importance for developing biomedical devices that contact human tissues. The main goal of this study was to establish correlations among surface morphology, roughness and chemistry with hydrophobicity and cell adhesion in polydimethylsiloxane (PDMS) nanocomposites loaded with titanium dioxide (TiO 2 ) nanoparticles. Firstly, wettability results showed that the nanocomposite loaded with 30 wt.% of TiO 2 exhibited a superhydrophobic behavior; however, the morphology and roughness analysis proved that there was no discernible difference between the surface structures of samples loaded with 20 and 30 wt.% of nanoparticles. Both cell culture and MTT assay experiments showed that, despite the similarity between the surface structures, the sample loaded with 30 wt.% nanoparticles exhibits the greatest reduction in the cell viability (80%) as compared with the pure PDMS film. According to the X-ray photoelectron spectroscopy results, the remarkable reduction in cell viability of the superhydrophobic sample could be majorly attributed to the role of surface chemistry. The obtained results emphasize the importance of adjusting the surface properties especially surface chemistry to gain the optimum cell adhesion behavior. Copyright © 2018 Elsevier B.V. All rights reserved.

Process of welding gamma prime-strengthened nickel-base superalloys

DOEpatents

Speigel, Lyle B.; White, Raymond Alan; Murphy, John Thomas; Nowak, Daniel Anthony

2003-11-25

A process for welding superalloys, and particularly articles formed of gamma prime-strengthened nickel-base superalloys whose chemistries and/or microstructures differ. The process entails forming the faying surface of at least one of the articles to have a cladding layer of a filler material. The filler material may have a composition that is different from both of the articles, or the same as one of the articles. The cladding layer is machined to promote mating of the faying surfaces, after which the faying surfaces are mated and the articles welded together. After cooling, the welded assembly is free of thermally-induced cracks.

Complex amine-based reagents

NASA Astrophysics Data System (ADS)

Suslov, S. Yu.; Kirilina, A. V.; Sergeev, I. A.; Zezyulya, T. V.; Sokolova, E. A.; Eremina, E. V.; Timofeev, N. V.

2017-03-01

Amines for a long time have been applied to maintaining water chemistry conditions (WCC) at power plants. However, making use of complex reagents that are the mixture of neutralizing and the filmforming amines, which may also contain other organic components, causes many disputes. This is mainly due to lack of reliable information about these components. The protective properties of any amine with regard to metal surfaces depend on several factors, which are considered in this article. The results of applying complex reagents to the protection of heating surfaces in industrial conditions and estimated behavior forecasts for various reagents under maintaining WCC on heat-recovery boilers with different thermal circuits are presented. The case of a two-drum heat-recovery boiler with in-line drums was used as an example, for which we present the calculated pH values for various brands of reagents under the same conditions. Work with different reagent brands and its analysis enabled us to derive a composition best suitable for the conditions of their practical applications in heat-recovery boilers at different pressures. Testing the new amine reagent performed at a CCPP power unit shows that this reagent is an adequate base for further development of reagents based on amine compounds. An example of testing a complex reagent is shown created with the participation of the authors within the framework the program of import substitution and its possible use is demonstrated for maintaining WCC of power-generating units of combined-cycle power plants (CCPP) and TPP. The compliance of the employed reagents with the standards of water chemistry conditions and protection of heating surfaces were assessed. The application of amine-containing reagents at power-generating units of TPP makes it possible to solve complex problems aimed at ensuring the sparing cleaning of heating surfaces from deposits and the implementation of conservation and management of water chemistry condition on the TPP equipment.

Molecular-level characterization of the structure and the surface chemistry of periodic mesoporous organosilicates using DNP-surface enhanced NMR spectroscopy.

PubMed

Grüning, Wolfram R; Rossini, Aaron J; Zagdoun, Alexandre; Gajan, David; Lesage, Anne; Emsley, Lyndon; Copéret, Christophe

2013-08-28

We present the molecular level characterization of a phenylpyridine-based periodic mesoporous organosilicate and its post-functionalized organometallic derivatives through the fast acquisition of high quality natural isotopic abundance 1D (13)C, (15)N, and (29)Si and 2D (1)H-(13)C and (1)H-(29)Si solid-state NMR spectra enhanced with dynamic nuclear polarization.

Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Loeffler, Mark J.

2012-01-01

Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

In vitro toxicity of carbon nanotubes, nano-graphite and carbon black, similar impacts of acid functionalization.

PubMed

Figarol, Agathe; Pourchez, Jérémie; Boudard, Delphine; Forest, Valérie; Akono, Céline; Tulliani, Jean-Marc; Lecompte, Jean-Pierre; Cottier, Michèle; Bernache-Assollant, Didier; Grosseau, Philippe

2015-12-25

Carbon nanotubes (CNT) and nano-graphite (NG) are graphene-based nanomaterials which share exceptional physicochemical properties, but whose health impacts are unfortunately still not well understood. On the other hand, carbon black (CB) is a conventional and widely studied material. The comparison of these three carbon-based nanomaterials is thus of great interest to improve our understanding of their toxicity. An acid functionalization was carried out on CNT, NG and CB so that, after a thorough characterization, their impacts on RAW 264.7 macrophages could be compared for a similar surface chemistry (15 to 120 μg·mL(-1) nanomaterials, 90-min to 24-h contact). Functionalized nanomaterials triggered a weak cytotoxicity similar to the pristine nanomaterials. Acid functionalization increased the pro-inflammatory response except for CB which did not trigger any TNF-α production before or after functionalization, and seemed to strongly decrease the oxidative stress. The toxicological impact of acid functionalization appeared thus to follow a similar trend whatever the carbon-based nanomaterial. At equivalent dose expressed in surface and equivalent surface chemistry, the toxicological responses from murine macrophages to NG were higher than for CNT and CB. It seemed to correspond to the hypothesis of a platelet and fiber paradigm. Copyright © 2015. Published by Elsevier Ltd.

A plant derived multifunctional tool for nanobiotechnology based on Tomato bushy stunt virus.

PubMed

Grasso, Simone; Lico, Chiara; Imperatori, Francesca; Santi, Luca

2013-06-01

Structure, size, physicochemical properties and production strategies make many plant viruses ideal protein based nanoscaffolds, nanocontainers and nano-building blocks expected to deliver a multitude of applications in different fields such as biomedicine, pharmaceutical chemistry, separation science, catalytic chemistry, crop pest control and biomaterials science. Functionalization of viral nanoparticles through modification by design of their external and internal surfaces is essential to fully exploit the potentiality of these objects. In the present paper we describe the development of a plant derived multifunctional tool for nanobiotechnology based on Tomato bushy stunt virus. We demonstrate the ability of this system to remarkably sustain genetic modifications and in vitro chemical derivatizations of its outer surface, which resulted in the successful display of large chimeric peptides fusions and small chemical molecules, respectively. Moreover, we have defined physicochemical conditions for viral swelling and reversible viral pore gating that we have successfully employed for foreign molecules loading and retention in the inner cavity of this plant virus nanoparticles system. Finally, a production and purification strategy from Nicotiana benthamiana plants has been addressed and optimized.

Evanescent field Sensors Based on Tantalum Pentoxide Waveguides – A Review

PubMed Central

Schmitt, Katrin; Oehse, Kerstin; Sulz, Gerd; Hoffmann, Christian

2008-01-01

Evanescent field sensors based on waveguide surfaces play an important role where high sensitivity is required. Particularly tantalum pentoxide (Ta2O5) is a suitable material for thin-film waveguides due to its high refractive index and low attenuation. Many label-free biosensor systems such as grating couplers and interferometric sensors as well as fluorescence-based systems benefit from this waveguide material leading to extremely high sensitivity. Some biosensor systems based on Ta2O5 waveguides already took the step into commercialization. This report reviews the various detection systems in terms of limit of detection, the applications, and the suitable surface chemistry. PMID:27879731

Giant magnetoresistive biosensors for molecular diagnosis: surface chemistry and assay development

NASA Astrophysics Data System (ADS)

Yu, Heng; Osterfeld, Sebastian J.; Xu, Liang; White, Robert L.; Pourmand, Nader; Wang, Shan X.

2008-08-01

Giant magnetoresistive (GMR) biochips using magnetic nanoparticle as labels were developed for molecular diagnosis. The sensor arrays consist of GMR sensing strips of 1.5 μm or 0.75 μm in width. GMR sensors are exquisitely sensitive yet very delicate, requiring ultrathin corrosion-resistive passivation and efficient surface chemistry for oligonucleotide probe immobilization. A mild and stable surface chemistry was first developed that is especially suitable for modifying delicate electronic device surfaces, and a practical application of our GMR biosensors was then demonstrated for detecting four most common human papillomavirus (HPV) subtypes in plasmids. We also showed that the DNA hybridization time could potentially be reduced from overnight to about ten minutes using microfluidics.

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

PubMed Central

2016-01-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of ‘polar ice’ mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm ‘carbonyl’ absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes. PMID:28083090

Surface water geochemical and isotopic variations in an area of accelerating Marcellus Shale gas development.

PubMed

Pelak, Adam J; Sharma, Shikha

2014-12-01

Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Controlling Short-Range Interactions by Tuning Surface Chemistry in HDPE/Graphene Nanoribbon Nanocomposites.

PubMed

Sadeghi, Soheil; Zehtab Yazdi, Alireza; Sundararaj, Uttandaraman

2015-09-03

Unique dispersion states of nanoparticles in polymeric matrices have the potential to create composites with enhanced mechanical, thermal, and electrical properties. The present work aims to determine the state of dispersion from the melt-state rheological behavior of nanocomposites based on carbon nanotube and graphene nanoribbon (GNR) nanomaterials. GNRs were synthesized from nitrogen-doped carbon nanotubes via a chemical route using potassium permanganate and some second acids. High-density polyethylene (HDPE)/GNR nanocomposite samples were then prepared through a solution mixing procedure. Different nanocomposite dispersion states were achieved using different GNR synthesis methods providing different surface chemistry, interparticle interactions, and internal compartments. Prolonged relaxation of flow induced molecular orientation was observed due to the presence of both carbon nanotubes and GNRs. Based on the results of this work, due to relatively weak interactions between the polymer and the nanofillers, it is expected that short-range interactions between nanofillers play the key role in the final dispersion state.

Influence of short chain organic acids and bases on the wetting properties and surface energy of submicrometer ceramic powders.

PubMed

Neirinck, Bram; Soccol, Dimitri; Fransaer, Jan; Van der Biest, Omer; Vleugels, Jef

2010-08-15

The effect of short chained organic acids and bases on the surface energy and wetting properties of submicrometer alumina powder was assessed. The surface chemistry of treated powders was determined by means of Diffuse Reflectance Infrared Fourier Transform spectroscopy and compared to untreated powder. The wetting of powders was measured using a modified Washburn method, based on the use of precompacted powder samples. The geometric factor needed to calculate the contact angle was derived from measurements of the porous properties of the powder compacts. Contact angle measurements with several probe liquids before and after modification allowed a theoretical estimation of the surface energy based on the surface tension component theory. Trends in the surface energy components were linked to observations in infrared spectra. The results showed that the hydrophobic character of the precompacted powder depends on both the chain length and polar group of the modifying agent. Copyright 2010 Elsevier Inc. All rights reserved.

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

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

Han, Sang-Don; Kim, Soojeong; Li, Dongguo

2017-05-19

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured delta-MnO2 cathode in association with a nonaqueous acetonitrile-Zn(TFSI)(2) electrolytemore » and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/delta-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

ERIC Educational Resources Information Center

Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

2015-01-01

Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

PubMed

Ryan, Robert G; Stacey, Alastair; O'Donnell, Kane M; Ohshima, Takeshi; Johnson, Brett C; Hollenberg, Lloyd C L; Mulvaney, Paul; Simpson, David A

2018-04-18

Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

Control of Surface Chemistry, Substrate Stiffness, and Cell Function in a Novel Terpolymer Methacrylate Library

PubMed Central

Joy, Abraham; Cohen, Daniel M.; Luk, Arnold; Anim-Danso, Emmanuel; Chen, Christopher; Kohn, Joachim

2011-01-01

A focused library of methacrylate terpolymers was synthesized to explore the effects of varying surface chemistry and adhesive peptide ligands on cell function. The chemical diversity of methacrylate monomers enabled construction of a library of polymers in which one can systematically vary the chemical composition to achieve a wide range of contact angle, Young's modulus, and Tg values. Furthermore, the materials were designed to allow surface immobilization of bioactive peptides. We then examined the effects of these material compositions on protein adsorption and cell attachment, proliferation, and differentiation. We observed that chemical composition of the polymers was an important determinant for NIH 3T3 cell attachment and proliferation, as well as human mesenchymal stem cell differentiation, and correlated directly with the ability of the polymers to adsorb proteins that mediate cell adhesion. Importantly, functionalization of the methacrylate terpolymer library with an adhesive GRGDS peptide normalized cellular responses. RGD-functionalized polymers uniformly exhibited robust attachment, proliferation, and differentiation irrespective of the underlying substrate chemistry. These studies provide a library-based approach to rapidly explore the biological functionality of biomaterials with a wide range of compositions, and highlights the importance of cell and protein cell adhesion in predicting their performance. PMID:21226505

Physico-chemical changes of ZnO nanoparticles with different size and surface chemistry under physiological pH conditions.

PubMed

Gwak, Gyeong-Hyeon; Lee, Won-Jae; Paek, Seung-Min; Oh, Jae-Min

2015-03-01

We studied the physico-chemical properties of ZnO nanoparticles under physiological pH conditions (gastric, intestinal and plasma) as functions of their size (20 and 70 nm) and surface chemistry (pristine, L-serine, or citrate coating). ZnO nanoparticles were dispersed in phosphate buffered saline under physiological pH conditions and aliquots were collected at specific time points (0.5, 1, 4, 10 and 24 h) for further characterization. The pH values of the aqueous ZnO colloids at each condition were in the neutral to slightly basic range and showed different patterns depending on the original size and surface chemistry of the ZnO nanoparticles. The gastric pH condition was found to significantly dissolve ZnO nanoparticles up to 18-30 wt%, while the intestinal or plasma pH conditions resulted in much lower dissolution amounts than expected. Based on the X-ray diffraction patterns and X-ray absorption spectra, we identified partial phase transition of the ZnO nanoparticles from wurtzite to Zn(OH)2 under the intestinal and plasma pH conditions. Using scanning electron microscopy, we verified that the overall particle size and morphology of all ZnO nanoparticles were maintained regardless of the pH. Copyright © 2015 Elsevier B.V. All rights reserved.

PRECP: the Department of Energy's program on the nonlinearity of acid precipitation processes

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

Tanner, R.L.; Tichler, J.; Brown, R.

During the period of 1 April to 3 May 1985, staff from Argonne National Laboratory (ANL), Brookhaven National Laboratory (BNL), and Pacific Northwest Laboratory (PNL), participated in a multifaceted, coordinated set of field studies from an aircraft logistical base in Columbus, OH, and a surface precipitation and air chemistry network in the Philadelphia area. The general goals of these activities, conducted within the DOE-sponsored PRocessing of Emissions by Clouds and Precipitation (PRECP) program were to obtain information concerning scavenging ratios and the vertical distribution of cloud and precipitation chemistry for sulfur and nitrogen oxides and oxyacids, and for oxidant speciesmore » in the vicinity of precipitating and nonprecipitating clouds. Profiling of pollutant concentrations and phase distributions, and studies of scavenging processes were accomplished principally by airborne measurements of aerosol and gaseous species in pre-cloud and below-cloud air and of aqueous-phase species in clouds and precipitation, accompanied by documentation of meteorological and cloud physics parameters in the sampled regimes. Studies in the Midwest utilized only limited surface precipitation collection and chemical measurements, whereas a more extensive ground precipitation network was deployed in the Philadelphia area studies together with surface air chemistry measurements at a single nonurban site.« less

Effect of gaseous ammonia on nicotine sorption

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

Webb, A.M.; Singer, B.C.; Nazaroff, W.W.

2002-06-01

Nicotine is a major constituent of environmental tobacco smoke. Sorptive interactions of nicotine with indoor surfaces can substantially alter indoor concentrations. The phenomenon is poorly understood, including whether sorption is fully reversible or partially irreversible. They hypothesize that acid-base chemistry on indoor surfaces might contribute to the apparent irreversibility of nicotine sorption under some circumstances. Specifically, they suggest that nicotine may become protonated on surfaces, markedly reducing its vapor pressure. If so, subsequent exposure of the surface to gaseous ammonia, a common base, could raise the surface pH, causing deprotonation and desorption of nicotine from surfaces. A series of experimentsmore » was conducted to explore the effect of ammonia on nicotine sorption to and reemission from surfaces. The results indicate that, under some conditions, exposure to gaseous ammonia can substantially increase the rate of desorption of previously sorbed nicotine from common indoor surface materials.« less

Improving Ionic Conductivity and Lithium-Ion Transference Number in Lithium-Ion Battery Separators.

PubMed

Zahn, Raphael; Lagadec, Marie Francine; Hess, Michael; Wood, Vanessa

2016-12-07

The microstructure of lithium-ion battery separators plays an important role in separator performance; however, here we show that a geometrical analysis falls short in predicting the lithium-ion transport in the electrolyte-filled pore space. By systematically modifying the surface chemistry of a commercial polyethylene separator while keeping its microstructure unchanged, we demonstrate that surface chemistry, which alters separator-electrolyte interactions, influences ionic conductivity and lithium-ion transference number. Changes in separator surface chemistry, particularly those that increase lithium-ion transference numbers can reduce voltage drops across the separator and improve C-rate capability.

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

NASA Technical Reports Server (NTRS)

Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

1991-01-01

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

The chemistry-climate model ECHAM6.3-HAM2.3-MOZ1.0

NASA Astrophysics Data System (ADS)

Schultz, Martin G.; Stadtler, Scarlet; Schröder, Sabine; Taraborrelli, Domenico; Franco, Bruno; Krefting, Jonathan; Henrot, Alexandra; Ferrachat, Sylvaine; Lohmann, Ulrike; Neubauer, David; Siegenthaler-Le Drian, Colombe; Wahl, Sebastian; Kokkola, Harri; Kühn, Thomas; Rast, Sebastian; Schmidt, Hauke; Stier, Philip; Kinnison, Doug; Tyndall, Geoffrey S.; Orlando, John J.; Wespes, Catherine

2018-05-01

The chemistry-climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

The Interaction of UV-Laser Radiation with Metal and Semiconductor Surfaces

DTIC Science & Technology

1992-05-26

order of magnitude larger than the typical widths of non- 43 R.C. Weast, ed., Handbook of Chemistry and Physics, p. D-185 (CRC Press, 1986). 25 resonant...fundamental chemistry and practical applications of laser chemical processing techniques involved photofragmentation of relatively 28 simple metal-alkyl...pressure of the gas was monitored with a capacitance manometer. A variety of techniques were used in this work to examine the surface-phase chemistry and

Chemistry Division: Annual progress report for period ending March 31, 1987

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

Not Available

1987-08-01

This report is divided into the following sections: coal chemistry; aqueous chemistry at high temperatures and pressures; geochemistry of crustal processes to high temperatures and pressures; chemistry of advanced inorganic materials; structure and dynamics of advanced polymeric materials; chemistry of transuranium elements and compounds; separations chemistry; reactions and catalysis in molten salts; surface science related to heterogeneous catalysis; electron spectroscopy; chemistry related to nuclear waste disposal; computational modeling of security document printing; and special topics. (DLC)

Diameter and Geometry Control of Vertically Aligned SWNTs through Catalyst Manipulation

NASA Astrophysics Data System (ADS)

Xiang, Rong; Einarsson, Erik; Okawa, Jun; Murakami, Yoichi; Maruyama, Shigeo

2009-03-01

We present our recent progress on manipulating our liquid-based catalyst loading process, which possesses greater potential than conventional deposition in terms of cost and scalability, to control the diameter and morphology of single-walled carbon nanotubes (SWNTs). We demonstrate that the diameter of aligned SWNTs synthesized by alcohol catalytic CVD can be tailored over a wide range by modifying the catalyst recipe. SWNT arrays with an average diameter as small as 1.2 nm were obtained by this method. Additionally, owing to the alignment of the array, the continuous change of the SWNT diameter during a single CVD process can be clearly observed and quantitatively characterized. We have also developed a versatile wet chemistry method to localize the growth of SWNTs to desired regions via surface modification. By functionalizing the silicon surface using a classic self-assembled monolayer, the catalyst can be selectively dip-coated onto hydrophilic areas of the substrate. This technique was successful in producing both random and aligned SWNTs with various patterns. The precise control of the diameter and morphology of SWNTs, achieved by simple and scalable liquid-based surface chemistry, could greatly facilitate the application of SWNTs as the building blocks of future nano-devices.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Monolayer of Hydrazine Facilitates the Direct Covalent Attachment of C60 Fullerene to a Silicon Surface.

PubMed

Gao, Fei; Teplyakov, Andrew V

2017-09-05

The development of oxygen-free organic-inorganic interfaces has led to new schemes for the functionalization of silicon surfaces with nitrogen-based chemical groups. However, building layers of large structures directly on this functionalized surface has remained elusive. This work confirms the path to form a stable interface between silicon and buckminsterfullerene C 60 based on covalent chemical bonds. The starting point for this modification is the hydrazine-reacted Si(111) surface with the diamine functionality, which is further reacted directly with the C 60 molecules. The chemistry of this process is confirmed spectroscopically and microscopically and can be used to form organic-inorganic interfaces separated by a single layer of nitrogen.

Self-referenced directional enhanced Raman scattering using plasmon waveguide resonance for surface and bulk sensing

NASA Astrophysics Data System (ADS)

Wan, Xiu-mei; Gao, Ran; Lu, Dan-feng; Qi, Zhi-mei

2018-01-01

Surface plasmon-coupled emission has been widely used in fluorescence imaging, biochemical sensing, and enhanced Raman spectroscopy. A self-referenced directional enhanced Raman scattering for simultaneous detection of surface and bulk effects by using plasmon waveguide resonance (PWR) based surface plasmon-coupled emission has been proposed and experimentally demonstrated. Raman scattering was captured on the prism side in Kretschmann-surface plasmon-coupled emission. The distinct penetration depths (δ) of the evanescent field for the transverse electric (TE) and transverse magnetic (TM) modes result in different detected distances of the Raman signal. The experimental results demonstrate that the self-referenced directional enhanced Raman scattering of the TE and TM modes based on the PWR can detect and distinguish the surface and bulk effects simultaneously, which appears to have potential applications in researches of chemistry, medicine, and biology.

Uniformity studies of inductively coupled plasma etching in fabrication of HgCdTe detector arrays

NASA Astrophysics Data System (ADS)

Bommena, R.; Velicu, S.; Boieriu, P.; Lee, T. S.; Grein, C. H.; Tedjojuwono, K. K.

2007-04-01

Inductively coupled plasma (ICP) chemistry based on a mixture of CH 4, Ar, and H II was investigated for the purpose of delineating HgCdTe mesa structures and vias typically used in the fabrication of second and third generation infrared photo detector arrays. We report on ICP etching uniformity results and correlate them with plasma controlling parameters (gas flow rates, total chamber pressure, ICP power and RF power). The etching rate and surface morphology of In-doped MWIR and LWIR HgCdTe showed distinct dependences on the plasma chemistry, total pressure and RF power. Contact stylus profilometry and cross-section scanning electron microscopy (SEM) were used to characterize the anisotropy of the etched profiles obtained after various processes and a standard deviation of 0.06 μm was obtained for etch depth on 128 x 128 format array vias. The surface morphology and the uniformity of the etched surfaces were studied by plan view SEM. Atomic force microscopy was used to make precise assessments of surface roughness.

Surface Chemistry and Nano-/Microstructure Engineering on Photocatalytic In2S3 Nanocrystals.

PubMed

Berestok, Taisiia; Guardia, Pablo; Portals, Javier Blanco; Estradé, Sònia; Llorca, Jordi; Peiró, Francesca; Cabot, Andreu; Brock, Stephanie L

2018-06-05

Colloidal nanocrystals (NCs) compete with molecular catalysts in the field of homogenous catalysis, offering easier recyclability and a number of potentially advantageous functionalities, such as tunable band gaps, plasmonic properties, or a magnetic moment. Using high-throughput printing technologies, colloidal NCs can also be supported onto substrates to produce cost-effective electronic, optoelectronic, electrocatalytic, and sensing devices. For both catalytic and technological application, NC surface chemistry and supracrystal organization are key parameters determining final performance. Here, we study the influence of the surface ligands and the NC organization on the catalytic properties of In 2 S 3 , both as a colloid and as a supported layer. As a colloid, NCs stabilized by inorganic ligands show the highest photocatalytic activities, which we associate with their large and more accessible surfaces. On the other hand, when NCs are supported on a substrate, their organization becomes an essential parameter determining performance. For instance, NC-based films produced through a gelation process provided five-fold higher photocurrent densities than those obtained from dense films produced by the direct printing of NCs.

Ferroelectric based catalysis: Switchable surface chemistry

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2015-03-01

We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

The Effects of Interactive Stratospheric Chemistry on Antarctic and Southern Ocean Climate Change in an AOGCM

NASA Technical Reports Server (NTRS)

Li, Feng; Newman, Paul; Pawson, Steven; Waugh, Darryn

2014-01-01

Stratospheric ozone depletion has played a dominant role in driving Antarctic climate change in the last decades. In order to capture the stratospheric ozone forcing, many coupled atmosphere-ocean general circulation models (AOGCMs) prescribe the Antarctic ozone hole using monthly and zonally averaged ozone field. However, the prescribed ozone hole has a high ozone bias and lacks zonal asymmetry. The impacts of these biases on model simulations, particularly on Southern Ocean and the Antarctic sea ice, are not well understood. The purpose of this study is to determine the effects of using interactive stratospheric chemistry instead of prescribed ozone on Antarctic and Southern Ocean climate change in an AOGCM. We compare two sets of ensemble simulations for the 1960-2010 period using different versions of the Goddard Earth Observing System 5 - AOGCM: one with interactive stratospheric chemistry, and the other with prescribed monthly and zonally averaged ozone and 6 other stratospheric radiative species calculated from the interactive chemistry simulations. Consistent with previous studies using prescribed sea surface temperatures and sea ice concentrations, the interactive chemistry runs simulate a deeper Antarctic ozone hole and consistently larger changes in surface pressure and winds than the prescribed ozone runs. The use of a coupled atmosphere-ocean model in this study enables us to determine the impact of these surface changes on Southern Ocean circulation and Antarctic sea ice. The larger surface wind trends in the interactive chemistry case lead to larger Southern Ocean circulation trends with stronger changes in northerly and westerly surface flow near the Antarctica continent and stronger upwelling near 60S. Using interactive chemistry also simulates a larger decrease of sea ice concentrations. Our results highlight the importance of using interactive chemistry in order to correctly capture the influences of stratospheric ozone depletion on climate change over Antarctic and the Southern Ocean.

Correlations between the interfacial chemistry and current-voltage behavior of n-GaAs/liquid junctions

NASA Technical Reports Server (NTRS)

Tufts, Bruce J.; Casagrande, Louis G.; Lewis, Nathan S.; Grunthaner, Frank J.

1990-01-01

Correlations between the surface chemistry of etched, (100) oriented n-GaAs electrodes and their subsequent photoelectrochemical behavior have been probed by high-resolution X-ray photoelectron spectroscopy. GaAs photoanodes were chemically treated to prepare either an oxide-free near stoichiometric surface, a surface enriched in zero-valent arsenic or a substrate-oxide terminated surface. The current-voltage (I-V) behavior of each surface type was subsequently monitored in contact with several electrolytes.

Various fates of neuronal progenitor cells observed on several different chemical functional groups

NASA Astrophysics Data System (ADS)

Liu, Xi; Wang, Ying; He, Jin; Wang, Xiu-Mei; Cui, Fu-Zhai; Xu, Quan-Yuan

2011-12-01

Neuronal progenitor cells cultured on gold-coated glass surfaces modified by different chemical functional groups, including hydroxyl (-OH), carboxyl (-COOH), amino (-NH2), bromo (-Br), mercapto (-SH), - Phenyl and methyl (-CH3), were studied here to investigate the influence of surface chemistry on the cells' adhesion, morphology, proliferation and functional gene expression. Focal adhesion staining indicated in the initial culture stage cells exhibited morphological changes in response to different chemical functional groups. Cells cultured on -NH2 grafted surface displayed focal adhesion plaque and flattened morphology and had the largest contact area. However, their counter parts on -CH3 grafted surface displayed no focal adhesion and rounded morphology and had the smallest contact area. After 6 days culture, the proliferation trend was as follows: -NH2 > -SH> -COOH> - Phenyl > - Br > -OH> -CH3. To determine the neural functional properties of the cells affected by surface chemistry, the expression of glutamate decarboxylase (GAD67), nerve growth factor (NGF) and brainderived neurotrophic factor (BDNF) were characterized. An increase of GAD67 expression was observed on -NH2, -COOH and -SH grafted surfaces, while no increase in NGF and BDNF expression was observed on any chemical surfaces. These results highlight the importance of surface chemistry in the fate determination of neuronal progenitor cells, and suggest that surface chemistry must be considered in the design of biomaterials for neural tissue engineering.

Benzotriazole a Corrosion Inhibitor for Antiques: Some Practical Surface Chemistry.

ERIC Educational Resources Information Center

Walker, Robert

1980-01-01

Describes the structure and inhibitive properties of Benzotriazole. The chemical may be employed as an inhibitor to reduce corrosion of articles during storage or display. It may be applied to copper and copper-based antiques as well as to silver and other metals. (Author/JN)

Building ultramicropores within organic polymers based on a thermosetting cyanate ester resin.

PubMed

Zhang, Bufeng; Wang, Zhonggang

2009-09-07

Ultramicropores with high surface areas (>530 m(2) g(-1)) and narrow micropore size distribution (4-6 A) were engineered within a new cyanate ester resin, extending the microporous concept (<20 A) to general thermosetting resins in the area of polymer chemistry.

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry.

PubMed

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf

2017-11-20

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two-step reaction mechanism-1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom-shows that it mirrors acid-catalyzed ether cleavage in solution. The O-Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell-Evans-Polanyi principle. Electron rearrangement during C-O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S N 2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Finlayson-Pitts, Barbara J

2009-09-28

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

Effects of soot-induced snow albedo change on snowpack and hydrological cycle in western U.S. based on WRF chemistry and regional climate simulations

NASA Astrophysics Data System (ADS)

Qian, Y.; Gustafson, W. I.; Leung, R.; Ghan, S. J.

2008-12-01

Radiative forcing induced by soot on snow is an important anthropogenic forcing affecting the global climate. In this study we simulated the deposition of soot aerosol on snow and the resulting impact on snowpack and the hydrological cycle in the western United States. A yearlong simulation was performed using the chemistry version of the Weather Research and Forecasting model (WRF-Chem) to determine the soot deposition, followed by three simulations using WRF in meteorology-only mode, with and without the soot-induced snow albedo perturbations. The chemistry simulation shows large spatial variability in soot deposition that reflects the localized emissions and the influence of the complex terrain. The soot-induced snow albedo perturbations increase the surface net solar radiation flux during late winter to early spring, increase the surface air temperature, and reduce the snow accumulation and spring snowmelt. These effects are stronger over the central Rockies and southern Alberta, where soot deposition and snowpack overlap the most. The indirect forcing of soot accelerates snowmelt and alters stream flows, including a trend toward earlier melt dates in the western United States. The soot-induced albedo reduction initiates a positive feedback process whereby dirty snow absorbs more solar radiation, heating the surface and warming the air. This warming causes reduced snow depth and fraction, which further reduces the regional surface albedo for the snow covered regions. For a doubled snow albedo perturbation, the change to surface energy and temperature is around 50-80%, however, snowpack reduction is nonlinearly accelerated.

Effects of soot-induced snow albedo change on snowpack and hydrological cycle in western United States based on Weather Research and Forecasting chemistry and regional climate simulations

NASA Astrophysics Data System (ADS)

Qian, Yun; Gustafson, William I.; Leung, L. Ruby; Ghan, Steven J.

2009-02-01

Radiative forcing induced by soot on snow is an important anthropogenic forcing affecting the global climate. In this study we simulated the deposition of soot aerosol on snow and the resulting impact on snowpack and the hydrological cycle in the western United States. A year-long simulation was performed using the chemistry version of the Weather Research and Forecasting model (WRF-Chem) to determine the soot deposition, followed by three simulations using WRF in meteorology-only mode, with and without the soot-induced snow albedo perturbations. The chemistry simulation shows large spatial variability in soot deposition that reflects the localized emissions and the influence of the complex terrain. The soot-induced snow albedo perturbations increase the surface net solar radiation flux during late winter to early spring, increase the surface air temperature, and reduce the snow accumulation and spring snowmelt. These effects are stronger over the central Rockies and southern Alberta, where soot deposition and snowpack overlap the most. The indirect forcing of soot accelerates snowmelt and alters stream flows, including a trend toward earlier melt dates in the western United States. The soot-induced albedo reduction initiates a positive feedback process whereby dirty snow absorbs more solar radiation, heating the surface and warming the air. This warming causes reduced snow depth and fraction, which further reduces the regional surface albedo for the snow-covered regions. For a doubled snow albedo perturbation, the change to surface energy and temperature is around 50-80%; however, snowpack reduction is nonlinearly accelerated.

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Dateo, Christopher e.; Schwenke, David W.; Halicioglu, Timur; Huo, winifred M.

2005-01-01

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. Study of the highly nonequilibrium rotational distribution of a nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into an atmosphere containing methane. A study of the etching of a Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

Wang, Dun-You; Stallcop, James R.; Dateo, Christopher E.; Schwenke, David W.; Haliciogiu, Timur; Huo, Winifred

2004-01-01

Recent advances in supercomputers and highly scalable quantum chemistry software render computational chemistry methods a viable means of providing chemistry data for aerothermal analysis at a specific level of confidence. Four examples of first principles quantum chemistry calculations will be presented. The study of the highly nonequilibrium rotational distribution of nitrogen molecule from the exchange reaction N + N2 illustrates how chemical reactions can influence the rotational distribution. The reaction C2H + H2 is one example of a radical reaction that occurs during hypersonic entry into a methane containing atmosphere. A study of the etching of Si surface illustrates our approach to surface reactions. A recently developed web accessible database and software tool (DDD) that provides the radiation profile of diatomic molecules is also described.

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

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

Pyrochlores, a class of complex oxides with formula A 2B 2O 7, are one of the candidates for nuclear waste encapsulation, due to the natural occurrence of actinide-bearing pyrochlore minerals and laboratory observations of high radiation tolerance. In this work, we use atomistic simulations to determine the role of surfaces, chemical interfaces, and cation disorder on the plutonium immobilization properties of pyrochlores as a function of pyrochlore chemistry. We find that both Pu 3+ and Pu 4+ segregate to the surface for the four low-index pyrochlore surfaces considered, and that the segregation energy varies with the chemistry of the compound.more » We also find that pyrochlore/pyrochlore bicrystals A 2B 2O 7/A 2'B 2'O 7 can be used to immobilize Pu 3+ and Pu 4+ either in the same or separate phases of the compound, depending on the chemistry of the material. Finally, we find that Pu 4+ segregates to the disordered phase of an order/disorder bicrystal, driven by the occurrence of local oxygen-rich environments. However, Pu 3+ is weakly sensitive to the oxygen environment, and therefore only slightly favors the disordered phase. This behavior suggests that, at some concentration, Pu incorporation can destabilize the pyrochlore structure. Together, these results provide new insight into the ability of pyrochlore compounds to encapsulate Pu and suggest new considerations in the development of waste forms based on pyrochlores. Particularly, the phase structure of a multi-phase pyrochlore composite can be used to independently getter decay products based on their valence and size.« less

Covalent Surface Modifications of Carbon Nanotubes.

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

Pavia Sanders, Adriana; O'Bryan, Greg

A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

COSMIC-RAY-MEDIATED FORMATION OF BENZENE ON THE SURFACE OF SATURN'S MOON TITAN

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

Zhou Li; Zheng Weijun; Kaiser, Ralf I.

2010-08-01

The aromatic benzene molecule (C{sub 6}H{sub 6})-a central building block of polycyclic aromatic hydrocarbon molecules-is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C{sub 2}H{sub 2}) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two ordersmore » of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene.« less

The Compatibility of Hepatocytes with Chemically Modified Porous Silicon with Reference to In Vitro Biosensors

PubMed Central

Alvarez, Sara D.; Derfus, Austin M.; Schwartz, Michael P.; Bhatia, Sangeeta N.; Sailor, Michael J.

2008-01-01

Porous Si is a nanostructured material that is of interest for molecular and cell-based biosensing, drug delivery, and tissue engineering applications. Surface chemistry is an important factor determining the stability of porous Si in aqueous media, its affinity for various biomolecular species, and its compatibility with tissues. In this study, the attachment and viability of a primary cell type to porous Si samples containing various surface chemistries is reported, and the ability of the porous Si films to retain their optical reflectivity properties relevant to molecular biosensing is assessed. Four chemical species grafted to the porous Si surface are studied: silicon oxide (via ozone oxidation), dodecyl (via hydrosilylation with dodecene), undecanoic acid (via hydrosilylation with undecylenic acid), and oligo(ethylene) glycol (via hydrosilylation with undecylenic acid followed by an oligo(ethylene) glycol coupling reaction). Fourier Transform Infrared (FTIR) spectroscopy and contact angle measurements are used to characterize the surface. Adhesion and short-term viability of primary rat hepatocytes on these surfaces, with and without pre-adsorption of collagen type I, are assessed using vital dyes (calcein-AM and ethidium homodimer I). Cell viability on undecanoic acid-terminated porous Si, oxide-terminated porous Si, and oxide-terminated flat (non-porous) Si are monitored by quantification of albumin production over the course of 8 days. The stability of porous Si thin films after 8 days in cell culture is probed by measuring the optical interferometric reflectance spectra. Results show that hepatocytes adhere better to surfaces coated with collagen, and that chemical modification does not exert a deleterious effect on primary rat hepatocytes. The hydrosilylation chemistry greatly improves the stability of porous Si in contact with cultured primary cells while allowing cell coverage levels comparable to standard culture preparations on tissue culture polystyrene. PMID:18845334

Effect of Concentration on the Interfacial and Bulk Structure of Ionic Liquids in Aqueous Solution.

PubMed

Cheng, H-W; Weiss, H; Stock, P; Chen, Y-J; Reinecke, C R; Dienemann, J-N; Mezger, M; Valtiner, M

2018-02-27

Bio and aqueous applications of ionic liquids (IL) such as catalysis in micelles formed in aqueous IL solutions or extraction of chemicals from biologic materials rely on surface-active and self-assembly properties of ILs. Here, we discuss qualitative relations of the interfacial and bulk structuring of a water-soluble surface-active IL ([C 8 MIm][Cl]) on chemically controlled surfaces over a wide range of water concentrations using both force probe and X-ray scattering experiments. Our data indicate that IL structuring evolves from surfactant-like surface adsorption at low IL concentrations, to micellar bulk structure adsorption above the critical micelle concentration, to planar bilayer formation in ILs with <1 wt % of water and at high charging of the surface. Interfacial structuring is controlled by mesoscopic bulk structuring at high water concentrations. Surface chemistry and surface charges decisively steer interfacial ordering of ions if the water concentration is low and/or the surface charge is high. We also demonstrate that controlling the interfacial forces by using self-assembled monolayer chemistry allows tuning of interfacial structures. Both the ratio of the head group size to the hydrophobic tail volume as well as the surface charging trigger the bulk structure and offer a tool for predicting interfacial structures. Based on the applied techniques and analyses, a qualitative prediction of molecular layering of ILs in aqueous systems is possible.

Quantification of air plasma chemistry for surface disinfection

NASA Astrophysics Data System (ADS)

Pavlovich, Matthew J.; Clark, Douglas S.; Graves, David B.

2014-12-01

Atmospheric-pressure air plasmas, created by a variety of discharges, are promising sources of reactive species for the emerging field of plasma biotechnology because of their convenience and ability to operate at ambient conditions. One biological application of ambient-air plasma is microbial disinfection, and the ability of air plasmas to decontaminate both solid surfaces and liquid volumes has been thoroughly established in the literature. However, the mechanism of disinfection and which reactive species most strongly correlate with antimicrobial effects are still not well understood. We describe quantitative gas-phase measurements of plasma chemistry via infrared spectroscopy in confined volumes, focusing on air plasma generated via surface micro-discharge (SMD). Previously, it has been shown that gaseous chemistry is highly sensitive to operating conditions, and the measurements we describe here extend those findings. We quantify the gaseous concentrations of ozone (O3) and nitrogen oxides (NO and NO2, or NOx) throughout the established ‘regimes’ for SMD air plasma chemistry: the low-power, ozone-dominated mode; the high-power, nitrogen oxides-dominated mode; and the intermediate, unstable transition region. The results presented here are in good agreement with previously published experimental studies of aqueous chemistry and parameterized models of gaseous chemistry. The principal finding of the present study is the correlation of bacterial inactivation on dry surfaces with gaseous chemistry across these time and power regimes. Bacterial decontamination is most effective in ‘NOx mode’ and less effective in ‘ozone mode’, with the weakest antibacterial effects in the transition region. Our results underscore the dynamic nature of air plasma chemistry and the importance of careful chemical characterization of plasma devices intended for biological applications.

The hydrochemistry of glacial Ebba River (Petunia Bay, Central Spitsbergen): Groundwater influence on surface water chemistry

NASA Astrophysics Data System (ADS)

Dragon, Krzysztof; Marciniak, Marek; Szpikowski, Józef; Szpikowska, Grażyna; Wawrzyniak, Tomasz

2015-10-01

The article presents the investigation of surface water chemistry changes of the glacial Ebba River (Central Spitsbergen) during three melting seasons of 2008, 2009 and 2010. The twice daily water chemistry analyses allow recognition of the surface water chemistry differentiation. The surface water chemistry changes are related to the river discharge and changes in the influence of different water balance components during each melting season. One of the most important process that influence river water component concentration increase is groundwater inflow from active layer occurring on the valley area. The significance of this process is the most important at the end of the melting season when temperatures below 0 °C occur on glaciers (resulting in a slowdown of melting of ice and snow and a smaller recharge of the river by the water from the glaciers) while the flow of groundwater is still active, causing a relatively higher contribution of groundwater to the total river discharge. The findings presented in this paper show that groundwater contribution to the total polar river water balance is more important than previously thought and its recognition allow a better understanding of the hydrological processes occurring in a polar environment.

Regional variations in water quality and relationships to soil and bedrock weathering in the southern Sacramento Valley, California, USA

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Morrison, J.M.; Lee, L.

2009-01-01

Regional patterns in ground- and surface-water chemistry of the southern Sacramento Valley in California were evaluated using publicly available geochemical data from the US Geological Survey's National Water Information System (NWIS). Within the boundaries of the study area, more than 2300 ground-water analyses and more than 20,000 surface-water analyses were available. Ground-waters from the west side of the Sacramento Valley contain greater concentrations of Na, Ca, Mg, B, Cl and SO4, while the east-side ground-waters contain greater concentrations of silica and K. These differences result from variations in surface-water chemistry as well as from chemical reactions between water and aquifer materials. Sediments that fill the Sacramento Valley were derived from highlands to the west (the Coast Ranges) and east (the Sierra Nevada Mountains), the former having an oceanic provenance and the latter continental. These geologic differences are at least in part responsible for the observed patterns in ground-water chemistry. Thermal springs that are common along the west side of the Sacramento Valley appear to have an effect on surface-water chemistry, which in turn may affect the ground-water chemistry.

75 FR 770 - Acrylic acid-benzyl methacrylate-1-propanesulfonic acid, 2-methyl-2-[(1-oxo-2-propenyl)amino...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-06

....960. Akzo Nobel Surface Chemistry LLC submitted a petition to EPA under the Federal Food, Drug, and... the receipt of a pesticide petition (PP 9E7599) filed by Akzo Nobel Surface Chemistry LLC. The...

Structural Chemistry of Human RNA Methyltransferases.

PubMed

Schapira, Matthieu

2016-03-18

RNA methyltransferases (RNMTs) play important roles in RNA stability, splicing, and epigenetic mechanisms. They constitute a promising target class that is underexplored by the medicinal chemistry community. Information of relevance to drug design can be extracted from the rich structural coverage of human RNMTs. In this work, the structural chemistry of this protein family is analyzed in depth. Unlike most methyltransferases, RNMTs generally feature a substrate-binding site that is largely open on the cofactor-binding pocket, favoring the design of bisubstrate inhibitors. Substrate purine or pyrimidines are often sandwiched between hydrophobic walls that can accommodate planar ring systems. When the substrate base is laying on a shallow surface, a 5' flanking base is sometimes anchored in a druggable cavity. The cofactor-binding site is structurally more diverse than in protein methyltransferases and more druggable in SPOUT than in Rossman-fold enzymes. Finally, conformational plasticity observed both at the substrate and cofactor binding sites may be a challenge for structure-based drug design. The landscape drawn here may inform ongoing efforts toward the discovery of the first human RNMT inhibitors.

Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

NASA Astrophysics Data System (ADS)

Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

2017-05-01

Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO42- based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

Protein Adsorption in Three Dimensions

PubMed Central

Vogler, Erwin A.

2011-01-01

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and initially-adsorbed protein. Interphase protein concentration CI increases as VI decreases, resulting in slow reduction in interfacial energetics. Steady-state is governed by a net partition coefficient P=(/CBCI). In the process of occupying space within the interphase, adsorbing protein molecules must displace an equivalent volume of interphase water. Interphase water is itself associated with surface-bound water through a network of transient hydrogen bonds. Displacement of interphase water thus requires an amount of energy that depends on the adsorbent surface chemistry/energy. This “adsorption-dehydration” step is the significant free-energy cost of adsorption that controls the maximum amount of protein that can be adsorbed at steady state to a unit adsorbent-surface area (the adsorbent capacity). As adsorbent hydrophilicity increases, protein adsorption monotonically decreases because the energetic cost of surface dehydration increases, ultimately leading to no protein adsorption near an adsorbent water wettability (surface energy) characterized by a water contact angle θ → 65°. Consequently, protein does not adsorb (accumulate at interphase concentrations greater than bulk solution) to more hydrophilic adsorbents exhibiting θ < 65° . For adsorbents bearing strong Lewis acid/base chemistry such as ion-exchange resins, protein/surface interactions can be highly favorable, causing protein to adsorb in multilayers in a relatively thick interphase. A straightforward, three-component free energy relationship captures salient features of protein adsorption to all surfaces predicting that the overall free energy of protein adsorption ΔGadso is a relatively small multiple of thermal energy for any surface chemistry (except perhaps for bioengineered surfaces bearing specific ligands for adsorbing protein) because a surface chemistry that interacts chemically with proteins must also interact with water through hydrogen bonding. In this way, water moderates protein adsorption to any surface by competing with adsorbing protein molecules. This Leading Opinion ends by proposing several changes to the protein-adsorption paradigm that might advance answers to the three core questions that frame the “protein-adsorption problem” that is so fundamental to biomaterials surface science. PMID:22088888

Evaluation of mean climate in a chemistry-climate model simulation

NASA Astrophysics Data System (ADS)

Hong, S.; Park, H.; Wie, J.; Park, R.; Lee, S.; Moon, B. K.

2017-12-01

Incorporation of the interactive chemistry is essential for understanding chemistry-climate interactions and feedback processes in climate models. Here we assess a newly developed chemistry-climate model (GRIMs-Chem), which is based on the Global/Regional Integrated Model system (GRIMs) including the aerosol direct effect as well as stratospheric linearized ozone chemistry (LINOZ). We conducted GRIMs-Chem with observed sea surface temperature during the period of 1979-2010, and compared the simulation results with observations and also with CMIP models. To measure the relative performance of our model, we define the quantitative performance metric using the Taylor diagram. This metric allow us to assess overall features in simulating multiple variables. Overall, our model better reproduce the zonal mean spatial pattern of temperature, horizontal wind, vertical motion, and relative humidity relative to other models. However, the model did not produce good simulations at upper troposphere (200 hPa). It is currently unclear which model processes are responsible for this. AcknowledgementsThis research was supported by the Korea Ministry of Environment (MOE) as "Climate Change Correspondence Program."

Simultaneous assessment of phase chemistry, phase abundance and bulk chemistry with statistical electron probe micro-analyses: Application to cement clinkers

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

Wilson, William; Krakowiak, Konrad J.; Ulm, Franz-Josef, E-mail: ulm@mit.edu

2014-01-15

According to recent developments in cement clinker engineering, the optimization of chemical substitutions in the main clinker phases offers a promising approach to improve both reactivity and grindability of clinkers. Thus, monitoring the chemistry of the phases may become part of the quality control at the cement plants, along with the usual measurements of the abundance of the mineralogical phases (quantitative X-ray diffraction) and the bulk chemistry (X-ray fluorescence). This paper presents a new method to assess these three complementary quantities with a single experiment. The method is based on electron microprobe spot analyses, performed over a grid located onmore » a representative surface of the sample and interpreted with advanced statistical tools. This paper describes the method and the experimental program performed on industrial clinkers to establish the accuracy in comparison to conventional methods. -- Highlights: •A new method of clinker characterization •Combination of electron probe technique with cluster analysis •Simultaneous assessment of phase abundance, composition and bulk chemistry •Experimental validation performed on industrial clinkers.« less

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

DOE PAGES

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan; ...

2017-04-27

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

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

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

Organic acid modeling and model validation: Workshop summary. Final report

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

Sullivan, T.J.; Eilers, J.M.

1992-08-14

A workshop was held in Corvallis, Oregon on April 9--10, 1992 at the offices of E&S Environmental Chemistry, Inc. The purpose of this workshop was to initiate research efforts on the entitled ``Incorporation of an organic acid representation into MAGIC (Model of Acidification of Groundwater in Catchments) and testing of the revised model using Independent data sources.`` The workshop was attended by a team of internationally-recognized experts in the fields of surface water acid-bass chemistry, organic acids, and watershed modeling. The rationale for the proposed research is based on the recent comparison between MAGIC model hindcasts and paleolimnological inferences ofmore » historical acidification for a set of 33 statistically-selected Adirondack lakes. Agreement between diatom-inferred and MAGIC-hindcast lakewater chemistry in the earlier research had been less than satisfactory. Based on preliminary analyses, it was concluded that incorporation of a reasonable organic acid representation into the version of MAGIC used for hindcasting was the logical next step toward improving model agreement.« less

Organic acid modeling and model validation: Workshop summary

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

Sullivan, T.J.; Eilers, J.M.

1992-08-14

A workshop was held in Corvallis, Oregon on April 9--10, 1992 at the offices of E S Environmental Chemistry, Inc. The purpose of this workshop was to initiate research efforts on the entitled Incorporation of an organic acid representation into MAGIC (Model of Acidification of Groundwater in Catchments) and testing of the revised model using Independent data sources.'' The workshop was attended by a team of internationally-recognized experts in the fields of surface water acid-bass chemistry, organic acids, and watershed modeling. The rationale for the proposed research is based on the recent comparison between MAGIC model hindcasts and paleolimnological inferencesmore » of historical acidification for a set of 33 statistically-selected Adirondack lakes. Agreement between diatom-inferred and MAGIC-hindcast lakewater chemistry in the earlier research had been less than satisfactory. Based on preliminary analyses, it was concluded that incorporation of a reasonable organic acid representation into the version of MAGIC used for hindcasting was the logical next step toward improving model agreement.« less

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes.

PubMed

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P; Steirer, K Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

2018-05-01

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg 2+ cannot penetrate such interphases. Here, we engineer an artificial Mg 2+ -conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V 2 O 5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

NASA Astrophysics Data System (ADS)

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.; Steirer, K. Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

2018-05-01

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays

PubMed Central

Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A.; Dew, Steven K.; McDermott, Mark T.; Evoy, Stephane

2015-01-01

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings. PMID:26263989

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays.

PubMed

Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A; Dew, Steven K; McDermott, Mark T; Evoy, Stephane

2015-07-30

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

Duplex aluminized coatings

NASA Technical Reports Server (NTRS)

Gedwill, M. A.; Grisaffe, S. J. (Inventor)

1975-01-01

The surface of a metallic base system is initially coated with a metallic alloy layer that is ductile and oxidation resistant. An aluminide coating is then applied to the metallic alloy layer. The chemistry of the metallic alloy layer is such that the oxidation resistance of the subsequently aluminized outermost layer is not seriously degraded.

Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

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

Osseo-Asare, K.; Boakye, E.; Vittal, M.

1995-04-01

This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

NASA Astrophysics Data System (ADS)

Lee, Chung-Ho; Kim, Youn-Jeong; Jang, Je-Hee; Park, Jin-Woo

2016-02-01

Nanoscale topographical modification and surface chemistry alteration using bioactive ions are centrally important processes in the current design of the surface of titanium (Ti) bone implants with enhanced bone healing capacity. Macrophages play a central role in the early tissue healing stage and their activity in response to the implant surface is known to affect the subsequent healing outcome. Thus, the positive modulation of macrophage phenotype polarization (i.e. towards the regenerative M2 rather than the inflammatory M1 phenotype) with a modified surface is essential for the osteogenesis funtion of Ti bone implants. However, relatively few advances have been made in terms of modulating the macrophage-centered early healing capacity in the surface design of Ti bone implants for the two important surface properties of nanotopography and and bioactive ion chemistry. We investigated whether surface bioactive ion modification exerts a definite beneficial effect on inducing regenerative M2 macrophage polarization when combined with the surface nanotopography of Ti. Our results indicate that nanoscale topographical modification and surface bioactive ion chemistry can positively modulate the macrophage phenotype in a Ti implant surface. To the best of our knowledge, this is the first demonstration that chemical surface modification using divalent cations (Ca and Sr) dramatically induces the regenerative M2 macrophage phenotype of J774.A1 cells in nanostructured Ti surfaces. In this study, divalent cation chemistry regulated the cell shape of adherent macrophages and markedly up-regulated M2 macrophage phenotype expression when combined with the nanostructured Ti surface. These results provide insight into the surface engineering of future Ti bone implants that are harmonized between the macrophage-governed early wound healing process and subsequent mesenchymal stem cell-centered osteogenesis function.

Block copolymer-templated chemistry on Si, Ge, InP, and GaAs surfaces.

PubMed

Aizawa, Masato; Buriak, Jillian M

2005-06-29

Patterning of semiconductor surfaces is an area of intense interest, not only for technological applications, such as molecular electronics, sensing, cellular recognition, and others, but also for fundamental understanding of surface reactivity, general control over surface properties, and development of new surface reactivity. In this communication, we describe the use of self-assembling block copolymers to direct semiconductor surface chemistry in a spatially defined manner, on the nanoscale. The proof-of-principle class of reactions evaluated here is galvanic displacement, in which a metal ion, M+, is reduced to M0 by the semiconductor, including Si, Ge, InP, and GaAs. The block copolymer chosen has a polypyridine block which binds to the metal ions and brings them into close proximity with the surface, at which point they undergo reaction; the pattern of resulting surface chemistry, therefore, mirrors the nanoscale structure of the parent block copolymer. This chemistry has the added advantage of forming metal nanostructures that result in an alloy or intermetallic at the interface, leading to strongly bound metal nanoparticles that may have interesting electronic properties. This approach has been shown to be very general, functioning on a variety of semiconductor substrates for both silver and gold deposition, and is being extended to organic and inorganic reactions on a variety of conducting, semiconducting, and insulating substrates.

Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

Surface chemistry associated with the cooling and subaerial weathering of recent basalt flows

USGS Publications Warehouse

White, A.F.; Hochella, M.F.

1992-01-01

The surface chemistry of fresh and weathered historical basalt flows was characterized using surface-sensitive X-ray photoelectron spectroscopy (XPS). Surfaces of unweathered 1987-1990 flows from the Kilauea Volcano, Hawaii, exhibited variable enrichment in Al, Mg, Ca, and F due to the formation of refractory fluoride compounds and pronounced depletion in Si and Fe from the volatilization of SiF4 and FeF3 during cooling. These reactions, as predicted from shifts in thermodynamic equilibrium with temperature, are induced by diffusion of HF from the flow interiors to the cooling surface. The lack of Si loss and solid fluoride formation for recent basalts from the Krafla Volcano, Iceland, suggest HF degassing at higher temperatures. Subsequent short-term subaerial weathering reactions are strongly influenced by the initial surface composition of the flow and therefore its cooling history. Successive samples collected from the 1987 Kilauea flow demonstrated that the fluoridated flow surfaces leached to a predominantly SiO2 composition by natural weathering within one year. These chemically depleted surfaces were also observed on Hawaiian basalt flows dating back to 1801 AD. Solubility and kinetic models, based on thermodynamic and kinetic data for crystalline AlF3, MgF2, and CaF2, support observed elemental depletion rates due to chemical weathering. Additional loss of alkalis from the Hawaiian basalt occurs from incongruent dissolution of the basalt glass substrate during weathering. ?? 1992.

Surface and interfacial chemistry of high-k dielectric and interconnect materials on silicon

NASA Astrophysics Data System (ADS)

Kirsch, Paul Daniel

Surfaces and interfaces play a critical role in the manufacture and function of silicon based integrated circuits. It is therefore reasonable to study the chemistries at these surfaces and interfaces to improve existing processes and to develop new ones. Model barium strontium titanate high-k dielectric systems have been deposited on ultrathin silicon oxynitride in ultrahigh vacuum. The resulting nanostructures are characterized with secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). An interfacial reaction between Ba and Sr atoms and SiOxNy was found to create silicates, BaSixOy or SrSi xOy. Inclusion of N in the interfacial oxide decreased silicate formation in both Ba and Sr systems. Furthermore, inclusion of N in the interfacial oxide decreased the penetration of Ba and Sr containing species, such as silicides and silicates. Sputter deposited HfO2 was studied on nitrided and unnitrided Si(100) surfaces. XPS and SIMS were used to verify the presence of interfacial HfSixOy and estimate its relative amount on both nitrided and unnitrided samples. More HfSixOy formed without the SiNx interfacial layer. These interfacial chemistry results are then used to explain the electrical measurements obtained from metal oxide semiconductor (MOS) capacitors. MOS capacitors with interfacial SiNx exhibit reduced leakage current and increased capacitance. Lastly, surface science techniques were used to develop a processing technique for reducing thin films of copper (II) and copper (I) oxide to copper. Deuterium atoms (D*) and methyl radicals (CH3*) were shown to reduce Cu 2+ and/or Cu1+ to Cu0 within 30 min at a surface temperature of 400 K under a flux of 1 x 1015 atoms/cm2s. Temperature programmed desorption experiments suggest that oxygen leaves the surface as D2O and CO2 for the D* and CH3* treated surfaces, respectively.

Model Amphiphilic Block Copolymers with Tailored Molecular Weight and Composition in PDMS-Based Films to Limit Soft Biofouling

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

Wenning, Brandon M.; Martinelli, Elisa; Mieszkin, Sophie

A set of controlled surface composition films was produced utilizing amphiphilic block copolymers dispersed in a cross-linked poly(dimethylsiloxane) network. These block copolymers contained oligo(ethylene glycol) (PEGMA) and fluoroalkyl (AF6) side chains in selected ratios and molecular weights to control surface chemistry including antifouling and fouling-release performance. Such properties were assessed by carrying out assays using two algae, the green macroalga Ulva linza (favors attachment to polar surfaces) and the unicellular diatom Navicula incerta (favors attachment to nonpolar surfaces). All films performed well against U. linza and exhibited high removal of attached sporelings (young plants) under an applied shear stress, withmore » the lower molecular weight block copolymers being the best performing in the set. The composition ratios from 50:50 to 60:40 of the AF6/PEGMA side groups were shown to be more effective, with several films exhibiting spontaneous removal of the sporelings. The cells of N. incerta were also removed from several coating compositions. All films were characterized by surface techniques including captive bubble contact angle, atomic force microscopy, and near edge X-ray absorption fine structure spectroscopy to correlate surface chemistry and morphology with biological performance.« less

Applications of Quantum Chemistry to the Study of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Jaffe, Richard L.

2005-01-01

For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:

Controls on surface water chemistry in the upper Merced River basin, Yosemite National Park, California

USGS Publications Warehouse

Clow, D.W.; Mast, M.A.; Campbell, D.H.

1996-01-01

Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 ??equiv. 1-1. Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 ??equiv. 1-1. Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock, Chloride concentrations in surface water samples varied widely, ranging from <1 to 96 ??equiv. 1-1. The annual volume-weighted mean chloride concentration in the Merced River at the Happy Isles gauge from 1968 to 1990 was 26 ??equiv. 1-1, which was five times higher than in atmospheric deposition (4-5 ??equiv. 1-1), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 ??equiv. 1-1. Concentrations of sulphate in quarterly samples collected at the watershed outlet also showed relatively little variation, suggesting that sulphate may be regulated to some extent by a within-watershed process, such as sulphate adsorption.

Density functional theory in surface chemistry and catalysis

PubMed Central

Nørskov, Jens K.; Abild-Pedersen, Frank; Studt, Felix; Bligaard, Thomas

2011-01-01

Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future challenges. PMID:21220337

INLAND DISSOLVED SALT CHEMISTRY: STATISTICAL EVALUATION OF BIVARIATE AND TERNARY DIAGRAM MODELS FOR SURFACE AND SUBSURFACE WATERS

EPA Science Inventory

We compared the use of ternary and bivariate diagrams to distinguish the effects of atmospheric precipitation, rock weathering, and evaporation on inland surface and subsurface water chemistry. The three processes could not be statistically differentiated using bivariate models e...

The Application of SERS (Surface Enhanced Raman Scattering) to Study Surface Oxidation Reactions of Phosphonates.

DTIC Science & Technology

1988-02-15

Center Attn: Dr. Ron Atkins Code 50C Chemistry Division Crane, Indiana 47522-5050 China Lake, California 93555 Scientific Advisor INaval Civil...Superintendent Marine Sciences Division Chemistry Division, Code 6100 San Diego, California 91232 Naval Research Laboratory Washington, D.C. 20375-5000 ,! .1

Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

PubMed

Reum, Jonathan C P; Alin, Simone R; Feely, Richard A; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

Seasonal Carbonate Chemistry Covariation with Temperature, Oxygen, and Salinity in a Fjord Estuary: Implications for the Design of Ocean Acidification Experiments

PubMed Central

Reum, Jonathan C. P.; Alin, Simone R.; Feely, Richard A.; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008–2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems. PMID:24586915

Multi-model study of mercury dispersion in the atmosphere: atmospheric processes and model evaluation

NASA Astrophysics Data System (ADS)

Travnikov, Oleg; Angot, Hélène; Artaxo, Paulo; Bencardino, Mariantonia; Bieser, Johannes; D'Amore, Francesco; Dastoor, Ashu; De Simone, Francesco; Diéguez, María del Carmen; Dommergue, Aurélien; Ebinghaus, Ralf; Feng, Xin Bin; Gencarelli, Christian N.; Hedgecock, Ian M.; Magand, Olivier; Martin, Lynwill; Matthias, Volker; Mashyanov, Nikolay; Pirrone, Nicola; Ramachandran, Ramesh; Read, Katie Alana; Ryjkov, Andrei; Selin, Noelle E.; Sena, Fabrizio; Song, Shaojie; Sprovieri, Francesca; Wip, Dennis; Wängberg, Ingvar; Yang, Xin

2017-04-01

Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air-surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM / GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM / GEM ratios from spring to summer. O3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere.

Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

PubMed

Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A

2011-08-14

Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1). This journal is © The Royal Society of Chemistry 2011

Carbon-Based Honeycomb Monoliths for Environmental Gas-Phase Applications

PubMed Central

Moreno-Castilla, Carlos; Pérez-Cadenas, Agustín F.

2010-01-01

Honeycomb monoliths consist of a large number of parallel channels that provide high contact efficiencies between the monolith and gas flow streams. These structures are used as adsorbents or supports for catalysts when large gas volumes are treated, because they offer very low pressure drop, short diffusion lengths and no obstruction by particulate matter. Carbon-based honeycomb monoliths can be integral or carbon-coated ceramic monoliths, and they take advantage of the versatility of the surface area, pore texture and surface chemistry of carbon materials. Here, we review the preparation methods of these monoliths, their characteristics and environmental applications.

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

DOE PAGES

Han, Sang-Don; Kim, Soojeong; Li, Dongguo; ...

2017-05-08

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn 2+ ion chemistry. There are several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. Our study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO 2 cathode in association withmore » a nonaqueous acetonitrile–Zn(TFSI) 2 electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. There are numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO 2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

Solid surface vs. liquid surface: nanoarchitectonics, molecular machines, and DNA origami.

PubMed

Ariga, Katsuhiko; Mori, Taizo; Nakanishi, Waka; Hill, Jonathan P

2017-09-13

The investigation of molecules and materials at interfaces is critical for the accumulation of new scientific insights and technological advances in the chemical and physical sciences. Immobilization on solid surfaces permits the investigation of different properties of functional molecules or materials with high sensitivity and high spatial resolution. Liquid surfaces also present important media for physicochemical innovation and insight based on their great flexibility and dynamicity, rapid diffusion of molecular components for mixing and rearrangements, as well as drastic spatial variation in the prevailing dielectric environment. Therefore, a comparative discussion of the relative merits of the properties of materials when positioned at solid or liquid surfaces would be informative regarding present-to-future developments of surface-based technologies. In this perspective article, recent research examples of nanoarchitectonics, molecular machines, DNA nanotechnology, and DNA origami are compared with respect to the type of surface used, i.e. solid surfaces vs. liquid surfaces, for future perspectives of interfacial physics and chemistry.

Model of coordination melting of crystals and anisotropy of physical and chemical properties of the surface

NASA Astrophysics Data System (ADS)

Bokarev, Valery P.; Krasnikov, Gennady Ya

2018-02-01

Based on the evaluation of the properties of crystals, such as surface energy and its anisotropy, the surface melting temperature, the anisotropy of the work function of the electron, and the anisotropy of adsorption, were shown the advantages of the model of coordination melting (MCM) in calculating the surface properties of crystals. The model of coordination melting makes it possible to calculate with an acceptable accuracy the specific surface energy of the crystals, the anisotropy of the surface energy, the habit of the natural crystals, the temperature of surface melting of the crystal, the anisotropy of the electron work function and the anisotropy of the adhesive properties of single-crystal surfaces. The advantage of our model is the simplicity of evaluating the surface properties of the crystal based on the data given in the reference literature. In this case, there is no need for a complex mathematical tool, which is used in calculations using quantum chemistry or modeling by molecular dynamics.

Downward-deployed tethered satellite systems, measurement techniques, and instrumentation - A review

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Melfi, Leonard T., Jr.; Upchurch, Billy T.; Wood, George M., Jr.

1992-01-01

This paper describes a number of scheduled and proposed Shuttle-based downward-deployed tethered satellite systems (TSSs) the purpose of which is to determine the structure of the lower thermosphere and to measure the atmospheric and aerodynamic effects in the vicinity of the satellite, the aerothermodynamic effects on the satellite's surface, and the dynamics of the tether and its endmass, the satellite. The instruments for the downward-deployed tethered missions will include mass spectrometers and other density sensors, plasma instrumentation, optical spectrophotometers, magnetometers, and instrumentation to measure the effects on satellite surface (such as the surface temperature, heat transfer, and pressure; gas adsorption on surfaces, chemistry with other gas molecules and surface material, and desorption from the surface; and surface charging).

Sol-Gel Chemistry for Carbon Dots.

PubMed

Malfatti, Luca; Innocenzi, Plinio

2018-03-14

Carbon dots are an emerging class of carbon-based nanostructures produced by low-cost raw materials which exhibit a widely-tunable photoluminescence and a high quantum yield. The potential of these nanomaterials as a substitute of semiconductor quantum dots in optoelectronics and biomedicine is very high, however they need a customized chemistry to be integrated in host-guest systems or functionalized in core-shell structures. This review is focused on recent advances of the sol-gel chemistry applied to the C-dots technology. The surface modification, the fine tailoring of the chemical composition and the embedding into a complex nanostructured material are the main targets of combining sol-gel processing with C-dots chemistry. In addition, the synergistic effect of the sol-gel precursor combined with the C-dots contribute to modify the intrinsic chemo-physical properties of the dots, empowering the emission efficiency or enabling the tuning of the photoluminescence over a wide range of the visible spectrum. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry

NASA Astrophysics Data System (ADS)

Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S.; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

2016-05-01

Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti4+ to form planar p-type [Ti4+n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B3+, Al3+ and Sn4+) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

Atomic scale characterization and surface chemistry of metal modified titanate nanotubes and nanowires

NASA Astrophysics Data System (ADS)

Kukovecz, Ákos; Kordás, Krisztián; Kiss, János; Kónya, Zoltán

2016-10-01

Titanates are salts of polytitanic acid that can be synthesized as nanostructures in a great variety concerning crystallinity, morphology, size, metal content and surface chemistry. Titanate nanotubes (open-ended hollow cylinders measuring up to 200 nm in length and 15 nm in outer diameter) and nanowires (solid, elongated rectangular blocks with length up to 1500 nm and 30-60 nm diameter) are the most widespread representatives of the titanate nanomaterial family. This review covers the properties and applications of these two materials from the surface science point of view. Dielectric, vibrational, electron and X-ray spectroscopic results are comprehensively discussed first, then surface modification methods including covalent functionalization, ion exchange and metal loading are covered. The versatile surface chemistry of one-dimensional titanates renders them excellent candidates for heterogeneous catalytic, photocatalytic, photovoltaic and energy storage applications, therefore, these fields are also reviewed.

Water chemistry in 179 randomly selected Swedish headwater streams related to forest production, clear-felling and climate.

PubMed

Löfgren, Stefan; Fröberg, Mats; Yu, Jun; Nisell, Jakob; Ranneby, Bo

2014-12-01

From a policy perspective, it is important to understand forestry effects on surface waters from a landscape perspective. The EU Water Framework Directive demands remedial actions if not achieving good ecological status. In Sweden, 44 % of the surface water bodies have moderate ecological status or worse. Many of these drain catchments with a mosaic of managed forests. It is important for the forestry sector and water authorities to be able to identify where, in the forested landscape, special precautions are necessary. The aim of this study was to quantify the relations between forestry parameters and headwater stream concentrations of nutrients, organic matter and acid-base chemistry. The results are put into the context of regional climate, sulphur and nitrogen deposition, as well as marine influences. Water chemistry was measured in 179 randomly selected headwater streams from two regions in southwest and central Sweden, corresponding to 10 % of the Swedish land area. Forest status was determined from satellite images and Swedish National Forest Inventory data using the probabilistic classifier method, which was used to model stream water chemistry with Bayesian model averaging. The results indicate that concentrations of e.g. nitrogen, phosphorus and organic matter are related to factors associated with forest production but that it is not forestry per se that causes the excess losses. Instead, factors simultaneously affecting forest production and stream water chemistry, such as climate, extensive soil pools and nitrogen deposition, are the most likely candidates The relationships with clear-felled and wetland areas are likely to be direct effects.

Bacterial response to different surface chemistries fabricated by plasma polymerization on electrospun nanofibers.

PubMed

Abrigo, Martina; Kingshott, Peter; McArthur, Sally L

2015-12-06

Control over bacterial attachment and proliferation onto nanofibrous materials constitutes a major challenge for a variety of applications, including filtration membranes, protective clothing, wound dressings, and tissue engineering scaffolds. To develop effective devices, the interactions that occur between bacteria and nanofibers with different morphological and physicochemical properties need to be investigated. This paper explores the influence of fiber surface chemistry on bacterial behavior. Different chemical functionalities were generated on the surface of electrospun polystyrene nanofibers through plasma polymerization of four monomers (acrylic acid, allylamine, 1,7-octadiene, and 1,8-cineole). The interactions of Escherichia coli with the surface modified fibers were investigated through a combination of scanning electron microscopy and confocal laser scanning microscopy. Fiber wettability, surface charge, and chemistry were found to affect the ability of bacterial cells to attach and proliferate throughout the nanofiber meshes. The highest proportion of viable cells attachment occurred on the hydrophilic amine rich coating, followed by the hydrophobic octadiene. The acrylic acid coating rich in carboxyl groups showed a significantly lower attraction of bacterial cells. The 1,8-cineole retained the antibacterial activity of the monomer, resulting with a high proportion of dead isolated cells attached onto the fibers. Results showed that the surface chemistry properties of nanofibrous membranes can be strategically tuned to control bacterial behavior.

Human Fetal Osteoblast Response on Poly(Methyl Methacrylate)/Polystyrene Demixed Thin Film Blends: Surface Chemistry Vs Topography Effects.

PubMed

D'Sa, Raechelle A; Raj, Jog; Dickinson, Peter J; McCabe, Fiona; Meenan, Brian J

2016-06-22

Recent advances in materials sciences have allowed for the development and fabrication of biomaterials that are capable of providing requisite cues to instigate cells to respond in a predictable fashion. We have developed a series of poly(methyl methacrylate)/polystyrene (PMMA/PS) polymer demixed thin films with nanotopographies ranging from nanoislands to nanopits to study the response of human fetal osteoblast cells (hFOBs). When PMMA was in excess in the blend composition, a nanoisland topography dominated, whereas a nanopit topography dominated when PS was in excess. PMMA was found to segregate to the top of the nanoisland morphology with PS preferring the substrate interface. To further ascertain the effects of surface chemistry vs topography, we plasma treated the polymer demixed films using an atmospheric pressure dielectric barrier discharge reactor to alter the surface chemistry. Our results have shown that hFOBs did not have an increased short-term cellular response on pristine polymer demixed surfaces. However, increasing the hydrophilicty/wettability of the surfaces by oxygen functionalization causes an increase in the cellular response. These results indicate that topography alone is not sufficient to induce a positive cellular response, but the underlying surface chemistry is also important in regulating cell function.

Non-covalently functionalized carbon nanostructures for synthesizing carbon-based hybrid nanomaterials.

PubMed

Li, Haiqing; Song, Sing I; Song, Ga Young; Kim, Il

2014-02-01

Carbon nanostructures (CNSs) such as carbon nanotubes, graphene sheets, and nanodiamonds provide an important type of substrate for constructing a variety of hybrid nanomaterials. However, their intrinsic chemistry-inert surfaces make it indispensable to pre-functionalize them prior to immobilizing additional components onto their surfaces. Currently developed strategies for functionalizing CNSs include covalent and non-covalent approaches. Conventional covalent treatments often damage the structure integrity of carbon surfaces and adversely affect their physical properties. In contrast, the non-covalent approach offers a non-destructive way to modify CNSs with desired functional surfaces, while reserving their intrinsic properties. Thus far, a number of surface modifiers including aromatic compounds, small-molecular surfactants, amphiphilic polymers, and biomacromolecules have been developed to non-covalently functionalize CNS surfaces. Mediated by these surface modifiers, various functional components such as organic species and inorganic nanoparticles were further decorated onto their surfaces, resulting in versatile carbon-based hybrid nanomaterials with broad applications in chemical engineering and biomedical areas. In this review, the recent advances in the generation of such hybrid nanostructures based on non-covalently functionalized CNSs will be reviewed.

Multimedia and Understanding: Expert and Novice Responses To Different Representations of Chemical Phenomena.

ERIC Educational Resources Information Center

Kozma, Robert B.; Russell, Joel

1997-01-01

Examines how professional chemists and undergraduate chemistry students respond to chemistry-related video segments, graphs, animations, and equations. Discusses the role that surface features of representations play in the understanding of chemistry. Contains 36 references. (DDR)

Tailored functionalization of iron oxide nanoparticles for MRI, drug delivery, magnetic separation and immobilization of biosubstances.

PubMed

Hola, Katerina; Markova, Zdenka; Zoppellaro, Giorgio; Tucek, Jiri; Zboril, Radek

2015-11-01

In this critical review, we outline various covalent and non-covalent approaches for the functionalization of iron oxide nanoparticles (IONPs). Tuning the surface chemistry and design of magnetic nanoparticles are described in relation to their applicability in advanced medical technologies and biotechnologies including magnetic resonance imaging (MRI) contrast agents, targeted drug delivery, magnetic separations and immobilizations of proteins, enzymes, antibodies, targeting agents and other biosubstances. We review synthetic strategies for the controlled preparation of IONPs modified with frequently used functional groups including amine, carboxyl and hydroxyl groups as well as the preparation of IONPs functionalized with other species, e.g., epoxy, thiol, alkane, azide, and alkyne groups. Three main coupling strategies for linking IONPs with active agents are presented: (i) chemical modification of amine groups on the surface of IONPs, (ii) chemical modification of bioactive substances (e.g. with fluorescent dyes), and (iii) the activation of carboxyl groups mainly for enzyme immobilization. Applications for drug delivery using click chemistry linking or biodegradable bonds are compared to non-covalent methods based on polymer modified condensed magnetic nanoclusters. Among many challenges, we highlight the specific surface engineering allowing both therapeutic and diagnostic applications (theranostics) of IONPs and magnetic/metallic hybrid nanostructures possessing a huge potential in biocatalysis, green chemistry, magnetic bioseparations and bioimaging. Copyright © 2015 Elsevier Inc. All rights reserved.

Synergistic responses of superficial chemistry and micro topography of titanium created by wire-type electric discharge machining.

PubMed

Kataoka, Yu; Tamaki, Yukimichi; Miyazaki, Takashi

2011-01-01

Wire-type electric discharge machining has been applied to the manufacture of endosseous titanium implants as this computer associated technique allows extremely accurate complex sample shaping with an optimal micro textured surface during the processing. Since the titanium oxide layer is sensitively altered by each processing, the authors hypothesized that this technique also up-regulates biological responses through the synergistic effects of the superficial chemistry and micro topography. To evaluate the respective in vitro cellular responses on the superficial chemistry and micro topography of titanium surface processed by wire-type electric discharge, we used titanium-coated epoxy resin replica of the surface. An oxide layer on the titanium surface processed by wire-type electric discharge activated the initial responses of osteoblastic cells through an integrin-mediated mechanism. Since the mRNA expression of ALP on those replicas was up-regulated compared to smooth titanium samples, the micro topography of a titanium surface processed by wire-type electric discharge promotes the osteogenic potential of cells. The synergistic response of the superficial chemistry and micro topography of titanium processed by wire-type electric discharge was demonstrated in this study.

Stabilized Lithium-Metal Surface in a Polysulfide-Rich Environment of Lithium-Sulfur Batteries.

PubMed

Zu, Chenxi; Manthiram, Arumugam

2014-08-07

Lithium-metal anode degradation is one of the major challenges of lithium-sulfur (Li-S) batteries, hindering their practical utility as next-generation rechargeable battery chemistry. The polysulfide migration and shuttling associated with Li-S batteries can induce heterogeneities of the lithium-metal surface because it causes passivation by bulk insulating Li2S particles/electrolyte decomposition products on a lithium-metal surface. This promotes lithium dendrite formation and leads to poor lithium cycling efficiency with complicated lithium surface chemistry. Here, we show copper acetate as a surface stabilizer for lithium metal in a polysulfide-rich environment of Li-S batteries. The lithium surface is protected from parasitic reactions with the organic electrolyte and the migrating polysulfides by an in situ chemical formation of a passivation film consisting of mainly Li2S/Li2S2/CuS/Cu2S and electrolyte decomposition products. This passivation film also suppresses lithium dendrite formation by controlling the lithium deposition sites, leading to a stabilized lithium surface characterized by a dendrite-free morphology and improved surface chemistry.

Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

PubMed

Lee, Austin W H; Gates, Byron D

2017-09-05

Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

Comparative hazard analysis and toxicological modeling of diverse nanomaterials using the embryonic zebrafish (EZ) metric of toxicity

NASA Astrophysics Data System (ADS)

Harper, Bryan; Thomas, Dennis; Chikkagoudar, Satish; Baker, Nathan; Tang, Kaizhi; Heredia-Langner, Alejandro; Lins, Roberto; Harper, Stacey

2015-06-01

The integration of rapid assays, large datasets, informatics, and modeling can overcome current barriers in understanding nanomaterial structure-toxicity relationships by providing a weight-of-the-evidence mechanism to generate hazard rankings for nanomaterials. Here, we present the use of a rapid, low-cost assay to perform screening-level toxicity evaluations of nanomaterials in vivo. Calculated EZ Metric scores, a combined measure of morbidity and mortality in developing embryonic zebrafish, were established at realistic exposure levels and used to develop a hazard ranking of diverse nanomaterial toxicity. Hazard ranking and clustering analysis of 68 diverse nanomaterials revealed distinct patterns of toxicity related to both the core composition and outermost surface chemistry of nanomaterials. The resulting clusters guided the development of a surface chemistry-based model of gold nanoparticle toxicity. Our findings suggest that risk assessments based on the size and core composition of nanomaterials alone may be wholly inappropriate, especially when considering complex engineered nanomaterials. Research should continue to focus on methodologies for determining nanomaterial hazard based on multiple sub-lethal responses following realistic, low-dose exposures, thus increasing the availability of quantitative measures of nanomaterial hazard to support the development of nanoparticle structure-activity relationships.

The physics of water droplets on surfaces: exploring the effects of roughness and surface chemistry

NASA Astrophysics Data System (ADS)

Eid, K. F.; Panth, M.; Sommers, A. D.

2018-03-01

This paper explores the fluid property commonly called surface tension, its effect on droplet shape and contact angle, and the major influences of contact angle behaviour (i.e. surface roughness and surface chemistry). Images of water droplets placed on treated copper surfaces are used to measure the contact angles between the droplets and the surface. The surface wettability is manipulated either by growing a self-assembled monolayer on the surface to make it hydrophobic or by changing the surface roughness. The main activities in this experiment, then, are (1) preparing and studying surfaces with different surface wettability and roughness; (2) determining the shape and contact angles of water droplets on these surfaces; and (3) demonstrating the spontaneous motion of water droplets using surface tension gradients.

Fast method for reactor and feature scale coupling in ALD and CVD

DOEpatents

Yanguas-Gil, Angel; Elam, Jeffrey W.

2017-08-08

Transport and surface chemistry of certain deposition techniques is modeled. Methods provide a model of the transport inside nanostructures as a single-particle discrete Markov chain process. This approach decouples the complexity of the surface chemistry from the transport model, thus allowing its application under general surface chemistry conditions, including atomic layer deposition (ALD) and chemical vapor deposition (CVD). Methods provide for determination of determine statistical information of the trajectory of individual molecules, such as the average interaction time or the number of wall collisions for molecules entering the nanostructures as well as to track the relative contributions to thin-film growth of different independent reaction pathways at each point of the feature.

Probing the nanoscale interaction forces and elastic properties of organic and inorganic materials using force-distance (F-D) spectroscopy

NASA Astrophysics Data System (ADS)

Vincent, Abhilash

Due to their therapeutic applications such as radical scavenging, MRI contrast imaging, Photoluminescence imaging, drug delivery, etc., nanoparticles (NPs) have a significant importance in bio-nanotechnology. The reason that prevents the utilizing NPs for drug delivery in medical field is mostly due to their biocompatibility issues (incompatibility can lead to toxicity and cell death). Changes in the surface conditions of NPs often lead to NP cytotoxicity. Investigating the role of NP surface properties (surface charges and surface chemistry) on their interactions with biomolecules (Cells, protein and DNA) could enhance the current understanding of NP cytotoxicity. Hence, it is highly beneficial to the nanotechnology community to bring more attention towards the enhancement of surface properties of NPs to make them more biocompatible and less toxic to biological systems. Surface functionalization of NPs using specific ligand biomolecules have shown to enhance the protein adsorption and cellular uptake through more favorable interaction pathways. Cerium oxide NPs (CNPs also known as nanoceria) are potential antioxidants in cell culture models and understanding the nature of interaction between cerium oxide NPs and biological proteins and cells are important due to their therapeutic application (especially in site specific drug delivery systems). The surface charges and surface chemistry of CNPs play a major role in protein adsorption and cellular uptake. Hence, by tuning the surface charges and by selecting proper functional molecules on the surface, CNPs exhibiting strong adhesion to biological materials can be prepared. By probing the nanoscale interaction forces acting between CNPs and protein molecules using Atomic Force Microscopy (AFM) based force-distance (F-D) spectroscopy, the mechanism of CNP-protein adsorption and CNP cellular uptake can be understood more quantitatively. The work presented in this dissertation is based on the application of AFM in studying the interaction forces as well as the mechanical properties of nanobiomaterials. The research protocol employed in the earlier part of the dissertation is specifically aimed to understand the operation of F-D spectroscopy technique. The elastic properties of thin films of silicon dioxide NPs were investigated using F-D spectroscopy in the high force regime of few 100 nN to 1 microN. Here, sol-gel derived porous nanosilica thin films of varying surface morphology, particle size and porosity were prepared through acid and base catalyzed process. AFM nanoindentation experiments were conducted on these films using the F-D spectroscopy mode and the nanoscale elastic properties of these films were evaluated. The major contribution of this dissertation is a study exploring the interaction forces acting between CNPs and transferrin proteins in picoNewton scale regime using the force-distance spectroscopy technique. This study projects the importance of obtaining appropriate surface charges and surface chemistry so that the NP can exhibit enhanced protein adsorption and NP cellular uptake.

Surface studies relevant to silicon carbide chemical vapor deposition

NASA Technical Reports Server (NTRS)

Stinespring, C. D.; Wormhoudt, J. C.

1989-01-01

Reactions of C2H4, C3H8, and CH4 on the Si(111) surface and C2H4 on the Si(100) surface were investigated for surface temperatures in the range of 1062-1495 K. Results led to the identification of the reaction products, a characterization of the solid-state transport process, a determination of the nucleation mechanism and growth kinetics, and an assessment of orientation effects. Based on these results and on the modeling studies of Stinespring and Wormhoudt (1988) on the associated gas phase chemistry, a physical model for the two-step beta-SiC CVD process is proposed.

Photogenerated Lectin Sensors Produced by Thiol-Ene/Yne Photo-Click Chemistry in Aqueous Solution

PubMed Central

Norberg, Oscar; Lee, Irene H.; Aastrup, Teodor; Yan, Mingdi; Ramström, Olof

2012-01-01

The photoinitiated radical reactions between thiols and alkenes/alkynes (thiol-ene and thiol-yne chemistry) have been applied to a functionalization methodology to produce carbohydrate-presenting surfaces for analyses of biomolecular interactions. Polymer-coated quartz surfaces were functionalized with alkenes or alkynes in a straightforward photochemical procedure utilizing perfluorophenylazide (PFPA) chemistry. The alkene/alkyne surfaces were subsequently allowed to react with carbohydrate thiols in water under UV-irradiation. The reaction can be carried out in a drop of water directly on the surface without photoinitiator and any disulfide side products were easily washed away after the functionalization process. The resulting carbohydrate-presenting surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with recurring injections of selected lectins with intermediate regeneration steps using low pH buffer. The resulting methodology proved fast, efficient and scalable to high-throughput analysis formats, and the produced surfaces showed significant protein binding with expected selectivities of the lectins used in the study. PMID:22341757

Surface chemistry of carbon dioxide revisited

NASA Astrophysics Data System (ADS)

Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas

2016-12-01

This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas-solid interface analysis, the present work goes further by describing surface-CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

Characterizing the Role of Nanoparticle Design on Tumor Transport and Stability in the Extracellular Environment

NASA Astrophysics Data System (ADS)

Albanese, Alexandre

Nanotechnology has emerged as an exciting strategy for the delivery of diagnostic and therapeutic agents into established tumors. Advancements in nanomaterial synthesis have generated an extensive number of nanoparticle designs made from different materials. Unfortunately, it remains impossible to predict a design's effectiveness for in vivo tumor accumulation. Little is known about how a nanoparticle's morphology and surface chemistry affect its interactions with cells and proteins inside the tumor tissue. This thesis focuses on the development of in vitro experimental tools to evaluate how nanoparticle design affects transport in a three-dimensional tumor tissue and stability in the tumor microenvironment. Nanoparticle transport was evaluated using a novel 'tumor-on-a-chip' system where multicellular tumor spheroids were immobilized in a microfluidic channel. This setup created a three-dimensional tumor environment displaying physiological cell density, extracellular matrix organization, and interstitial flow rates. The tumor-on-a-chip demonstrated that accumulation of nanoparticles was limited to diameters below 110 nm and was improved by receptor targeting. Nanoparticle stability in the tumor microenvironment was evaluated using media isolated from different tumor cell lines. Nanoparticle diameter and surface chemistry were important determinants of stability in cancer cell-conditioned media. Small nanoparticles with unstable surface chemistries adsorbed cellular proteins on their surface and were prone to aggregation. Nanoparticle aggregation altered cellular interactions leading to changes in cell uptake. Using a novel technique to generate different aggregate sizes possessing a uniform surface composition, it was determined that aggregation can change receptor affinity, cell internalization mechanisms and sub-cellular sequestration patterns. Data from this thesis characterize the behavior of nanoparticles within modeled tumor environments and provide some preliminary design guidelines for maximizing nanoparticle tumor accumulation. This work highlights the importance of characterizing nano-bio interactions for engineering successful nanomaterial-based delivery systems.

Fundamental interfacial studies of advanced solid lubricants and their operating environments

NASA Astrophysics Data System (ADS)

Gilley, Kevin

Solid lubricants are a class of materials that are utilized in applications and environments where traditional lubrication schemes cannot be implemented. A variety of materials display solid lubrication, and in this study a number of solid lubricants were investigated. Firstly, electrolessly deposited nickel boride alloys were annealed at different temperatures under a flow of oxygen. The surface chemistry, friction, and wear behavior of the coating were then investigated. It was found that when annealed above 550°C the coatings had a dramatic change in surface chemistry, where the Ni 3B had formed a thick layer of B2O3 on the surface. This oxide then reacted at ambient temperatures with moist air to form the lubricious compound H3BO3. This led to a coefficient of friction below 0.1 and a slight increase of the wear rate from 10 -8 mm3/Nm to 10-7 mm3/Nm. Secondly, the surface chemistry of advanced MoS2 based coatings that had been exposed to low earth orbit was investigated. It was found that this exposure produced the complete oxidation of the coatings. Also, exposure to the unique space environments resulted in the deposition of large amounts of contaminant SiO2 on the surface. Lastly the tribological properties of single crystal cadmium sulfide were investigated. There is nearly no knowledge of the tribological activity of cadmium sulfide in the literature, so the study was performed as an initial investigation into the material. It was discovered that cadmium sulfide did not show low friction, with a coefficient of friction of approximately 0.25, but did show low wear, with a wear rate of approximately 3x10-7 mm3/Nm.

Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

NASA Astrophysics Data System (ADS)

Hoang, Michelle V.; Chung, Hyun-Joong; Elias, Anastasia L.

2016-10-01

Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm-1) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ~0.2 N mm-1 (method 1) and  >0.3 N mm-1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication.

Surface modification of model hydrogel contact lenses with hyaluronic acid via thiol-ene "click" chemistry for enhancing surface characteristics.

PubMed

Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

2017-10-01

Discontinuation of contact lens wear as a result of ocular dryness and discomfort is extremely common; as many as 26% of contact lens wearers discontinue use within the first year. While patients are generally satisfied with conventional hydrogel lenses, improving on-eye comfort continues to remain a goal. Surface modification with a biomimetic, ocular friendly hydrophilic layer of a wetting agent is hypothesized to improve the interfacial interactions of the contact lens with the ocular surface. In this work, the synthesis and characterization of poly(2-hydroxyethyl methacrylate) surfaces grafted with a hydrophilic layer of hyaluronic acid are described. The immobilization reaction involved the covalent attachment of thiolated hyaluronic acid (20 kDa) on acrylated poly(2-hydroxyethyl methacrylate) via nucleophile-initiated Michael addition thiol-ene "click" chemistry. The surface chemistry of the modified surfaces was analyzed by Fourier transform infrared spectroscopy-attenuated total reflectance and X-ray photoelectron spectroscopy. The appearance of N (1s) and S (2p) peaks on the low resolution X-ray photoelectron spectroscopy spectra confirmed successful immobilization of hyaluronic acid. Grafting hyaluronic acid to the poly(2-hydroxyethyl methacrylate) surfaces decreased the contact angle, the dehydration rate, and the amount of nonspecific sorption of lysozyme and albumin in comparison to pristine hydrogel materials, suggesting the development of more wettable surfaces with improved water-retentive and antifouling properties, while maintaining optical transparency (>92%). In vitro testing also showed excellent viability of human corneal epithelial cells with the hyaluronic acid-grafted poly(2-hydroxyethyl methacrylate) surfaces. Hence, surface modification with hyaluronic acid via thiol-ene "click" chemistry could be useful in improving contact lens surface properties, potentially alleviating symptoms of contact lens related dryness and discomfort during wear.

Challenges in Teaching "Colloid and Surface Chemistry"--A Danish Experience

ERIC Educational Resources Information Center

Kontogeorgis, Georgios M.; Vigild, Martin E.

2009-01-01

Seven years ago we were asked, as one of our first teaching duties at the Technical University of Denmark (DTU), to teach a 5 ECTS point course on "Colloid and Surface Chemistry". The topic is itself at the same time exciting and demanding, largely due to its multidisciplinary nature. Several "local" requirements posed…

Trends in Surface Water Chemistry in Acidified Areas in Europe and North America from 1990 to 2008

EPA Science Inventory

Acidification of lakes and rivers is still an environmental concern despite reduced emissions of acidifying compounds. We analyzed trends in surface water chemistry of 173 acid-sensitive sites from 12 regions in Europe and North America. In 11 of 12 regions, non-marine sulphate (...

The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry

NASA Astrophysics Data System (ADS)

Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R.; Vasilev, Krasimir; Hayball, John D.

2016-05-01

Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes.

Environmental chemistry at vapor/water interfaces: insights from vibrational sum frequency generation spectroscopy.

PubMed

Jubb, Aaron M; Hua, Wei; Allen, Heather C

2012-01-01

The chemistry that occurs at surfaces has been an intense area of study for many years owing to its complexity and importance in describing a wide range of physical phenomena. The vapor/water interface is particularly interesting from an environmental chemistry perspective as this surface plays host to a wide range of chemistries that influence atmospheric and geochemical interactions. The application of vibrational sum frequency generation (VSFG), an inherently surface-specific, even-order nonlinear optical spectroscopy, enables the direct interrogation of various vapor/aqueous interfaces to elucidate the behavior and reaction of chemical species within the surface regime. In this review we discuss the application of VSFG to the study of a variety of atmospherically important systems at the vapor/aqueous interface. Chemical systems presented include inorganic ionic solutions prevalent in aqueous marine aerosols, small molecular solutes, and long-chain fatty acids relevant to fat-coated aerosols. The ability of VSFG to probe both the organization and reactions that may occur for these systems is highlighted. A future perspective toward the application of VSFG to the study of environmental interfaces is also provided.

Adsorption of Phosphate on Goethite: An Undergraduate Research Laboratory Project

ERIC Educational Resources Information Center

Tribe, Lorena; Barja, Beatriz C.

2004-01-01

A laboratory experiment on the adsorption of phosphate on goethite is presented, which also includes discussion on surface properties, interfaces, acid-base equilibrium, molecular structure and solid state chemistry. It was seen that many students were able to produce qualitatively correct results for a complex system of real interest and they…

Peptide interfaces with graphene: an emerging intersection of analytical chemistry, theory, and materials.

PubMed

Russell, Shane R; Claridge, Shelley A

2016-04-01

Because noncovalent interface functionalization is frequently required in graphene-based devices, biomolecular self-assembly has begun to emerge as a route for controlling substrate electronic structure or binding specificity for soluble analytes. The remarkable diversity of structures that arise in biological self-assembly hints at the possibility of equally diverse and well-controlled surface chemistry at graphene interfaces. However, predicting and analyzing adsorbed monolayer structures at such interfaces raises substantial experimental and theoretical challenges. In contrast with the relatively well-developed monolayer chemistry and characterization methods applied at coinage metal surfaces, monolayers on graphene are both less robust and more structurally complex, levying more stringent requirements on characterization techniques. Theory presents opportunities to understand early binding events that lay the groundwork for full monolayer structure. However, predicting interactions between complex biomolecules, solvent, and substrate is necessitating a suite of new force fields and algorithms to assess likely binding configurations, solvent effects, and modulations to substrate electronic properties. This article briefly discusses emerging analytical and theoretical methods used to develop a rigorous chemical understanding of the self-assembly of peptide-graphene interfaces and prospects for future advances in the field.

Chemistry of Protostellar Envelopes and Disks

NASA Astrophysics Data System (ADS)

Flores Rivera, Lizxandra; Terebey, Susan; Willacy, Karen

2018-06-01

Molecule formation is dynamic during the protostar collapse phase, driven by changes in temperature, density, and UV radiation as gas and dust flows from the envelope onto the forming protoplanetary disk. In this work, we compare physical models based on two different collapse solutions. We modeled the chemistry (created by Karen Willacy) for C18O to see how its abundance changes over time using as primary input parameters the temperature and density profile that were produced by the dust Radiative Transfer (MCRT) model called HOCHUNK3D from Whitney (2003). Given this model, we produce synthetic line emission maps from L1527 IRS to simulate the Class 0/I protostar L1527 IRS using RADMC3D code and compare them with previous observations from ALMA. High concentrations of gas phase molecules of C18O are found within the 20 AU in areas in the envelope that are close to the surface of the disk. In the outermost part of the disk surface, the C18O freezes out beyond 400 AU, showing a much reduced abundance where the temperature profile drops down below 25 K. In cold regions, the radiation field plays an important role in the chemistry.

Role of monomer sequence and backbone chemistry in polypeptoid copolymers for marine antifouling coatings

NASA Astrophysics Data System (ADS)

Patterson, Anastasia; Wenning, Brandon; Rizis, Georgios; Calabrese, David; Finlay, John; Franco, Sofia; Clare, Anthony; Kramer, Edward; Ober, Christopher; Segalman, Rachel

The design rules elucidated in this work suggest that antifouling coatings bearing pendant peptoid side chains perform better overall in marine fouling tests than those with peptide side chains, with extremely low attachment of N. incerta and high removal of U. linza. This difference in performance is likely due to the lack of a hydrogen bond donor in the peptoid backbone. Furthermore, we show that the bulk polymer material of these hierarchical coatings (based on PEO or PDMS) plays a key role in determining both surface presentation and fouling release performance. We demonstrate these trends utilizing a modular coating based on a triblock copolymer consisting of polystyrene and a vinyl-containing midblock, to which sequence-defined pendant oligomers (peptides or peptoids with sequences of oligo-PEO and fluoroalkyl groups) are attached via thiol-ene ``click'' chemistry. Surface presentation was analyzed with X-ray photoelectron spectroscopy and captive bubble water contact angle, and antifouling performance was evaluated with attachment and removal bioassays of the marine macroalga U. linza and diatom N. incerta. NSF GRFP and ONR PECASE.

Surface design for controlled crystallization: the role of surface chemistry and nanoscale pores in heterogeneous nucleation.

PubMed

Diao, Ying; Myerson, Allan S; Hatton, T Alan; Trout, Bernhardt L

2011-05-03

Current industrial practice for control of primary nucleation (nucleation from a system without pre-existing crystalline matter) during crystallization from solution involves control of supersaturation generation, impurity levels, and solvent composition. Nucleation behavior remains largely unpredictable, however, due to the presence of container surfaces, dust, dirt, and other impurities that can provide heterogeneous nucleation sites, thus making the control and scale-up of processes that depend on primary nucleation difficult. To develop a basis for the rational design of surfaces to control nucleation during crystallization from solution, we studied the role of surface chemistry and morphology of various polymeric substrates on heterogeneous nucleation using aspirin as a model compound. Nucleation induction time statistics were utilized to investigate and quantify systematically the effectiveness of polymer substrates in inducing nucleation. The nucleation induction time study revealed that poly(4-acryloylmorpholine) and poly(2-carboxyethyl acrylate), each cross-linked by divinylbenzene, significantly lowered the nucleation induction time of aspirin while the other polymers were essentially inactive. In addition, we found the presence of nanoscopic pores on certain polymer surfaces led to order-of-magnitude faster aspirin nucleation rates when compared with surfaces without pores. We studied the preferred orientation of aspirin crystals on polymer films and found the nucleation-active polymer surfaces preferentially nucleated the polar facets of aspirin, guided by hydrogen bonds. A model based on interfacial free energies was also developed which predicted the same trend of polymer surface nucleation activities as indicated by the nucleation induction times.

Characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems.

PubMed

Bryant, M; Ward, M; Farrar, R; Freeman, R; Brummitt, K; Nolan, J; Neville, A

2014-04-01

This study presents the characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems. Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FI-IR) were utilised in order to assess the surface morphology of retrieved Metal-on-Metal Total Hip Replacements and surface chemistry of the films found on the surface. Gross slip, plastic deformation and directionality of the surface were extensively seen on the proximal surfaces of the retrievals. A more corrosive phenomenon was observed in the distal regions of the stem, demonstrating a seemingly intergranular attack. Tribochemical reactions were seen to occur within the stem-cement interfaces with tribofilms being observed on the femoral stem and counterpart PMMA bone cement. XPS, TEM-EDX and FT-IR analyses demonstrated that the films present in the stem surfaces were a complex mixture of chromium oxide and amorphous organic material. A comparison between current experimental and clinical literature has been conducted and findings from this study demonstrate that the formation and chemistry of films are drastically influenced by the type of wear or degradation mechanism. Films formed in the stem-cement interface are thought to further influence the biological environment outside the stem-cement interface due to the formation of Cr and O rich films within the interface whilst Co is free to migrate away. © 2013 Elsevier Ltd. All rights reserved.

Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films

DOE PAGES

Hong, Wesley T.; Stoerzinger, Kelsey; Crumlin, Ethan J.; ...

2016-02-11

Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr 2Co 2O 5 (SCO) epitaxial thin films with different crystallographic orientations. Detailedmore » analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La 0.8Sr 0.2CoO 3-δ thin films by SCO surface particles observed previously.« less

Long-term changes in soil and stream chemistry across an acid deposition gradient in the northeastern United States

USGS Publications Warehouse

Siemion, Jason; McHale, Michael; Lawrence, Gregory B.; Burns, Douglas A.; Antidormi, Michael

2018-01-01

Declines in acidic deposition across Europe and North America have led to decreases in surface water acidity and signs of chemical recovery of soils from acidification. To better understand the link between recovery of soils and surface waters, chemical trends in precipitation, soils, and streamwater were investigated in three watersheds representing a depositional gradient from high to low across the northeastern United States. Significant declines in concentrations of H+ (ranging from −1.2 to −2.74 microequivalents [μeq] L−1 yr−1), NO3− (ranging from −0.6 to −0.84 μeq L−1 yr−1), and SO42− (ranging from −0.95 to −2.13 μeq L−1 yr−1) were detected in precipitation in the three watersheds during the period 1999 to 2013. Soil chemistry in the A horizon of the watershed with the greatest decrease in deposition showed significant decreases in exchangeable Al and increases in exchangeable bases. Soil chemistry did not significantly improve during the study in the other watersheds, and base saturation in the Oa and upper B horizons significantly declined in the watershed with the smallest decrease in deposition. Streamwater SO42−concentrations significantly declined in all three streams (ranging from −2.01 to −2.87 μeq L−1 yr−1) and acid neutralizing capacity increased (ranging from 1.38 to 1.60 μeq L−1 yr−1) in the two streams with the greatest decreases in deposition. Recovery of soils has likely been limited by decades of acid deposition that have leached base cations from soils with base-poor parent material.

Partner-facilitating transmembrane penetration of nanoparticles: a biological test in silico.

PubMed

Wang, W; Yang, R; Zhang, F; Yuan, B; Yang, K; Ma, Y

2018-06-21

Transmembrane penetration of nanoparticles (NPs) promises an effective pathway for cargo delivery into cells, and offers the possibility of organelle-specific targeting for biomedical applications. However, a full understanding of the underlying NP-membrane interaction mechanism is still lacking. In this work, the membrane penetration behavior of NPs is statistically analyzed based on the simulations of over 2.2 ms, which are performed with dissipative particle dynamics (DPD). Influences from multiple factors including the NP concentration, shape and surface chemistry are taken into account. It is interesting to find that, the introduction of a partner NP would greatly facilitate the transmembrane penetration of a host spherical NP. This is probably due to the membrane-mediated cooperation between the NPs. Moreover, the proper selection of a partner NP with specific surface chemistry is of great significance. For example, the best partner for a hydrophilic NP to achieve transmembrane penetration is a Janus-like one, in comparison with the hydrophilic, hydrophobic or randomly surface-decorated NPs. Furthermore, such a partner-facilitating effect in NP translocation also works for a shaped NP although less pronounced. Our results are helpful for a better understanding of the complicated nano-bio interactions, and offer a practical guide to the NP-based drug delivery strategy with high efficiency.

Interfacing Nanoparticles and Biology: New Strategies for Biomedicine

PubMed Central

Tonga, Gulen Yesilbag; Saha, Krishnendu; Rotello, Vincent M.

2014-01-01

The exterior surface of nanoparticles (NPs) dictates the behavior of these systems with the outside world. Understanding the interactions of NP surface functionality with biosystems enables the design and fabrication of effective platforms for therapeutics, diagnostics, and imaging agents. In this review, we highlight the role of chemistry in the engineering of nanomaterials, focusing on the fundamental role played by surface chemistry in controlling the interaction of NPs with proteins and cells. PMID:24105763

Biocompatible Surface Chemistry Manipulation of Gold Nanorods Preserves Optical Properties for Bio-Imaging Applications

DTIC Science & Technology

2015-12-18

3. DATES COVERED (From - To) March 2014 – Sept 2014 4. TITLE AND SUBTITLE Biocompatible surface chemistry manipulation of gold nanorods preserves...Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable...intracellular aggregation of MTAB-TA GNRs, and identify them as prime andidates for use in nanobased bio-imaging applications. 15. SUBJECT TERMS Gold

Mars Atmospheric Chemistry and Astrobiology Workshop Summary

NASA Astrophysics Data System (ADS)

Allen, M.; Wennberg, P.

2002-09-01

The Mars Atmospheric Chemistry and Astrobiology (MACA) Workshop was held on the California Institute of Technology campus December 17-18, 2001. The prime objective of the workshop was to consider whether extant life beneath the surface, if it exists, would be in contact with the atmosphere and introduce a detectable signature in the atmosphere. To answer this question, the workshop also explored how well we understood the abiotic chemistry of the current atmosphere and other drivers of atmospheric composition (volcanoes, surface-atmosphere interactions, escape). The conclusions from this workshop will be presented.

Ionic-Liquid-Infused Nanostructures as Repellent Surfaces.

PubMed

Galvan, Yaraset; Phillips, Katherine R; Haumann, Marco; Wasserscheid, Peter; Zarraga, Ramon; Vogel, Nicolas

2018-06-12

In order to prepare lubricant-infused repellent coatings on silica nanostructures using low vapor pressure ionic liquids as lubricants, we study the wetting behavior of a set of imidazolium-based ionic liquids with different alkyl side chains as a function of the applied surface functionalities. We take advantage of the structural color of inverse opals prepared from a colloidal coassembly technique to study the infiltration of ionic liquids into these nanoporous structures. We find that the more hydrophobic ionic liquids with butyl and hexyl side chains can completely infiltrate inverse opals functionalized with mixed self-assembled monolayers composed of imidazole groups and aliphatic hydrocarbon chains, which we introduce via silane chemistry. These molecular species reflect the chemical nature of the ionic liquid, thereby increasing the affinity between the liquid and solid surface. The mixed surface chemistry provides sufficiently small contact angles with the ionic liquid to infiltrate the nanopores while maximizing the contact angle with water. As a result, the mixed monolayers enable the design of a stable ionic liquid/solid interface that is able to repel water as a test liquid. Our results underline the importance of matching chemical affinities to predict and control the wetting behavior in complex, multiphase systems.

From crystal chemistry to colloid stability

NASA Astrophysics Data System (ADS)

Gilbert, B.; Burrows, N.; Penn, R. L.

2008-12-01

Aqueous suspensions of ferrihydrite nanoparticles form a colloid with properties that can be understood using classical theories but which additionally exhibit the distinctive phenomenon of nanocluster formation. While use of in situ light and x-ray scattering methods permit the quantitative determination of colloid stability, interparticle interactions, and cluster or aggregate geometry, there are currently few approaches to predict the colloidal behavior of mineral nanoparticles. A longstanding goal of aqueous geochemistry is the rationalization and prediction of the chemical properties of hydrated mineral interfaces from knowledge of interface structure at the molecular scale. Because interfacial acid-base reactions typically lead to the formation of a net electrostatic charge at the surfaces of oxide, hydroxide, and oxyhydroxide mineral surfaces, quantitative descriptions of this behavior have the potential to permit the prediction of long-range interactions between mineral particles. We will evaluate the feasibility of this effort by constructing a model for surface charge formation for ferrihydrite that combines recent insights into the crystal structure of this phase and proposed methods for estimating the pKa of acidic surface groups. We will test the ability of this model to predict the colloidal stability of ferrihydrite suspensions as a function of solution chemistry.

Effects of hydrophobic helix length and side chain chemistry on biomimicry in peptoid analogues of SP-C.

PubMed

Brown, Nathan J; Wu, Cindy W; Seurynck-Servoss, Shannon L; Barron, Annelise E

2008-02-12

The hydrophobic proteins of lung surfactant (LS), SP-B and SP-C, are critical constituents of an effective surfactant replacement therapy for the treatment of respiratory distress syndrome. Because of concerns and difficulties associated with animal-derived surfactants, recent investigations have focused on the creation of synthetic analogues of the LS proteins. However, creating an accurate mimic of SP-C that retains its biophysical surface activity is extraordinarily challenging given the lipopeptide's extreme hydrophobicity and propensity to misfold and aggregate. One successful approach that overcomes these difficulties is the use of poly-N-substituted glycines, or peptoids, to mimic SP-C. To develop a non-natural, bioactive mimic of SP-C and to investigate the effects of side chain chemistry and length of the helical hydrophobic region, we synthesized, purified, and performed in vitro testing of two classes of peptoid SP-C mimics: those having a rigid alpha-chiral aromatic helix and those having a biomimetic alpha-chiral aliphatic helix. The length of the two classes of mimics was also systematically altered. Circular dichroism spectroscopy gave evidence that all of the peptoid-based mimics studied here emulated SP-C's secondary structure, forming stable helical structures in solution. Langmuir-Wilhelmy surface balance, fluorescence microscopy, and pulsating bubble surfactometry experiments provide evidence that the aromatic-based SP-C peptoid mimics, in conjunction with a synthetic lipid mixture, have superior surface activity and biomimetic film morphology in comparison to the aliphatic-based mimics and that there is an increase in surface activity corresponding to increasing helical length.

Mechanism of wear and tribofilm formation with ionic liquids and ashless antiwear additives

NASA Astrophysics Data System (ADS)

Sharma, Vibhu

Increasingly stringent government regulation on emissions (EPA Emissions Standard Reference Guide and latest CAFE standards requiring an average fuel economy of 54.5 mpg (combined cars and trucks) by 2025) impose significant challenges to the automotive and lubricant industries calling for the development and implementation of lower viscosity ILSAC GF-5&6 and API-CJ4&5 oils which further limit the amount of SAPS and deposits in engines. Development of additives that result in lower ash content, volatility and anti-wear property plays a crucial role in being able to reach these standards. The current industrial additive technology i.e. zinc dialkyldithiophosphate (ZDDP) forms harmful deposits on catalytic convertor due to the volatility of Zn, S and P which, impairs its functionality and consequently results in higher emission from vehicles. In this research work, ionic liquids (IL's) that are non-volatile have been studied as new generation environment friendly antiwear additives along with other ashless anti-wear additives including boron based additives to overcome the current challenges of improving the fuel efficiency and reducing the amount of hazardous emissions. The goal of this thesis work is to study the tribological performance of selected IL's and develop a comprehensive understating of IL's chemistry and its consequences to their friction and wear outcomes. As first approach, various P, S and F based ionic liquids are studied for their tribological properties by analyzing the friction and wear results generated using standard tribological experiments. Following this, advanced surface characterization techniques such as X-ray absorption near edge structure (XANES) spectroscopy, SEM, Nano-indentation, SPM techniques are used to investigate the chemical-mechanical properties of the antiwear films. Results indicate that the tribological properties of ionic liquids depend on their solubility in base oil (BO) as well as their chemical interaction with the rubbing surfaces. To address the solubility issue of IL's in BO, ILs with longer alkyl chain structure were carefully selected which helped enhance the van der waals interaction between strongly polar ILs and non-polar base oil. The interaction of IL's with the metal surfaces was examined by analyzing the chemical-mechanical properties of the antiwear films formed. Results indicate that ionic liquids do react with the steel surfaces and form a protective antiwear film composed of iron polyphosphates i.e. short to medium chain length which results in improved wear protection. In addition, soluble boron additive (SB) chemistries were blended with ionic liquids to study the synergism between these two ashless antiwear chemistries. Addition of soluble boron additive (SB) to phosphorous based IL (P_DEHP) reduces the incubation time for antiwear film formation by forming boron oxide/boron phosphate film as early as the rubbing starts and subsequently a more durable iron phosphate film is formed providing long lasting wear protection. The synergistic interaction of boron chemistry with phosphorous based ionic liquids provides superior antiwear properties while eliminating volatile elements such as Zn and S from the additive technology.

Auger spectroscopy of fracture surfaces of ceramics

NASA Technical Reports Server (NTRS)

Marcus, H. L.; Harris, J. M.; Szalkowski, F. J.

1974-01-01

Results of Auger electron spectroscopy (AES) studies of fracture surfaces in a series of ceramic materials, including Al2O3, MgO, and Si3N4, which were formed using different processing techniques. AES on the fractured surface of a lunar sample is also discussed. Scanning electron micrograph fractography is used to relate the surface chemistry to the failure mode. Combined argon ion sputtering and AES studies demonstrate the local variations in chemistry near the fracture surface. The problems associated with doing AES in insulators are also discussed, and the experimental techniques directed toward solving them are described.

Smaller to larger biomolecule detection using a lab-built surface plasmon resonance based instrument

NASA Astrophysics Data System (ADS)

Lukose, J.; Kulal, V.; Chidangil, S.; Sinha, R. K.

2016-10-01

We have developed a low-cost surface plasmon resonance (SPR) instrument based on the Kretschmann configuration for biosensing applications. The fabricated instrument is capable of operating in both angular and intensity interrogation schemes. The proposed sensor has proved enormously versatile by detecting a range of analytes with low to high molecular weights. The refractive index based sensor has been used for detecting the variation in the concentration of the aqueous solution of glucose and glycerine. Real time immobilization of protein molecules, bovine serum albumin on a gold (Au) film surface, has also been detected using the SPR imaging technique. Alkanethiol functionalization of the Au surface was performed, and bovine serum albumin was immobilized onto the carboxyl functionalized surface using amine reactive cross linker chemistry. In future, the present approach can also be utilized for the selective detection of a wide range of target biomolecules with the help of specific capture probes, as well as for monitoring protein-drug interactions.

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

DOE PAGES

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; ...

2017-02-01

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

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

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Surface chemistry of gold nanorods: origin of cell membrane damage and cytotoxicity

NASA Astrophysics Data System (ADS)

Wang, Liming; Jiang, Xiumei; Ji, Yinglu; Bai, Ru; Zhao, Yuliang; Wu, Xiaochun; Chen, Chunying

2013-08-01

We investigated how surface chemistry influences the interaction between gold nanorods (AuNRs) and cell membranes and the subsequent cytotoxicity arising from them in a serum-free cell culture system. Our results showed that the AuNRs coated with cetyl trimethylammonium bromide (CTAB) molecules can generate defects in the cell membrane and induce cell death, mainly due to the unique bilayer structure of CTAB molecules on the surface of the rods rather than their charge. Compared to CTAB-capped nanorods, positively charged polyelectrolyte-coated, i.e. poly(diallyldimethyl ammonium chloride) (PDDAC), AuNRs show improved biocompatibility towards cells. Thus, the present results indicate that the nature of surface molecules, especially their packing structures on the surface of AuNRs rather than surface charge, play a more crucial role in determining cytotoxicity. These findings about interfacial interactions could also explain the effects of internalized AuNRs on the structures or functions of organelles. This study will help understanding of the toxic nature of AuNRs and guide rational design of the surface chemistry of AuNRs for good biocompatibility in pharmaceutical therapy.

Regenerative biomaterials that "click": simple, aqueous-based protocols for hydrogel synthesis, surface immobilization, and 3D patterning.

PubMed

Nimmo, Chelsea M; Shoichet, Molly S

2011-11-16

The click chemistry era has generated a library of versatile "spring-loaded" reactions that offer high yields, regio- and stereospecificity, and outstanding functional group tolerance. These powerful transformations are particularly advantageous for the design of sophisticated biomaterials that require high levels of precision and control, namely, materials that promote tissue regeneration such as hydrogels, 2D functionalized substrates, and 3D biomimetic scaffolds. In this review, the synthesis and application of regenerative biomaterials via click chemistry are summarized. Particular emphasis is placed on the copper(I)-catalyzed alkyne-azide cycloaddition, Diels-Alder cycloadditions, and thiol-click coupling.

Molecular Monolayers for Electrical Passivation and Functionalization of Silicon-Based Solar Energy Devices.

PubMed

Veerbeek, Janneke; Firet, Nienke J; Vijselaar, Wouter; Elbersen, Rick; Gardeniers, Han; Huskens, Jurriaan

2017-01-11

Silicon-based solar fuel devices require passivation for optimal performance yet at the same time need functionalization with (photo)catalysts for efficient solar fuel production. Here, we use molecular monolayers to enable electrical passivation and simultaneous functionalization of silicon-based solar cells. Organic monolayers were coupled to silicon surfaces by hydrosilylation in order to avoid an insulating silicon oxide layer at the surface. Monolayers of 1-tetradecyne were shown to passivate silicon micropillar-based solar cells with radial junctions, by which the efficiency increased from 8.7% to 9.9% for n + /p junctions and from 7.8% to 8.8% for p + /n junctions. This electrical passivation of the surface, most likely by removal of dangling bonds, is reflected in a higher shunt resistance in the J-V measurements. Monolayers of 1,8-nonadiyne were still reactive for click chemistry with a model catalyst, thus enabling simultaneous passivation and future catalyst coupling.

Surface immobilization of heparin on functional polyisobutylene-based thermoplastic elastomer as a potential artificial vascular graft

NASA Astrophysics Data System (ADS)

Wu, Yi-Bo; Li, Kang; Xiang, Dong; Zhang, Min; Yang, Dan; Zhang, Jin-Han; Mao, Jing; Wang, Hao; Guo, Wen-Li

2018-07-01

Polyisobutylene-based thermoplastic elastomer (TPE) is a new soft biomaterial. Hydroxyl functional dendritic polyisobutylene-based TPEs (arb-SIBS-OH), which satisfy the design requirements for small-diameter vascular substitutes, were synthesized by controlled carbocationic polymerization. Creep property, which is the destructive weakness of polyisobutylene-based TPEs, was significantly improved with the formation of a "double network" promoted by branched structure and microphase separation. Compatibility of arb-SIBS-OH with rabbit blood was markedly enhanced by modifying heparin grafted from these hydroxyl functional groups. Application of "click chemistry" to immobilize heparin on arb-SIBS-OH surface was apparently effective in enhancing the bioactivity of heparin. Immobilized heparin, which directly bonded by ester bonds, was more likely to form multi-point binding on arb-SIBS-OH surface. This process hindered the accessibility of the heparin active sequence to antithrombin.

Innovative and water based stripping approach for thick and bulk photoresists

NASA Astrophysics Data System (ADS)

Rudolph, Matthias; Schumann, Dirk; Thrun, Xaver; Esche, Silvio; Hohle, Christoph

2014-10-01

The usage of phase fluid based stripping agents to remove photoresists from silicon substrates was studied. Photoresists are required for many silicon based technologies such as MEMS patterning, 3D-Integration or frontend and backend of line semiconductor applications [1]. Although the use of resists is very common, their successful integration often depends on the ability to remove the resist after certain processing steps. On the one hand the resist is changing during subsequent process steps that can cause a thermally activated cross-linking which increases the stripping complexity. Resist removal is also challenging after the formation of a hard polymer surface layer during plasma or implant processes which is called skin or crust [2]. On the other hand the choice of stripping chemistry is often limited due to the presence of functional materials such as metals which can be damaged by aggressive stripping chemistries [3].

Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries.

PubMed

Pang, Quan; Kundu, Dipan; Cuisinier, Marine; Nazar, L F

2014-08-26

The lithium-sulphur battery relies on the reversible conversion between sulphur and Li2S and is highly appealing for energy storage owing to its low cost and high energy density. Porous carbons are typically used as sulfur hosts, but they do not adsorb the hydrophilic polysulphide intermediates or adhere well to Li2S, resulting in pronounced capacity fading. Here we report a different strategy based on an inherently polar, high surface area metallic oxide cathode host and show that it mitigates polysulphide dissolution by forming an excellent interface with Li2S. Complementary physical and electrochemical probes demonstrate strong polysulphide/Li2S binding with this 'sulphiphilic' host and provide experimental evidence for surface-mediated redox chemistry. In a lithium-sulphur cell, Ti4O7/S cathodes provide a discharge capacity of 1,070 mAh g(-1) at intermediate rates and a doubling in capacity retention with respect to a typical conductive carbon electrode, at practical sulphur mass fractions up to 70 wt%. Stable cycling performance is demonstrated at high rates over 500 cycles.

Effect of accelerated weathering on surface chemistry of modified wood

NASA Astrophysics Data System (ADS)

Temiz, Ali; Terziev, Nasko; Eikenes, Morten; Hafren, Jonas

2007-04-01

In this study, the effects of UV-light irradiation and water spray on colour and surface chemistry of scots pine sapwood samples were investigated. The specimens were treated with chromated copper arsenate (CCA), a metal-free propiconazol-based formulation, chitosan, furfuryl alcohol and linseed and tall oils. The weathering experiment was performed by cycles of 2 h UV-light irradiation followed by water spray for 18 min. The changes at the surface of the weathered samples were characterised by Fourier transform infrared spectroscopy (FT-IR); colour characterizations were performed by measuring CIELab parameters. The results show that all treatment methods except chitosan treatment provided lower colour changes than the control groups after 800 h exposure in weathering test cycle, but differences between chitosan and control were also small. The lowest colour changes were found on linseed oil (full cell process) and CCA treated wood. FT-IR results show that oil treatment (linseed and tall oil) decreased the intensities of a lignin specific peak (1500-1515 cm -1). Absorption band changes at 1630-1660 cm -1 were reduced by all treatments.

Constraints on Europa's Ocean Composition Imposed by Its Surface Composition

NASA Astrophysics Data System (ADS)

Johnson, P. V.; Hodyss, R. P.; Vu, T. H.; Choukroun, M.

2017-12-01

Of the non-terrestrial environments within our Solar System, Europa's global liquid water ocean is arguably the most likely to be habitable. As such, understanding the habitability of Europa's ocean is of great interest to astrobiology and is the focus of missions currently being considered for further exploration of Europa. However, direct analysis of the ocean is unlikely in the foreseeable future. As such, our best means of constraining the subsurface ocean composition and its subsequent habitability currently is by further study of Europa's surface chemical composition. Recently, there has been a body of work published that looks at the chemistry of frozen brines representing putative ocean compositions. Here we take a simplified model of a four ionic component (Na, Mg, SO4, Cl) solution and map out what minerals are formed upon freezing as a function of relative ionic concentration, pH, etc. A `flow-chart' of the freezing sequence was developed based on both published and recently acquired experimental results. In performing this exercise, we are able to begin making meaningful links between observations of the surface chemistry and the chemical environment of the internal ocean.

Polypeptide Functional Surface for the Aptamer Immobilization: Electrochemical Cocaine Biosensing.

PubMed

Bozokalfa, Guliz; Akbulut, Huseyin; Demir, Bilal; Guler, Emine; Gumus, Z Pınar; Odaci Demirkol, Dilek; Aldemir, Ebru; Yamada, Shuhei; Endo, Takeshi; Coskunol, Hakan; Timur, Suna; Yagci, Yusuf

2016-04-05

Electroanalytical technologies as a beneficial subject of modern analytical chemistry can play an important role for abused drug analysis which is crucial for both legal and social respects. This article reports a novel aptamer-based biosensing procedure for cocaine analysis by combining the advantages of aptamers as selective recognition elements with the well-known advantages of biosensor systems such as the possibility of miniaturization and automation, easy fabrication and modification, low cost, and sensitivity. In order to construct the aptasensor platform, first, polythiophene bearing polyalanine homopeptide side chains (PT-Pala) was electrochemically coated onto the surface of an electrode and then cocaine aptamer was attached to the polymer via covalent conjugation chemistry. The stepwise modification of the surface was confirmed by electrochemical characterization. The designed biosensing system was applied for the detection of cocaine and its metabolite, benzoylecgonine (BE), which exhibited a linear correlation in the range from 2.5 up to 10 nM and 0.5 up to 50 μM for cocaine and BE, respectively. In order to expand its practical application, the proposed method was successfully tested for the analysis of synthetic biological fluids.

A New Approach for Detection Improvement of the Creutzfeldt-Jakob Disorder through a Specific Surface Chemistry Applied onto Titration Well

PubMed Central

Mille, Caroline; Debarnot, Dominique; Zorzi, Willy; Moualij, Benaissa El; Quadrio, Isabelle; Perret-Liaudet, Armand; Coudreuse, Arnaud; Legeay, Gilbert; Poncin-Epaillard, Fabienne

2012-01-01

This work illustrates the enhancement of the sensitivity of the ELISA titration for recombinant human and native prion proteins, while reducing other non-specific adsorptions that could increase the background signal and lead to a low sensitivity and false positives. It is achieved thanks to the association of plasma chemistry and coating with different amphiphilic molecules bearing either ionic charges and/or long hydrocarbon chains. The treated support by 3-butenylamine hydrochloride improves the signal detection of recombinant protein, while surface modification with the 3,7-dimethylocta-2,6-dien-1-diamine (geranylamine) enhances the sensitivity of the native protein. Beside the surface chemistry effect, these different results are associated with protein conformation. PMID:25586034

Influence of activated carbon characteristics on toluene and hexane adsorption: Application of surface response methodology

NASA Astrophysics Data System (ADS)

Izquierdo, Mª Teresa; de Yuso, Alicia Martínez; Valenciano, Raquel; Rubio, Begoña; Pino, Mª Rosa

2013-01-01

The objective of this study was to evaluate the adsorption capacity of toluene and hexane over activated carbons prepared according an experimental design, considering as variables the activation temperature, the impregnation ratio and the activation time. The response surface methodology was applied to optimize the adsorption capacity of the carbons regarding the preparation conditions that determine the physicochemical characteristics of the activated carbons. The methodology of preparation produced activated carbons with surface areas and micropore volumes as high as 1128 m2/g and 0.52 cm3/g, respectively. Moreover, the activated carbons exhibit mesoporosity, ranging from 64.6% to 89.1% the percentage of microporosity. The surface chemistry was characterized by TPD, FTIR and acid-base titration obtaining different values of surface groups from the different techniques because the limitation of each technique, but obtaining similar trends for the activated carbons studied. The exhaustive characterization of the activated carbons allows to state that the measured surface area does not explain the adsorption capacity for either toluene or n-hexane. On the other hand, the surface chemistry does not explain the adsorption results either. A compromise between physical and chemical characteristics can be obtained from the appropriate activation conditions, and the response surface methodology gives the optimal activated carbon to maximize adsorption capacity. Low activation temperature, intermediate impregnation ratio lead to high toluene and n-hexane adsorption capacities depending on the activation time, which a determining factor to maximize toluene adsorption.

Friction and Wear Management Using Solvent Partitioning of Hydrophilic-Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor)

2015-01-01

Lubrication additives of the current invention require formation of emulsions in base lubricants, created with an aqueous salt solution plus a single-phase compound such that partitioning within the resulting emulsion provides thermodynamically targeted compounds for boundary layer organization thus establishing anti-friction and/or anti-wear. The single-phase compound is termed "boundary layer organizer", abbreviated BLO. These emulsion-contained compounds energetically favor association with tribologic surfaces in accord with the Second Law of Thermodynamics, and will organize boundary layers on those surfaces in ways specific to the chemistry of the salt and BLO additives. In this way friction modifications may be provided by BLOs targeted to boundary layers via emulsions within lubricating fluids, wherein those lubricating fluids may be water-based or oil-based.

Surface chemistry from wettability and charge for the control of mesenchymal stem cell fate through self-assembled monolayers.

PubMed

Hao, Lijing; Fu, Xiaoling; Li, Tianjie; Zhao, Naru; Shi, Xuetao; Cui, Fuzhai; Du, Chang; Wang, Yingjun

2016-12-01

Self-assembled monolayers (SAMs) of alkanethiols on gold are highly controllable model substrates and have been employed to mimic the extracellular matrix for cell-related studies. This study aims to systematically explore how surface chemistry influences the adhesion, morphology, proliferation and osteogenic differentiation of mouse mesenchymal stem cells (mMSCs) using various functional groups (-OEG, -CH 3 , -PO 3 H 2 , -OH, -NH 2 and -COOH). Surface analysis demonstrated that these functional groups produced a wide range of wettability and charge: -OEG (hydrophilic and moderate iso-electric point (IEP)), -CH 3 (strongly hydrophobic and low IEP), -PO 3 H 2 (moderate wettability and low IEP), -OH (hydrophilic and moderate IEP), -NH 2 (moderate wettability and high IEP) and -COOH (hydrophilic and low IEP). In terms of cell responses, the effect of wettability may be more influential than charge for these groups. Moreover, compared to -OEG and -CH 3 groups, -PO 3 H 2 , -OH, -NH 2 and -COOH functionalities tended to promote not only cell adhesion, proliferation and osteogenic differentiation but also the expression of α v and β 1 integrins. This finding indicates that the surface chemistry may guide mMSC activities through α v and β 1 integrin signaling pathways. Model surfaces with controllable chemistry may provide insight into biological responses to substrate surfaces that would be useful for the design of biomaterial surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

A topological screening heuristic for low-energy, high-index surfaces

NASA Astrophysics Data System (ADS)

Sun, Wenhao; Ceder, Gerbrand

2018-03-01

Robust ab initio investigations of nanoparticle surface properties require a method to identify candidate low-energy surface facets a priori. By assuming that low-energy surfaces are planes with high atomic density, we devise an efficient algorithm to screen for low-energy surface orientations, even if they have high (hkl) miller indices. We successfully predict the observed low-energy, high-index { 10 12 bar } and { 10 1 bar 4 } surfaces of hematite α-Fe2O3, the {311} surfaces of cuprite Cu2O, and the {112} surfaces of anatase TiO2. We further tabulate candidate low-energy surface orientations for nine of the most common binary oxide structures. Screened surfaces are found to be generally applicable across isostructural compounds with varying chemistries, although relative surface energies between facets may vary based on the preferred coordination of the surface atoms.

Loch Vale Watershed Long-Term Ecological Research and Monitoring Program: Quality Assurance Report, 2003-09

USGS Publications Warehouse

Richer, Eric E.; Baron, Jill S.

2011-01-01

The Loch Vale watershed project is a long-term research and monitoring program located in Rocky Mountain National Park that addresses watershed-scale ecosystem processes, particularly as they respond to atmospheric deposition and climate variability. Measurements of precipitation depth, precipitation chemistry, discharge, and surface-water quality are made within the watershed and elsewhere in Rocky Mountain National Park. As data collected for the program are used by resource managers, scientists, policy makers, and students, it is important that all data collected in Loch Vale watershed meet high standards of quality. In this report, data quality was evaluated for precipitation, discharge, and surface-water chemistry measurements collected during 2003-09. Equipment upgrades were made at the Loch Vale National Atmospheric Deposition Program monitoring site to improve precipitation measurements and evaluate variability in precipitation depth and chemistry. Additional solar panels and batteries have been installed to improve the power supply, and data completeness, at the NADP site. As a result of equipment malfunction, discharge data for the Loch Outlet were estimated from October 18, 2005, to August 17, 2006. Quality-assurance results indicate that more than 98 percent of all surface-water chemistry measurements were accurate and precise. Records that did not meet quality criteria were removed from the database. Measurements of precipitation depth, precipitation chemistry, discharge, and surface-water quality were all sufficiently complete and consistent to support project data needs.

Impacts of Interactive Stratospheric Chemistry on Antarctic and Southern Ocean Climate Change in the Goddard Earth Observing System Version 5 (GEOS-5)

NASA Technical Reports Server (NTRS)

Li, Feng; Vikhliaev, Yury V.; Newman, Paul A.; Pawson, Steven; Perlwitz, Judith; Waugh, Darryn W.; Douglass, Anne R.

2016-01-01

Stratospheric ozone depletion plays a major role in driving climate change in the Southern Hemisphere. To date, many climate models prescribe the stratospheric ozone layer's evolution using monthly and zonally averaged ozone fields. However, the prescribed ozone underestimates Antarctic ozone depletion and lacks zonal asymmetries. In this study we investigate the impact of using interactive stratospheric chemistry instead of prescribed ozone on climate change simulations of the Antarctic and Southern Ocean. Two sets of 1960-2010 ensemble transient simulations are conducted with the coupled ocean version of the Goddard Earth Observing System Model, version 5: one with interactive stratospheric chemistry and the other with prescribed ozone derived from the same interactive simulations. The model's climatology is evaluated using observations and reanalysis. Comparison of the 1979-2010 climate trends between these two simulations reveals that interactive chemistry has important effects on climate change not only in the Antarctic stratosphere, troposphere, and surface, but also in the Southern Ocean and Antarctic sea ice. Interactive chemistry causes stronger Antarctic lower stratosphere cooling and circumpolar westerly acceleration during November-December-January. It enhances stratosphere-troposphere coupling and leads to significantly larger tropospheric and surface westerly changes. The significantly stronger surface wind stress trends cause larger increases of the Southern Ocean Meridional Overturning Circulation, leading to year-round stronger ocean warming near the surface and enhanced Antarctic sea ice decrease.

Coastal groundwater/surface-water interactions: a Great Lakes case study

USGS Publications Warehouse

Neff, Brian P.; Haack, Sheridan K.; Rosenberry, Donald O.; Savino, Jacqueline F.; Lundstrom, Scott C.

2006-01-01

Key similarities exist between marine and Great Lakes coastal environments. Water and nutrient fluxes across lakebeds in the Great Lakes are influenced by seiche and wind set-up and set-down, analogous to tidal influence in marine settings. Groundwater/surface-water interactions also commonly involve a saline-fresh water interface, although in the Great-Lakes cases, it is groundwater that is commonly saline and surface water that is fresh. Evapotranspiration also affects nearshore hydrology in both settings. Interactions between groundwater and surface water have recently been identified as an important component of ecological processes in the Great Lakes. Water withdrawals and the reversal of the groundwater/surface water seepage gradient are also common to many coastal areas around the Great Lakes. As compared to surface water, regional groundwater that discharges to western Lake Erie from Michigan is highly mineralized. Studies conducted by the U.S. Geological Survey at Erie State Game Area in southeastern Michigan, describe groundwater flow dynamics and chemistry, shallow lake-water chemistry, and fish and invertebrate communities. Results presented here provide an overview of recent progress of ongoing interdisciplinary studies of Great Lakes nearshore systems and describe a conceptual model that identifies relations among geologic, hydrologic, chemical, and biological processes in the coastal habitats of Lake Erie. This conceptual model is based on analysis of hydraulic head in piezometers at the study site and chemical analysis of deep and shallow coastal groundwater.

Surface Functionalized Nanostructured Ceramic Sorbents for the Effective Collection and Recovery of Uranium from Seawater

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

Chouyyok, Wilaiwan; Pittman, Jonathan W.; Warner, Marvin G.

2016-05-02

The ability to collect uranium from seawater offers the potential for a nearly limitless fuel supply for nuclear energy. We evaluated the use of functionalized nanostructured sorbents for the collection and recovery of uranium from seawater. Extraction of trace minerals from seawater and brines is challenging due to the high ionic strength of seawater, low mineral concentrations, and fouling of surfaces over time. We demonstrate that rationally assembled sorbent materials that integrate high affinity surface chemistry and high surface area nanostructures into an application relevant micro/macro structure enables collection performance that far exceeds typical sorbent materials. High surface area nanostructuredmore » silica with surface chemistries composed of phosphonic acid, phosphonates, 3,4 hydroxypyridinone, and EDTA showed superior performance for uranium collection. A few phosphorous-based commercial resins, specifically Diphonix and Ln Resin, also performed well. We demonstrate an effective and environmentally benign method of stripping the uranium from the high affinity sorbents using inexpensive nontoxic carbonate solutions. The cyclic use of preferred sorbents and acidic reconditioning of materials was shown to improve performance. Composite thin films composed of the nanostructured sorbents and a porous polymer binder are shown to have excellent kinetics and good capacity while providing an effective processing configuration for trace mineral recovery from solutions. Initial work using the composite thin films shows significant improvements in processing capacity over the previously reported sorbent materials.« less

Raman-atomic force microscopy of the ommatidial surfaces of Dipteran compound eyes.

PubMed

Anderson, Mark S; Gaimari, Stephen D

2003-06-01

The ommatidial lens surfaces of the compound eyes in several species of files (Insecta: Diptera) and a related order (Mecoptera) were analyzed using a recently developed Raman-atomic force microscope. We demonstrate in this work that the atomic force microscope (AFM) is a potentially useful instrument for gathering phylogenetic data and that the newly developed Raman-AFM may extend this application by revealing nanometer-scale surface chemistry. This is the first demonstration of apertureless near-field Raman spectroscopy on an intact biological surface. For Chrysopilus testaceipes Bigot (Rhagionidae), this reveals unique cerebral cortex-like surface ridges with periodic variation in height and surface chemistry. Most other Brachyceran flies, and the "Nematoceran" Sylvicola fenestralis (Scopoli) (Anisopodidae), displayed the same morphology, while other taxa displayed various other characteristics, such as a nodule-like (Tipula (Triplicitipula) sp. (Tipulidae)) or coalescing nodule-like (Tabanus punctifer Osten Sacken (Tabanidae)) morphology, a smooth morphology with distinct pits and grooves (Dilophus orbatus (Say) (Bibionidae)), or an entirely smooth surface (Bittacus chlorostigma MacLachlan (Mecoptera: Bittacidae)). The variation in submicrometer structure and surface chemistry provides a new information source of potential phylogenetic importance, suggesting the Raman-atomic force microscope could provide a new tool useful to systematic and evolutionary inquiry.

Raman-atomic force microscopy of the ommatidial surfaces of Dipteran compound eyes

NASA Technical Reports Server (NTRS)

Anderson, Mark S.; Gaimari, Stephen D.

2003-01-01

The ommatidial lens surfaces of the compound eyes in several species of files (Insecta: Diptera) and a related order (Mecoptera) were analyzed using a recently developed Raman-atomic force microscope. We demonstrate in this work that the atomic force microscope (AFM) is a potentially useful instrument for gathering phylogenetic data and that the newly developed Raman-AFM may extend this application by revealing nanometer-scale surface chemistry. This is the first demonstration of apertureless near-field Raman spectroscopy on an intact biological surface. For Chrysopilus testaceipes Bigot (Rhagionidae), this reveals unique cerebral cortex-like surface ridges with periodic variation in height and surface chemistry. Most other Brachyceran flies, and the "Nematoceran" Sylvicola fenestralis (Scopoli) (Anisopodidae), displayed the same morphology, while other taxa displayed various other characteristics, such as a nodule-like (Tipula (Triplicitipula) sp. (Tipulidae)) or coalescing nodule-like (Tabanus punctifer Osten Sacken (Tabanidae)) morphology, a smooth morphology with distinct pits and grooves (Dilophus orbatus (Say) (Bibionidae)), or an entirely smooth surface (Bittacus chlorostigma MacLachlan (Mecoptera: Bittacidae)). The variation in submicrometer structure and surface chemistry provides a new information source of potential phylogenetic importance, suggesting the Raman-atomic force microscope could provide a new tool useful to systematic and evolutionary inquiry.

Concept-Oriented Task Design: Making Purposeful Case Comparisons in Organic Chemistry

ERIC Educational Resources Information Center

Graulich, Nicole; Schween, Michael

2018-01-01

Acquiring conceptual understanding seems to be one of the main challenges students face when studying organic chemistry. Traditionally, organic chemistry presents an extensive variety of chemical transformations, which often lead students to recall an organic transformation rather than apply conceptual knowledge. Strong surface level focus and…

76 FR 62149 - American Chemistry Council, The Chlorine Institute, Inc., the Fertilizer Institute, and PPG...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-06

... DEPARTMENT OF TRANSPORTATION Surface Transportation Board [Docket No. NOR 42129; Docket No. FD 35517] American Chemistry Council, The Chlorine Institute, Inc., the Fertilizer Institute, and PPG... both cases. \\1\\ In Docket No. NOR 42129, the complainants are American Chemistry Council, The Chlorine...

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

NASA Astrophysics Data System (ADS)

Hudson, R.; Loeffler, M. J.; Gerakines, P.

2017-12-01

The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

Contribution of Surface Chemistry to the Shear Thickening of Silica Nanoparticle Suspensions.

PubMed

Yang, Wufang; Wu, Yang; Pei, Xiaowei; Zhou, Feng; Xue, Qunji

2017-01-31

Shear thickening is a general process crucial for many processed products ranging from food and personal care to pharmaceuticals. Theoretical calculations and mathematical simulations of hydrodynamic interactions and granular-like contacts have proved that contact forces between suspended particles dominate the rheological characteristic of colloidal suspensions. However, relevant experimental studies are very rare. This study was conducted to reveal the influence of nanoparticle (NP) interactions on the rheological behavior of shear-thickening fluids (STFs) by changing the colloidal surface chemistries. Silica NPs with various surface chemical compositions are fabricated and used to prepare dense suspensions. Rheological experiments are conducted to determine the influence of NP interactions on corresponding dense suspension systems. The results suggest that the surface chemistries of silica NPs determine the rheological behavior of dense suspensions, including shear-thickening behavior, onset stress, critical volume fraction, and jamming volume fraction. This study provides useful reference for designing effective STFs and regulating their characteristics.

Representation of the Community Earth System Model (CESM1) CAM4-chem within the Chemistry-Climate Model Initiative (CCMI)

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

Tilmes, Simone; Lamarque, Jean -Francois; Emmons, Louisa K.

The Community Earth System Model (CESM1) CAM4-chem has been used to perform the Chemistry Climate Model Initiative (CCMI) reference and sensitivity simulations. In this model, the Community Atmospheric Model version 4 (CAM4) is fully coupled to tropospheric and stratospheric chemistry. Details and specifics of each configuration, including new developments and improvements are described. CESM1 CAM4-chem is a low-top model that reaches up to approximately 40 km and uses a horizontal resolution of 1.9° latitude and 2.5° longitude. For the specified dynamics experiments, the model is nudged to Modern-Era Retrospective Analysis for Research and Applications (MERRA) reanalysis. We summarize the performance ofmore » the three reference simulations suggested by CCMI, with a focus on the last 15 years of the simulation when most observations are available. Comparisons with selected data sets are employed to demonstrate the general performance of the model. We highlight new data sets that are suited for multi-model evaluation studies. Most important improvements of the model are the treatment of stratospheric aerosols and the corresponding adjustments for radiation and optics, the updated chemistry scheme including improved polar chemistry and stratospheric dynamics and improved dry deposition rates. These updates lead to a very good representation of tropospheric ozone within 20 % of values from available observations for most regions. In particular, the trend and magnitude of surface ozone is much improved compared to earlier versions of the model. Furthermore, stratospheric column ozone of the Southern Hemisphere in winter and spring is reasonably well represented. In conclusion, all experiments still underestimate CO most significantly in Northern Hemisphere spring and show a significant underestimation of hydrocarbons based on surface observations.« less

Representation of the Community Earth System Model (CESM1) CAM4-chem within the Chemistry-Climate Model Initiative (CCMI)

DOE PAGES

Tilmes, Simone; Lamarque, Jean -Francois; Emmons, Louisa K.; ...

2016-05-20

The Community Earth System Model (CESM1) CAM4-chem has been used to perform the Chemistry Climate Model Initiative (CCMI) reference and sensitivity simulations. In this model, the Community Atmospheric Model version 4 (CAM4) is fully coupled to tropospheric and stratospheric chemistry. Details and specifics of each configuration, including new developments and improvements are described. CESM1 CAM4-chem is a low-top model that reaches up to approximately 40 km and uses a horizontal resolution of 1.9° latitude and 2.5° longitude. For the specified dynamics experiments, the model is nudged to Modern-Era Retrospective Analysis for Research and Applications (MERRA) reanalysis. We summarize the performance ofmore » the three reference simulations suggested by CCMI, with a focus on the last 15 years of the simulation when most observations are available. Comparisons with selected data sets are employed to demonstrate the general performance of the model. We highlight new data sets that are suited for multi-model evaluation studies. Most important improvements of the model are the treatment of stratospheric aerosols and the corresponding adjustments for radiation and optics, the updated chemistry scheme including improved polar chemistry and stratospheric dynamics and improved dry deposition rates. These updates lead to a very good representation of tropospheric ozone within 20 % of values from available observations for most regions. In particular, the trend and magnitude of surface ozone is much improved compared to earlier versions of the model. Furthermore, stratospheric column ozone of the Southern Hemisphere in winter and spring is reasonably well represented. In conclusion, all experiments still underestimate CO most significantly in Northern Hemisphere spring and show a significant underestimation of hydrocarbons based on surface observations.« less

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

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

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysismore » studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.« less

Plasticity and Kinky Chemistry of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Dzegilenko, Fedor

2000-01-01

Since their discovery in 1991, carbon nanotubes have been the subject of intense research interest based on early predictions of their unique mechanical, electronic, and chemical properties. Materials with the predicted unique properties of carbon nanotubes are of great interest for use in future generations of aerospace vehicles. For their structural properties, carbon nanotubes could be used as reinforcing fibers in ultralight multifunctional composites. For their electronic properties, carbon nanotubes offer the potential of very high-speed, low-power computing elements, high-density data storage, and unique sensors. In a continuing effort to model and predict the properties of carbon nanotubes, Ames accomplished three significant results during FY99. First, accurate values of the nanomechanics and plasticity of carbon nanotubes based on quantum molecular dynamics simulations were computed. Second, the concept of mechanical deformation catalyzed-kinky-chemistry as a means to control local chemistry of nanotubes was discovered. Third, the ease of nano-indentation of silicon surfaces with carbon nanotubes was established. The elastic response and plastic failure mechanisms of single-wall nanotubes were investigated by means of quantum molecular dynamics simulations.

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

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

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements formore » electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.« less

Surface and Interface Chemistry for Gate Stacks on Silicon

NASA Astrophysics Data System (ADS)

Frank, M. M.; Chabal, Y. J.

This chapter addresses the fundamental silicon surface science associated with the continued progress of nanoelectronics along the path prescribed by Moore's law. Focus is on hydrogen passivation layers and on ultrathin oxide films encountered during silicon cleaning and gate stack formation in the fabrication of metal-oxide-semiconductor field-effect transistors (MOSFETs). Three main topics are addressed. (i) First, the current practices and understanding of silicon cleaning in aqueous solutions are reviewed, including oxidizing chemistries and cleans leading to a hydrogen passivation layer. The dependence of the final surface termination and morphology/roughness on reactant choice and pH and the influence of impurities such as dissolved oxygen or metal ions are discussed. (ii) Next, the stability of hydrogen-terminated silicon in oxidizing liquid and gas phase environments is considered. In particular, the remarkable stability of hydrogen-terminated silicon surface in pure water vapor is discussed in the context of atomic layer deposition (ALD) of high-permittivity (high-k) gate dielectrics where water is often used as an oxygen precursor. Evidence is also provided for co-operative action between oxygen and water vapor that accelerates surface oxidation in humid air. (iii) Finally, the fabrication of hafnium-, zirconium- and aluminum-based high-k gate stacks is described, focusing on the continued importance of the silicon/silicon oxide interface. This includes a review of silicon surface preparation by wet or gas phase processing and its impact on high-k nucleation during ALD growth, and the consideration of gate stack capacitance and carrier mobility. In conclusion, two issues are highlighted: the impact of oxygen vacancies on the electrical characteristics of high-k MOS devices, and the way alloyed metal ions (such as Al in Hf-based gate stacks) in contact with the interfacial silicon oxide layer can be used to control flatband and threshold voltages.

Synthetic Fabrication of Nanoscale MoS2-Based Transition Metal Sulfides

PubMed Central

Wang, Shutao; An, Changhua; Yuan, Jikang

2010-01-01

Transition metal sulfides are scientifically and technologically important materials. This review summarizes recent progress on the synthetic fabrication of transition metal sulfides nanocrystals with controlled shape, size, and surface functionality. Special attention is paid to the case of MoS2 nanoparticles, where organic (surfactant, polymer), inorganic (support, promoter, doping) compounds and intercalation chemistry are applied.

Improved performance of protected catecholic polysiloxanes for bio-inspired wet adhesion to surface oxides

PubMed Central

Heo, Jinhwa; Kang, Taegon; Jang, Se Gyu; Hwang, Dong Soo; Spruell, Jason M.; Killops, Kato L.; Waite, J. Herbert; Hawker, Craig J.

2012-01-01

A facile synthetic strategy for introducing catecholic moieties into polymeric materials based on a readily available precursor – eugenol – and efficient chemistries – tris(pentafluorophenyl)borane catalyzed silation and thiol-ene coupling is reported. Silyl-protection is shown to be critical for the oxidative stability of catecholic moieties during synthesis and processing which allows functionalized polysiloxane derivatives to be fabricated into 3-D microstructures as well as 2-D patterned surfaces. Deprotection gives stable catechol surfaces with adhesion to a variety of oxide surfaces being precisely tuned by the level of catechol incorporation. The advantage of silyl-protection for catechol functionalized polysiloxanes is demonstrated and represents a promising and versatile new platform for underwater surface treatments. PMID:23181614

THE DISTRIBUTION AND CHEMISTRY OF H{sub 2}CO IN THE DM TAU PROTOPLANETARY DISK

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

Loomis, Ryan A.; Öberg, Karin I.; Guzman, Viviana V.

H{sub 2}CO ice on dust grains is an important precursor of complex organic molecules (COMs). H{sub 2}CO gas can be readily observed in protoplanetary disks and may be used to trace COM chemistry. However, its utility as a COM probe is currently limited by a lack of constraints on the relative contributions of two different formation pathways: on icy grain surfaces and in the gas phase. We use archival Atacama Large (sub-)Millimeter Array observations of the resolved distribution of H{sub 2}CO emission in the disk around the young low-mass star DM Tau to assess the relative importance of these formationmore » routes. The observed H{sub 2}CO emission has a centrally peaked and radially broad brightness profile (extending out to 500 AU). We compare these observations with disk chemistry models with and without grain-surface formation reactions and find that both gas and grain-surface chemistry are necessary to explain the spatial distribution of the emission. Gas-phase H{sub 2}CO production is responsible for the observed central peak, while grain-surface chemistry is required to reproduce the emission exterior to the CO snow line (where H{sub 2}CO mainly forms through the hydrogenation of CO ice before being non-thermally desorbed). These observations demonstrate that both gas and grain-surface pathways contribute to the observed H{sub 2}CO in disks and that their relative contributions depend strongly on distance from the host star.« less

Quantum chemistry study of dielectric materials deposition

NASA Astrophysics Data System (ADS)

Widjaja, Yuniarto

The drive to continually decrease the device dimensions of integrated circuits in the microelectronics industry requires that deposited films approach subnanometer thicknesses. Hence, a fundamental understanding of the physics and chemistry of film deposition is important to obtain better control of the properties of the deposited film. We use ab initio quantum chemistry calculations to explore chemical reactions at the atomic level. Important thermodynamic and kinetic parameters are then obtained, which can then be used as inputs in constructing first-principles based reactor models. Studies of new systems for which data are not available can be conducted as well. In this dissertation, we use quantum chemistry simulations to study the deposition of gate dielectrics for metal-oxide-semiconductor (MOS) devices. The focus of this study is on heterogeneous reactions between gaseous precursors and solid surfaces. Adsorbate-surface interactions introduce additional degrees of complexity compared to the corresponding gas-phase or solid-state reactions. The applicability and accuracy of cluster approximations to represent solid surfaces are first investigated. The majority of our results are obtained using B3LYP density functional theory (DFT). The structures of reactants, products, and transition states are obtained, followed by calculations of thermochemical and kinetic properties. Whenever experimental data are available, qualitative and/or quantitative comparisons are drawn. Atomistic mechanisms and the energetics of several reactions leading to the deposition of SiO2, Si3N4, and potential new high-kappa materials such as ZrO2, HfO2, and Al 2O3 have been explored in this dissertation. Competing reaction pathways are explored for each of the deposition reactions studied. For example, the potential energy surface (PES) for ZrO2 ALD shows that the reactions proceed through a trapping-mediated mechanism, which results in a competition between desorption and decomposition of the gaseous reactants, i.e. ZrCl4 and H2O, on the ZrO2 surface. This competition results in relatively low saturation coverage, which consequently leads to a slow growth rate and possibly affects the thickness uniformity and conformality. The insights gained are then used to systematically improve deposition reactions. For instance, from the ZrO2 ALD PES, we are able to suggest the use of high temperature and pressure to obtain higher surface coverage.

Marcus-Hush-Chidsey theory of electron transfer to and from species bound at a non-uniform electrode surface: Theory and experiment

NASA Astrophysics Data System (ADS)

Henstridge, Martin C.; Batchelor-McAuley, Christopher; Gusmão, Rui; Compton, Richard G.

2011-11-01

Two simple models of electrode surface inhomogeneity based on Marcus-Hush theory are considered; a distribution in formal potentials and a distribution in electron tunnelling distances. Cyclic voltammetry simulated using these models is compared with that simulated using Marcus-Hush theory for a flat, uniform and homogeneous electrode surface, with the two models of surface inhomogeneity yielding broadened peaks with decreased peak-currents. An edge-plane pyrolytic graphite electrode is covalently modified with ferrocene via 'click' chemistry and the resulting voltammetry compared with each of the three previously considered models. The distribution of formal potentials is seen to fit the experimental data most closely.

Temperature dependent droplet impact dynamics on flat and textured surfaces

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

Azar Alizadeh; Vaibhav Bahadur; Sheng Zhong

Droplet impact dynamics determines the performance of surfaces used in many applications such as anti-icing, condensation, boiling and heat transfer. We study impact dynamics of water droplets on surfaces with chemistry/texture ranging from hydrophilic to superhydrophobic and across a temperature range spanning below freezing to near boiling conditions. Droplet retraction shows very strong temperature dependence especially for hydrophilic surfaces; it is seen that lower substrate temperatures lead to lesser retraction. Physics-based analyses show that the increased viscosity associated with lower temperatures can explain the decreased retraction. The present findings serve to guide further studies of dynamic fluid-structure interaction at variousmore » temperatures.« less

Io. [history of studies and current level of understanding of this satellite

NASA Technical Reports Server (NTRS)

Nash, Douglas B.; Yoder, Charles F.; Carr, Michael H.; Gradie, Jonathan; Hunten, Donald M.

1986-01-01

The present work reviews the history of Io studies and describes the current level of understanding of Io's physics, chemistry, geology, orbital dynamics, and geophysics. Consideration is given to the satellite's internal, superficial, atmospheric, plasma, and magnetospheric properties and how they interrelate. A pictorial map of Io's surface based on Voyager 1 and 2 images is presented. It is found that Io's surface color and spectra are dominated by sulfur compounds which may include various sulfur allotropes. Volcanic processes yielding three kinds of surface features (vent regions, plains, and mountains) dominate Io's surface geology. The Io plasma torus corotates with Jupiter's magnetic field in the plane of Jupiter's centrifugal equator centered at Io's orbital radius.

Lunar soil and surface processes studies

NASA Technical Reports Server (NTRS)

Glass, B. P.

1975-01-01

Glass particles in lunar soil were characterized and compared to terrestrial analogues. In addition, useful information was obtained concerning the nature of lunar surface processes (e.g. volcanism and impact), maturity of soils and chemistry and heterogeneity of lunar surface material. It is felt, however, that the most important result of the study was that it demonstrated that the investigation of glass particles from the regolith of planetary bodies with little or no atmospheres can be a powerful method for learning about the surface processes and chemistry of planetary surfaces. Thus, the return of samples from other planetary bodies (especially the terrestrial planets and asteroids) using unmanned spacecraft is urged.

The relative effect of surface strontium chemistry and super-hydrophilicity on the early osseointegration of moderately rough titanium surface in the rabbit femur.

PubMed

Park, Jin-Woo; Kwon, Tae-Geon; Suh, Jo-Young

2013-06-01

It is unclear whether surface bioactive chemistry or hydrophilicity plays a more dominant role in the osseointegration of micro-structured titanium implants having the same surface topography at the micrometer and submicrometer scales. To understand their comparative effect on enhancing the early osseointegration of micro-rough-surfaced implants, this study compared the bone healing-promoting effect of surface strontium (Sr) chemistry that has been shown in numerous studies to super-hydrophilicity in the early osseointegration of moderately rough-surfaced clinical oral implants (SLA(®) implant) in rabbit cancellous bone. Hydrothermal treatment was performed to incorporate Sr ions into the surface of clinical SLA implants (SLA/Sr implant). The surface characteristics were evaluated by using field emission-scanning electron microscopy, X-ray photoelectron spectroscopy and optical profilometry. Twenty screw implants (10 control and 10 experimental) were placed in the femoral condyles of 10 New Zealand White rabbits. The early osseointegration of the SLA/Sr implant was compared with a chemically modified super-hydrophilic SLA implant (SLActive(®) implant) by histomorphometric and resonance frequency analysis after 2 weeks of implantation. The SLA/Sr and SLActive implants exhibited an identical surface topography and average R(a) values at the micron and submicron scales. The SLA/Sr implant displayed a high amount of surface Sr content (15.6 at.%). There was no significant difference in the implant stability quotient (ISQ) values between the two groups. However, histomorphometric analysis revealed a significantly higher bone-to-implant contact percentage in the SLA/Sr implants compared with the SLActive implants in rabbit cancellous bone (P < 0.01). The results indicate that the surface Sr chemistry surpasses the effect of super-hydrophilicity in promoting the early bone apposition of moderately rough Ti surface in cancellous bone. © 2012 John Wiley & Sons A/S.

Composition, structure, and chemistry of interstellar dust

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.; Allamandola, L. J.

1987-01-01

Different dust components present in the interstellar medium (IM) such as amorphous carbon, polycyclic aromatic hydrocarbons, and those IM components which are organic refractory grains and icy grain mantles are discussed as well as their relative importance. The physical properties of grain surface chemistry are discussed with attention given to the surface structure of materials, the adsorption energy and residence time of species on a grain surface, and the sticking probability. Consideration is also given to the contribution of grains to the gas-phase composition of molecular clouds.

Using Raman Spectroscopy and Surface-Enhanced Raman Scattering to Identify Colorants in Art: An Experiment for an Upper-Division Chemistry Laboratory

ERIC Educational Resources Information Center

Mayhew, Hannah E.; Frano, Kristen A.; Svoboda, Shelley A.; Wustholz, Kristin L.

2015-01-01

Surface-enhanced Raman scattering (SERS) studies of art represent an attractive way to introduce undergraduate students to concepts in nanoscience, vibrational spectroscopy, and instrumental analysis. Here, we present an undergraduate analytical or physical chemistry laboratory wherein a combination of normal Raman and SERS spectroscopy is used to…

Color and surface chemistry changes of extracted wood flour after heating at 120 °C

Treesearch

Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark

2013-01-01

To investigate the effect of heat on color and surface chemistry of wood flour (WF), unextracted, extracted and delignified samples of commercial WF were heated at 120 °C for 24 h and analyzed by colorimetry, diffuse reflectance visible (DRV), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Fourier transform Raman (FT-Raman) spectroscopies....

Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

ERIC Educational Resources Information Center

Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

2010-01-01

Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

The Surface Chemistry of Metal Chalcogenide Nanocrystals

NASA Astrophysics Data System (ADS)

Anderson, Nicholas Charles

The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu3P complex of cadmium chloride. Nuclear magnetic resonance spectroscopy supports complete cleavage of the X-type carboxylate ligands. Combined with measurements of the Se:Cd:Cl ratio using Rutherford backscattering spectrometry, these studies support a structural model of nanocrystals where chloride ligands terminate the crystal lattice by balancing the charges of excess Cd2+ ions. The adsorption of dative phosphine ligands leads to nanocrystals who's solubility is afforded by reversibly bound and readily exchanged L-type ligands, e.g. primary amines and phosphines. The other halides (Br and I) can also be used to prepare Bu 3P-bound, halide-terminated CdSe nanocrystals, however these nanocrystals are not soluble after exchange. The change in binding affinity of Bu 3P over the halide series is briefly discussed. Next, we report a series of L-type ligand exchanges using Bu3P-bound, chloride-terminated CdSe nanocrystals with several Lewis bases, including aromatic, cyclic, and non-cyclic sulfides, and ethers; primary, secondary, and tertiary amines and phosphines; tertiary phosphine chalcogenides; primary alcohols, isocyanides, and isothiocyanides. Using 31P nuclear magnetic resonance spectroscopy, we establish a relative binding affinity for these ligands that reflects electronic considerations but is dominated primarily by steric interactions, as determined by comparing binding affinity to Tolmann cone angles. We also used chloride-terminated CdSe nanocrystals to explore the reactivity of ionic salts at nanocrystal surfaces. These salts, particularly [Bu3P-H]+[Cl]-, bind nanocrystals surfaces as L-type ligands, making them soluble in polar solvents such as acetonitrile. This information should provide insight for rational ligand design for future applications involving metal chalcogenide nanocrystals. The strongest ligand, primary n-alkylamine, rapidly displace the Bu3P from halide-terminated CdSe nanocrystals, leading to amine-bound nanocrystals with higher dative ligand coverages and greatly increased photoluminescence quantum yields. The importance of ligand coverage to both the UV-visible absorption and photoluminescence spectra are discussed. (Abstract shortened by UMI.).

Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

PubMed

Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

2014-12-10

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

The effects of engine operating conditions on CCD chemistry and morphology

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

Yeh, S.W.; Moore, S.M.; Sabourin, E.T.

1996-10-01

The effects of engine driving cycle and engine coolant temperature on combustion chamber deposit (CCD) surface chemistry and morphology were assessed by the use of XPS and scanning electron micrographs. A 3.1L V6 test cell engine was used to generate a six test matrix that compared deposit surface chemistry and morphology under two distinctly different driving cycles, each cycle being evaluated at three separate engine coolant temperatures. Deposit material for each respective test was collected by removable combustion chamber sample probes that were subjected to XPS surface analysis and SEM evaluation. Discernible trends were observed in surface chemistry and depositmore » amounts with respect to changes in both driving cycle and coolant temperature. However, much more pronounced were deposit morphological changes recorded by SEM in different engine coolant temperature regimes for both of the utilized driving cycles. Deposit nodules formed in one temperature regime were seen to be typically much larger in size, highly irregular in shape, and appeared to be porous in structure. At a different operating temperature, the deposit nodules were observed to be extremely uniform and more tightly packed.« less

Carbon Dots as Versatile Photosensitizers for Solar-Driven Catalysis with Redox Enzymes.

PubMed

Hutton, Georgina A M; Reuillard, Bertrand; Martindale, Benjamin C M; Caputo, Christine A; Lockwood, Colin W J; Butt, Julea N; Reisner, Erwin

2016-12-28

Light-driven enzymatic catalysis is enabled by the productive coupling of a protein to a photosensitizer. Photosensitizers used in such hybrid systems are typically costly, toxic, and/or fragile, with limited chemical versatility. Carbon dots (CDs) are low-cost, nanosized light-harvesters that are attractive photosensitizers for biological systems as they are water-soluble, photostable, nontoxic, and their surface chemistry can be easily modified. We demonstrate here that CDs act as excellent light-absorbers in two semibiological photosynthetic systems utilizing either a fumarate reductase (FccA) for the solar-driven hydrogenation of fumarate to succinate or a hydrogenase (H 2 ase) for reduction of protons to H 2 . The tunable surface chemistry of the CDs was exploited to synthesize positively charged ammonium-terminated CDs (CD-NHMe 2 + ), which were capable of transferring photoexcited electrons directly to the negatively charged enzymes with high efficiency and stability. Enzyme-based turnover numbers of 6000 mol succinate (mol FccA) -1 and 43,000 mol H 2 (mol H 2 ase) -1 were reached after 24 h. Negatively charged carboxylate-terminated CDs (CD-CO 2 - ) displayed little or no activity, and the electrostatic interactions at the CD-enzyme interface were determined to be essential to the high photocatalytic activity observed with CD-NHMe 2 + . The modular surface chemistry of CDs together with their photostability and aqueous solubility make CDs versatile photosensitizers for redox enzymes with great scope for their utilization in photobiocatalysis.

Effects of coal mining, forestry, and road construction on southern Appalachian stream invertebrates and habitats.

PubMed

Gangloff, Michael M; Perkins, Michael; Blum, Peter W; Walker, Craig

2015-03-01

Coal has been extracted via surface and sub-surface mining for decades throughout the Appalachian Mountains. New interest in ridge-top mining has raised concerns about possible waterway impacts. We examined effects of forestry, mining, and road construction-based disturbance on physico-chemistry and macroinvertebrate communities in east-central Tennessee headwater streams. Although 11 of 30 sites failed Tennessee's biocriteria scoring system, invertebrate richness was moderately high and we did not find significant differences in any water chemistry or habitat parameters between sites with passing and failing scores. However, conductivity and dissolved solid concentrations appeared elevated in the majority of study streams. Principal components (PCs) analysis indicated that six PCs accounted for ~77 % of among-site habitat variability. One PC associated with dissolved oxygen and specific conductance explained the second highest proportion of among-site variability after catchment area. Specific conductance was not correlated with catchment area but was strongly correlated with mining activity. Composition and success of multivariate models using habitat PCs to predict macroinvertebrate metrics was highly variable. PC scores associated with water chemistry and substrate composition were most frequently included in significant models. These results suggest that impacts of historical and current coal mining remain a source of water quality and macroinvertebrate community impairment in this region, but effects are subtle. Our results suggest that surface mining may have chronic and system-wide effects on habitat conditions and invertebrate communities in Cumberland Plateau streams.

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

NASA Astrophysics Data System (ADS)

Purkait, Tapas Kumar

Germanium nanoparticles (Ge NPs) may be fascinating for their electronic and optoelectronic properties, as the band gap of Ge NPs can be tuned from the infrared into the visible range of solar spectru. Further functionalization of those nanoparticles may potentially lead to numerous applications ranging from surface attachment, bioimaging, drug delivery and nanoparticles based devices. Blue luminescent germanium nanoparticles were synthesized from a novel top-down mechanochemical process using high energy ball milling (HEBM) of bulk germanium. Various reactive organic molecules (such as, alkynes, nitriles, azides) were used in this process to react with fresh surface and passivate the surface through Ge-C or Ge-N bond. Various purification process, such as gel permeation chromatography (GPC), Soxhlet dailysis etc. were introduced to purify nanoparticles from molecular impurities. A size separation technique was developed using GPC. The size separated Ge NPs were characterize by TEM, small angle X-ray scattering (SAXS), UV-vis absorption and photoluminescence (PL) emission spectroscopy to investigate their size selective properties. Germanium nanoparticles with alkyne termini group were prepared by HEBM of germanium with a mixture of n-alkynes and alpha, o-diynes. Additional functionalization of those nanoparticles was achieved by copper(I) catalyzed azide-alkyne "click" reaction. A variety of organic and organometallic azides including biologically important glucals have been reacted in this manner resulting in nanopartilces adorned with ferrocenyl, trimethylsilyl, and glucal groups. Additional functionalization of those nanoparticles was achieved by reactions with various azides via a Cu(I) catalyzed azide-alkyne "click" reaction. Various azides, including PEG derivatives and cylcodextrin moiety, were grafted to the initially formed surface. Globular nanoparticle arrays were formed through interparticle linking via "click" chemistry or "host-guest" chemistry. Copper(I) catalyzed "click" chemistry also can be explored with azido-terminated Ge NPs which were synthesized by azidation of chloro-terminated Ge NPs. Water soluble PEGylated Ge NPs were synthesized by "click" reaction for biological application. PEGylated Ge NP clusters were prepared using alpha, o-bis alkyno or bis-azido polyethylene glycol (PEG) derivatives by copper catalyzed "click" reaction via inter-particle linking. These nanoparticles were further functionalized by azido beta-cyclodextrin (beta-CD) and azido adamantane via alkyne-azide "click" reactions. Nanoparticle clusters were made from the functionalized Ge NPs by "host-guest" chemistry of beta-CD functionalized Ge NPs either with adamantane functionalized Ge NPs or fullerene, C60.

Students' Perceptions of Teaching in Context-based and Traditional Chemistry Classrooms: Comparing content, learning activities, and interpersonal perspectives

NASA Astrophysics Data System (ADS)

Overman, Michelle; Vermunt, Jan D.; Meijer, Paulien C.; Bulte, Astrid M. W.; Brekelmans, Mieke

2014-07-01

Context-based curriculum reforms in chemistry education are thought to bring greater diversity to the ways in which chemistry teachers organize their teaching. First and foremost, students are expected to perceive this diversity. However, empirical research on how students perceive their teacher's teaching in context-based chemistry classrooms, and whether this teaching differs from traditional chemistry lessons, is scarce. This study aims to develop our understanding of what teaching looks like, according to students, in context-based chemistry classrooms compared with traditional chemistry classrooms. As such, it might also provide a better understanding of whether teachers implement and attain the intentions of curriculum developers. To study teacher behaviour we used three theoretical perspectives deemed to be important for student learning: a content perspective, a learning activities perspective, and an interpersonal perspective. Data were collected from 480 students in 24 secondary chemistry classes in the Netherlands. Our findings suggest that, according to the students, the changes in teaching in context-based chemistry classrooms imply a lessening of the emphasis on fundamental chemistry and the use of a teacher-centred approach, compared with traditional chemistry classrooms. However, teachers in context-based chemistry classrooms seem not to display more 'context-based' teaching behaviour, such as emphasizing the relation between chemistry, technology, and society and using a student-centred approach. Furthermore, students in context-based chemistry classrooms perceive their teachers as having less interpersonal control and showing less affiliation than teachers in traditional chemistry classrooms. Our findings should be interpreted in the context of former and daily experiences of both teachers and students. As only chemistry is reformed in the schools in which context-based chemistry is implemented, it is challenging for both students and teachers to deal with these reforms.

A Thematic Review of Studies into the Effectiveness of Context-Based Chemistry Curricula

ERIC Educational Resources Information Center

Ultay, Neslihan; Calik, Muammer

2012-01-01

Context-based chemistry education aims at making connections between real life and the scientific content of chemistry courses. The purpose of this study was to evaluate context-based chemistry studies. In looking for the context-based chemistry studies, the authors entered the keywords "context-based", "contextual learning" and "chemistry…

Chemistry Division annual progress report for period ending April 30, 1993

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

Poutsma, M.L.; Ferris, L.M.; Mesmer, R.E.

1993-08-01

The Chemistry Division conducts basic and applied chemical research on projects important to DOE`s missions in sciences, energy technologies, advanced materials, and waste management/environmental restoration; it also conducts complementary research for other sponsors. The research are arranged according to: coal chemistry, aqueous chemistry at high temperatures and pressures, geochemistry, chemistry of advanced inorganic materials, structure and dynamics of advanced polymeric materials, chemistry of transuranium elements and compounds, chemical and structural principles in solvent extraction, surface science related to heterogeneous catalysis, photolytic transformations of hazardous organics, DNA sequencing and mapping, and special topics.

Magmatic and fragmentation controls on volcanic ash surface chemistry

NASA Astrophysics Data System (ADS)

Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

2016-04-01

The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that partitioning effect, but crucially, disparities between surface and bulk chemistry remain evident. Simple glass-plagioclase mixing calculations suggest that this feature may indicate differences in bulk and surface mineral distributions; future QEMSCAN analysis will investigate this possibility further. Additionally, surface iron enrichments observed in our high temperature experiments suggest that hot oxidation effects can have a near-instantaneous, measurable effect on ash surface chemistry at the nanometre scale. Our preliminary results suggest that the chemical and mineral properties of the source magma, coupled with high temperature fragmentation processes, may have a significant influence on ash surface chemistry and mineralogy, and subsequently, on the post-eruptive alteration of ash particles and their reactivity within biotic and abiotic systems.

Laser surface structuring of AZ31 Mg alloy for controlled wettability.

PubMed

Gökhan Demir, Ali; Furlan, Valentina; Lecis, Nora; Previtali, Barbara

2014-06-01

Structured surfaces exhibit functional properties that can enhance the performance of a bioimplant in terms of biocompatibility, adhesion, or corrosion behavior. In order to tailor the surface property, chemical and physical methods can be used in a sequence of many steps. On the other hand, laser surface processing can provide a single step solution to achieve the designated surface function with the use of simpler equipment and high repeatability. This work provides the details on the surface structuring of AZ31, a biocompatible and biodegradable Mg alloy, by a single-step laser surface structuring based on remelting. The surfaces are characterized in terms of topography, chemistry, and physical integrity, as well as the effective change in the surface wetting behavior is demonstrated. The results imply a great potential in local or complete surface structuring of medical implants for functionalization by the flexible positioning of the laser beam.

Measuring restoration progress using pore- and surface-water chemistry across a chronosequence of formerly afforested blanket bogs.

PubMed

Gaffney, Paul P J; Hancock, Mark H; Taggart, Mark A; Andersen, Roxane

2018-08-01

During the restoration of degraded bogs and other peatlands, both habitat and functional recovery can be closely linked with nutrient cycling, which is reflected in pore- and surface-water chemistry. Several peatland restoration studies have shown that the time required for recovery of target conditions is slow (>10 years); for heavily-impacted, drained and afforested peatlands of northern Scotland, recovery time is unknown. We monitored pore- and surface-water chemistry across a chronosequence of formerly drained, afforested bog restoration sites spanning 0-17 years, using a space-for-time substitution, and compared them with open blanket bog control sites. Our aims were to measure rate of recovery towards bog conditions and to identify the best suite of water chemistry variables to indicate recovery. Our results show progress in recovery towards bog conditions over a 0-17 year period post-restoration. Elements scavenged by trees (Mg, Na, S) completely recovered within that period. Many water chemistry variables were affected by the restoration process itself, but recovered within 11 years, except ammonium (NH 4 + ), Zn and dissolved organic carbon (DOC) which remained elevated (when compared to control bogs) 17 years post restoration. Other variables did not completely recover (water table depth (WTD), pH), exhibiting what we term "legacy" effects of drainage and afforestation. Excess N and a lowered WTD are likely to slow the recovery of bog vegetation including key bog plants such as Sphagnum mosses. Over 17 years, we measured near-complete recovery in the chemistry of surface-water and deep pore-water but limited progress in shallow pore-water. Our results suggest that at least >17 years are required for complete recovery of water chemistry to bog conditions. However, we expect that newer restoration methods including conifer harvesting (stem plus brash) and the blocking of plough furrows (to increase the WTD) are likely to accelerate the restoration process (albeit at greater cost); this should be evaluated in future studies. We conclude that monitoring pore- and surface-water chemistry is useful in terms of indicating recovery towards bog conditions and we recommend monitoring WTD, pH, conductivity, Ca, NH 4 + , phosphate (PO 4 3- ), K, DOC, Al and Zn as key variables. Copyright © 2018 Elsevier Ltd. All rights reserved.

LiNbO3 surfaces from a microscopic perspective

NASA Astrophysics Data System (ADS)

Sanna, Simone; Gero Schmidt, Wolf

2017-10-01

A large number of oxides has been investigated in the last twenty years as possible new materials for various applications ranging from opto-electronics to heterogeneous catalysis. In this context, ferroelectric oxides are particularly promising. The electric polarization plays a crucial role at many oxide surfaces, and it largely determines their physical and chemical properties. Ferroelectrics offer in addition the possibility to control/switch the electric polarization and hence the surface chemistry, allowing for the realization of domain-engineered nanoscale devices such as molecular detectors or highly efficient catalysts. Lithium niobate (LiNbO3) is a ferroelectric with a high spontaneous polarization, whose surfaces have a huge and largely unexplored potential. Owing to recent advances in experimental techniques and sample preparation, peculiar and exclusive properties of LiNbO3 surfaces could be demonstrated. For example, water films freeze at different temperatures on differently polarized surfaces, and the chemical etching properties of surfaces with opposite polarization are strongly different. More important, the ferroelectric domain orientation affects temperature dependent surface stabilization mechanisms and molecular adsorption phenomena. Various ab initio theoretical investigations have been performed in order to understand the outcome of these experiments and the origin of the exotic behavior of the lithium niobate surfaces. Thanks to these studies, many aspects of their surface physics and chemistry could be clarified. Yet other puzzling features are still not understood. This review gives a résumé on the present knowledge of lithium niobate surfaces, with a particular view on their microscopic properties, explored in recent years by means of ab initio calculations. Relevant aspects and properties of the surfaces that need further investigation are briefly discussed. The review is concluded with an outlook of challenges and potential payoff for LiNbO3 based applications.

Soil calcium status and the response of stream chemistry to changing acidic deposition rates

USGS Publications Warehouse

Lawrence, G.B.; David, M.B.; Lovett, Gary M.; Murdoch, Peter S.; Burns, Douglas A.; Stoddard, J.L.; Baldigo, Barry P.; Porter, J.H.; Thompson, A.W.

1999-01-01

Despite a decreasing trend in acidic deposition rates over the past two to three decades, acidified surface waters in the northeastern United States have shown minimal changes. Depletion of soil Ca pools has been suggested as a cause, although changes in soil Ca pools have not been directly related to long-term records of stream chemistry. To investigate this problem, a comprehensive watershed study was conducted in the Neversink River Basin, in the Catskill Mountains of New York, during 1991-1996. Spatial variations of atmospheric deposition, soil chemistry, and stream chemistry were evaluated over an elevation range of 817-1234 m to determine whether these factors exhibited elevational patterns. An increase in atmospheric deposition of SO4 with increasing elevation corresponded with upslope decreases of exchangeable soil base concentrations and acid-neutralizing capacity of stream water. Exchangeable base concentrations in homogeneous soil incubated within the soil profile for one year also decreased with increasing elevation. An elevational gradient in precipitation was not observed, and effects of a temperature gradient on soil properties were not detected. Laboratory leaching experiments with soils from this watershed showed that (1) concentrations of Ca in leachate increased as the concentrations of acid anions in added solution increased, and (2) the slope of this relationship was positively correlated with base saturation. Field and laboratory soil analyses are consistent with the interpretation that decreasing trends in acid-neutralizing capacity in stream water in the Neversink Basin, dating back to 1984, are the result of decreases in soil base saturation caused by acidic deposition.

Understanding the Reaction Chemistry of 2,2':5',2''-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

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

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding the Reaction Chemistry of 2,2':5',2"-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

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

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

PubMed

Williams, David; Viti, Serena

2013-07-13

We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day.

Next Steps Forward in Understanding Martian Surface and Subsurface Chemistry

NASA Astrophysics Data System (ADS)

Carrier, Brandi L.

2017-09-01

The presence of oxidants such as hydrogen peroxide (H2O2) and perchlorate (ClO4-), which have been detected on Mars, has significant implications for chemistry and astrobiology. These oxidants can increase the reactivity of the Martian soil, accelerate the decomposition of organic molecules, and depress the freezing point of water. The study by Crandall et al. "Can Perchlorates be Transformed to Hydrogen Peroxide Products by Cosmic Rays on the Martian Surface" reveals a new formation mechanism by which hydrogen peroxide and other potential oxidants can be generated via irradiation of perchlorate by cosmic rays. This study represents an important next step in developing a full understanding of Martian surface and subsurface chemistry, particularly with respect to degradation of organic molecules and potential biosignatures.

Influence of surface structure and chemistry on water droplet splashing.

PubMed

Koch, Kerstin; Grichnik, Roland

2016-08-06

Water droplet splashing and aerosolization play a role in human hygiene and health systems as well as in crop culturing. Prevention or reduction of splashing can prevent transmission of diseases between animals and plants and keep technical systems such as pipe or bottling systems free of contamination. This study demonstrates to what extent the surface chemistry and structures influence the water droplet splashing behaviour. Smooth surfaces and structured replicas of Calathea zebrina (Sims) Lindl. leaves were produced. Modification of their wettability was done by coating with hydrophobizing and hydrophilizing agents. Their wetting was characterized by contact angle measurement and splashing behaviour was observed with a high-speed video camera. Hydrophobic and superhydrophilic surfaces generally showed fewer tendencies to splash than hydrophobic ones. Structuring amplified the underlying behaviour of the surface chemistries, increasing hydrophobic surfaces' tendency to splash and decreasing splash on hydrophilic surfaces by quickly transporting water off the impact point by capillary forces. The non-porous surface structures found in C. zebrina could easily be applied to technical products such as plastic foils or mats and coated with hydrophilizing agents to suppress splash in areas of increased hygiene requirements or wherever pooling of liquids is not desirable.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'. © 2016 The Author(s).

Cellular Responses Evoked by Different Surface Characteristics of Intraosseous Titanium Implants

PubMed Central

Feller, Liviu; Jadwat, Yusuf; Khammissa, Razia A. G.; Meyerov, Robin; Lemmer, Johan

2015-01-01

The properties of biomaterials, including their surface microstructural topography and their surface chemistry or surface energy/wettability, affect cellular responses such as cell adhesion, proliferation, and migration. The nanotopography of moderately rough implant surfaces enhances the production of biological mediators in the peri-implant microenvironment with consequent recruitment of differentiating osteogenic cells to the implant surface and stimulates osteogenic maturation. Implant surfaces with moderately rough topography and with high surface energy promote osteogenesis, increase the ratio of bone-to-implant contact, and increase the bonding strength of the bone to the implant at the interface. Certain features of implant surface chemistry are also important in enhancing peri-implant bone wound healing. It is the purpose of this paper to review some of the more important features of titanium implant surfaces which have an impact on osseointegration. PMID:25767803

Surface chemistry reactions of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone and air on a glass and a vinyl tile.

PubMed

Ham, J E; Wells, J R

2008-10-01

The surface-phase reaction products of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone (O(3)), air or nitrogen (N(2)) on both a glass and vinyl flooring tile were investigated using the recently published FLEC Automation and Control System (FACS). The FACS was used to deliver O(3) (100 ppb), air or N(2) to the surface at a specified flow rate (300 ml/min) and relative humidity (50%) after application of a 1.6%alpha-terpineol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine and N,O-bis(trimethysilyl)trifluoroacetamide. The positively identified reaction products were glyoxal, methylglyoxal and 4-oxopentanal. The proposed oxidation products based on previously published VOC/O(3) reaction mechanisms were: 4-methylcyclohex-3-en-1-one, 6-hydroxyhept-en-2-one, 3-(1-hydroxy-1-methylethyl)-6-methylcyclohex-2-en-1-one) and one surface-enhanced reaction product: 5-(1-hydroxy-1-methylethyl)-2-methylcyclohex-2-en-1-one. Though similar products were observed in gas-phase alpha-terpineol/O(3) reactions, the ratio of the reaction products were different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. Volatile organic compounds (VOCs) can interact with indoor initiators [such as hydroxyl radicals (OH*), ozone and nitrate radicals (NO(3)*)] to form a number of oxygenated by-products in the gas-phase. However, when VOCs are applied to or are present on the surface, heterogeneous chemistry with indoor initiators can also occur. The surface can influence the reaction mechanism to produce new surface reaction products. The work, described here, shows the interaction of alpha-terpineol (major component of pine oil) with ozone and air on both glass and vinyl flooring. These results demonstrated emissions of oxygenated organic compounds as a result of reaction and that further investigations of this chemistry are required to accurately estimate indoor occupant exposures.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

NASA Astrophysics Data System (ADS)

Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

2018-05-01

The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

Surface topography and chemistry shape cellular behavior on wide band-gap semiconductors.

PubMed

Bain, Lauren E; Collazo, Ramon; Hsu, Shu-Han; Latham, Nicole Pfiester; Manfra, Michael J; Ivanisevic, Albena

2014-06-01

The chemical stability and electrical properties of gallium nitride make it a promising material for the development of biocompatible electronics, a range of devices including biosensors as well as interfaces for probing and controlling cellular growth and signaling. To improve the interface formed between the probe material and the cell or biosystem, surface topography and chemistry can be applied to modify the ways in which the device interacts with its environment. PC12 cells are cultured on as-grown planar, unidirectionally polished, etched nanoporous and nanowire GaN surfaces with and without a physisorbed peptide sequence that promotes cell adhesion. While cells demonstrate preferential adhesion to roughened surfaces over as-grown flat surfaces, the topography of that roughness also influences the morphology of cellular adhesion and differentiation in neurotypic cells. Addition of the peptide sequence generally contributes further to cellular adhesion and promotes development of stereotypic long, thin neurite outgrowths over alternate morphologies. The dependence of cell behavior on both the topographic morphology and surface chemistry is thus demonstrated, providing further evidence for the importance of surface modification for modulating bio-inorganic interfaces. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of denture cleansers on color stability, surface roughness, and hardness of different denture base resins

PubMed Central

Porwal, Anand; Khandelwal, Meenakshi; Punia, Vikas; Sharma, Vivek

2017-01-01

Aim: The purpose of this study was to evaluate the effect of different denture cleansers on the color stability, surface hardness, and roughness of different denture base resins. Materials and Methods: Three denture base resin materials (conventional heat cure resin, high impact resin, and polyamide denture base resin) were immersed for 180 days in commercially available two denture cleansers (sodium perborate and sodium hypochlorite). Color, surface roughness, and hardness were measured for each sample before and after immersion procedure. Statistical Analysis: One-way analysis of variance and Tukey's post hoc honestly significant difference test were used to evaluate color, surface roughness, and hardness data before and after immersion in denture cleanser (α =0.05). Results: All denture base resins tested exhibited a change in color, surface roughness, and hardness to some degree in both denture cleansers. Polyamides resin immersed in sodium perborate showed a maximum change in color after immersion for 180 days. Conventional heat cure resin immersed in sodium hypochlorite showed a maximum change in surface roughness and conventional heat cure immersed in sodium perborate showed a maximum change in hardness. Conclusion: Color changes of all denture base resins were within the clinically accepted range for color difference. Surface roughness change of conventional heat cure resin was not within the clinically accepted range of surface roughness. The choice of denture cleanser for different denture base resins should be based on the chemistry of resin and cleanser, denture cleanser concentration, and duration of immersion. PMID:28216847

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

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

Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney

The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further themore » similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.« less

Global transcriptomic analysis of model human cell lines exposed to surface-modified gold nanoparticles: the effect of surface chemistry

NASA Astrophysics Data System (ADS)

Grzincic, E. M.; Yang, J. A.; Drnevich, J.; Falagan-Lotsch, P.; Murphy, C. J.

2015-01-01

Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected.Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected. Electronic supplementary information (ESI) available: UV-Vis spectra of Au NPs, the most significantly changed genes of HDF cells after Au NP incubation under GO accession number GO:0007049 ``cell cycle'', detailed information about the primer/probe sets used for RT-PCR validation of results. See DOI: 10.1039/c4nr05166a

Towards "Bildung"-Oriented Chemistry Education

ERIC Educational Resources Information Center

Sjöström, Jesper

2013-01-01

This paper concerns "Bildung"-oriented chemistry education, based on a reflective and critical discourse of chemistry. It is contrasted with the dominant type of chemistry education, based on the mainstream discourse of chemistry. "Bildung"-oriented chemistry education includes not only content knowledge in chemistry, but also…

Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

PubMed

Yang, Zhenyu; Gonzalez, Christina M; Purkait, Tapas K; Iqbal, Muhammad; Meldrum, Al; Veinot, Jonathan G C

2015-09-29

Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials

PubMed Central

Valentine, M. T.; Perlman, Z. E.; Gardel, M. L.; Shin, J. H.; Matsudaira, P.; Mitchison, T. J.; Weitz, D. A.

2004-01-01

Characterization of the properties of complex biomaterials using microrheological techniques has the promise of providing fundamental insights into their biomechanical functions; however, precise interpretations of such measurements are hindered by inadequate characterization of the interactions between tracers and the networks they probe. We here show that colloid surface chemistry can profoundly affect multiple particle tracking measurements of networks of fibrin, entangled F-actin solutions, and networks of cross-linked F-actin. We present a simple protocol to render the surface of colloidal probe particles protein-resistant by grafting short amine-terminated methoxy-poly(ethylene glycol) to the surface of carboxylated microspheres. We demonstrate that these poly(ethylene glycol)-coated tracers adsorb significantly less protein than particles coated with bovine serum albumin or unmodified probe particles. We establish that varying particle surface chemistry selectively tunes the sensitivity of the particles to different physical properties of their microenvironments. Specifically, particles that are weakly bound to a heterogeneous network are sensitive to changes in network stiffness, whereas protein-resistant tracers measure changes in the viscosity of the fluid and in the network microstructure. We demonstrate experimentally that two-particle microrheology analysis significantly reduces differences arising from tracer surface chemistry, indicating that modifications of network properties near the particle do not introduce large-scale heterogeneities. Our results establish that controlling colloid-protein interactions is crucial to the successful application of multiple particle tracking techniques to reconstituted protein networks, cytoplasm, and cells. PMID:15189896

Defining the Post-Machined Sub-surface in Austenitic Stainless Steels

NASA Astrophysics Data System (ADS)

Srinivasan, N.; Sunil Kumar, B.; Kain, V.; Birbilis, N.; Joshi, S. S.; Sivaprasad, P. V.; Chai, G.; Durgaprasad, A.; Bhattacharya, S.; Samajdar, I.

2018-04-01

Austenitic stainless steels grades, with differences in chemistry, stacking fault energy, and thermal conductivity, were subjected to vertical milling. Anodic potentiodynamic polarization was able to differentiate (with machining speed/strain rate) between different post-machined sub-surfaces in SS 316L and Alloy A (a Cu containing austenitic stainless steel: Sanicroe 28™), but not in SS 304L. However, such differences (in the post-machined sub-surfaces) were revealed in surface roughness, sub-surface residual stresses and misorientations, and in the relative presence of sub-surface Cr2O3 films. It was shown, quantitatively, that higher machining speed reduced surface roughness and also reduced the effective depths of the affected sub-surface layers. A qualitative explanation on the sub-surface microstructural developments was provided based on the temperature-dependent thermal conductivity values. The results herein represent a mechanistic understanding to rationalize the corrosion performance of widely adopted engineering alloys.

Defining the Post-Machined Sub-surface in Austenitic Stainless Steels

NASA Astrophysics Data System (ADS)

Srinivasan, N.; Sunil Kumar, B.; Kain, V.; Birbilis, N.; Joshi, S. S.; Sivaprasad, P. V.; Chai, G.; Durgaprasad, A.; Bhattacharya, S.; Samajdar, I.

2018-06-01

Austenitic stainless steels grades, with differences in chemistry, stacking fault energy, and thermal conductivity, were subjected to vertical milling. Anodic potentiodynamic polarization was able to differentiate (with machining speed/strain rate) between different post-machined sub-surfaces in SS 316L and Alloy A (a Cu containing austenitic stainless steel: Sanicroe 28™), but not in SS 304L. However, such differences (in the post-machined sub-surfaces) were revealed in surface roughness, sub-surface residual stresses and misorientations, and in the relative presence of sub-surface Cr2O3 films. It was shown, quantitatively, that higher machining speed reduced surface roughness and also reduced the effective depths of the affected sub-surface layers. A qualitative explanation on the sub-surface microstructural developments was provided based on the temperature-dependent thermal conductivity values. The results herein represent a mechanistic understanding to rationalize the corrosion performance of widely adopted engineering alloys.

Gordon Research Conference on Plasma Chemistry (10th), Held in Tilton, New Hampshire on August 15-19, 1988

DTIC Science & Technology

1989-10-01

The 1988 Gordon Research Conference on Plasma Chemistry was divided into nine sessions. Eight had two or three invited talks and two or three...findings in low pressure, non-equilibrium plasma chemistry , covering the topics of plasmas in device technology, and plasma enhanced processing...applications and surface-plasma interactions. Six joint sessions included sessions on future plasma chemistry , nucleation and growth, plasma modeling, one each

Steam based conversion coating on AA6060 alloy: Effect of sodium silicate chemistry and corrosion performance

NASA Astrophysics Data System (ADS)

Din, Rameez Ud; Bordo, Kirill; Tabrizian, Naja; Jellesen, Morten Stendahl; Ambat, Rajan

2017-11-01

Surface treatment of aluminium alloy AA6060 using an industrially applicable pilot steam jet system with and without silicate chemistry has been investigated. Treatment using steam alone and steam with silicate, resulted in an oxide layer formation with thickness ∼425 nm and ∼160 nm, respectively. Moreover, the use of sodium silicate resulted in the formation of distinct microstructure and incorporation of silicate into the oxide film. These oxide films reduced the anodic activity 4 times, while the corrosion protection by silicate containing oxide was the function of its concentration. Further, in acid salt spray and filiform corrosion tests, oxide layer containing silicate exhibited two times higher corrosion resistance.

Peptide-Decorated Tunable-Fluorescence Graphene Quantum Dots.

PubMed

Sapkota, Bedanga; Benabbas, Abdelkrim; Lin, Hao-Yu Greg; Liang, Wentao; Champion, Paul; Wanunu, Meni

2017-03-22

We report here the synthesis of graphene quantum dots with tunable size, surface chemistry, and fluorescence properties. In the size regime 15-35 nm, these quantum dots maintain strong visible light fluorescence (mean quantum yield of 0.64) and a high two-photon absorption (TPA) cross section (6500 Göppert-Mayer units). Furthermore, through noncovalent tailoring of the chemistry of these quantum dots, we obtain water-stable quantum dots. For example, quantum dots with lysine groups bind strongly to DNA in solution and inhibit polymerase-based DNA strand synthesis. Finally, by virtue of their mesoscopic size, the quantum dots exhibit good cell permeability into living epithelial cells, but they do not enter the cell nucleus.

Functionality in Electrospun Nanofibrous Membranes Based on Fiber's Size, Surface Area, and Molecular Orientation

PubMed Central

Matsumoto, Hidetoshi; Tanioka, Akihiko

2011-01-01

Electrospinning is a versatile method for forming continuous thin fibers based on an electrohydrodynamic process. This method has the following advantages: (i) the ability to produce thin fibers with diameters in the micrometer and nanometer ranges; (ii) one-step forming of the two- or three-dimensional nanofiber network assemblies (nanofibrous membranes); and (iii) applicability for a broad spectrum of molecules, such as synthetic and biological polymers and polymerless sol-gel systems. Electrospun nanofibrous membranes have received significant attention in terms of their practical applications. The major advantages of nanofibers or nanofibrous membranes are the functionalities based on their nanoscaled-size, highly specific surface area, and highly molecular orientation. These functionalities of the nanofibrous membranes can be controlled by their fiber diameter, surface chemistry and topology, and internal structure of the nanofibers. This report focuses on our studies and describes fundamental aspects and applications of electrospun nanofibrous membranes. PMID:24957735

Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions

NASA Astrophysics Data System (ADS)

Podkościelny, P.; László, K.

2007-08-01

The heterogeneity of activated carbons (ACs) prepared from different precursors is investigated on the basis of adsorption isotherms of aniline from dilute aqueous solutions at various pH values. The APET carbon prepared from polyethyleneterephthalate (PET), as well as, commercial ACP carbon prepared from peat were used. Besides, to investigate the influence of carbon surface chemistry, the adsorption was studied on modified carbons based on ACP carbon. Its various oxygen surface groups were changed by both nitric acid and thermal treatments. The Dubinin-Astakhov (DA) equation and Langmuir-Freundlich (LF) one have been used to model the phenomenon of aniline adsorption from aqueous solutions on heterogeneous carbon surfaces. Adsorption-energy distribution (AED) functions have been calculated by using an algorithm based on a regularization method. Analysis of these functions for activated carbons studied provides important comparative information about their surface heterogeneity.

The role of surface chemistry in the cytotoxicity profile of graphene.

PubMed

Majeed, Waqar; Bourdo, Shawn; Petibone, Dayton M; Saini, Viney; Vang, Kieng Bao; Nima, Zeid A; Alghazali, Karrer M; Darrigues, Emilie; Ghosh, Anindya; Watanabe, Fumiya; Casciano, Daniel; Ali, Syed F; Biris, Alexandru S

2017-04-01

Graphene and its derivative, because of their unique physical, electrical and chemical properties, are an important class of nanomaterials being proposed as foundational materials in nanomedicine as well as for a variety of industrial applications. A major limitation for graphene, when used in biomedical applications, is its poor solubility due to its rather hydrophobic nature. Therefore, chemical functionalities are commonly introduced to alter both its surface chemistry and biochemical activity. Here, we show that surface chemistry plays a major role in the toxicological profile of the graphene structures. To demonstrate this, we chemically increased the oxidation level of the pristine graphene and compared the corresponding toxicological effects along with those for the graphene oxide. X-ray photoelectron spectroscopy revealed that pristine graphene had the lowest amount of surface oxygen, while graphene oxide had the highest at 2.5% and 31%, respectively. Low and high oxygen functionalized graphene samples were found to have 6.6% and 24% surface oxygen, respectively. Our results showed a dose-dependent trend in the cytotoxicity profile, where pristine graphene was the most cytotoxic, with decreasing toxicity observed with increasing oxygen content. Increased surface oxygen also played a role in nanomaterial dispersion in water or cell culture medium over longer periods. It is likely that higher dispersity might result in graphene entering into cells as individual flakes ~1 nm thick rather than as more cytotoxic aggregates. In conclusion, changes in graphene's surface chemistry resulted in altered solubility and toxicity, suggesting that a generalized toxicity profile would be rather misleading. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

A Thematic Review of Studies into the Effectiveness of Context-Based Chemistry Curricula

NASA Astrophysics Data System (ADS)

Ültay, Neslihan; Çalık, Muammer

2012-12-01

Context-based chemistry education aims at making connections between real life and the scientific content of chemistry courses. The purpose of this study was to evaluate context-based chemistry studies. In looking for the context-based chemistry studies, the authors entered the keywords `context-based', `contextual learning' and `chemistry education' in well-known databases (i.e. Academic Search Complete, Education Research Complete, ERIC, Springer LINK Contemporary). Further, in case the computer search by key words may have missed a rather substantial part of the important literature in the area, the authors also conducted a hand search of the related journals. To present a detailed thematic review of context-based chemistry studies, a matrix was used to summarize the findings by focusing on insights derived from the related studies. The matrix incorporates the following themes: needs, aims, methodologies, general knowledge claims, and implications for teaching and learning, implications for curriculum development and suggestions for future research. The general knowledge claims investigated in this paper were: (a) positive effects of the context-based chemistry studies; (b) caveats, both are examined in terms of students' attitudes and students' understanding/cognition. Implications were investigated for practice in context- based chemistry studies, for future research in context- based chemistry studies, and for curriculum developers in context- based chemistry studies. Teachers of context-based courses claimed that the application of the context-based learning approach in chemistry education improved students' motivation and interest in the subject. This seems to have generated an increase in the number of the students who wish to continue chemistry education at higher levels. However, despite the fact that the majority of the studies have reported advantages of context-based chemistry studies, some of them have also referred to pitfalls, i.e. dominant structure of out-of-school learning, tough nature of some chemistry topics, and teacher anxiety of lower-ability students.

Chemical Gradients on Graphene to Drive Droplet Motion

DTIC Science & Technology

2013-05-09

the flexibility of carbon chemistry, graphene provides many options in designing such gradients. Moreover, to effectively move a liquid droplet, the...surface chemistry gradientmust be both continuous (x and y direction) and uniform in the direc - tion perpendicular to the droplet motion (y direction) to...directing the transport of liquid droplets. This work demonstrates that with careful consideration of the surface chem- istry, electron beam-generated

Knowledge Production at Industrial Research Institutes: Institutional Logics and Struggles for Relevance in the Swedish Institute for Surface Chemistry, 1980-2005

ERIC Educational Resources Information Center

Bruno, Karl; Larsen, Katarina; van Leeuwen, Thed N.

2017-01-01

This article examines dynamics of knowledge production and discourses of basic-applied science and relevance at the Swedish Institute for Surface Chemistry, a semi-public industrially oriented research institute, from 1980 to 2005. We employ a three-pronged method, consisting of (1) an analysis of how the institute articulated its research…

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Saturn's satellites: Potential for organic chemistry

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Lane, A. L.; Henry-Riyad, H.; Tidwell, T. T.

2003-05-01

The surfaces of the Saturnian satellites are subjected to irradiation from solar wind ions, photons, and magnetospheric ions and electrons. This bombardment will transform the chemical nature of the surfaces. At present, only water ice has been detected on their surfaces. Further studies by the Cassini spacecraft may reveal other molecules. If CO2 ice is found there, a whole panoply of new species may be detected. As nitrogen ions in the magnetosphere are thought to be an important species bombarding the satellites, Delitsky and Lane (2002) outlined the nitrogen oxides chemistry that may result from implantation of N+ into the water ice surfaces. Sittler et al (2002) showed that N+ ions originating from Titan will be enriched in the magnetospheric ion population as they move inwards towards Saturn, making the nitrogen oxides chemistry more likely. If CO2 is present, a complicated C-H-N-O chemistry may result from deposition of the N+ into a H2O/CO2 mixed ice, including nitriles, isocyanates, polymers, and amino acids. The combination of H2O/CO2 upon irradiation may also yield a complex mixture of hydrocarbons, esters, alcohols, organic acids and ketones. Possible chemical pathways and computations of their energetics will be presented. -Ref:- 1. Delitsky and Lane, Saturn's inner satellites: Ice chemistry and magnetosphere effects, JGR (Planets), Nov 2002, 3-1;; 2. Sittler et al., Energetic nitrogen ions within the inner magnetosphere of Saturn, Fall AGU meeting, Dec 2002, abstracts, pg F858, P21B-0379

Early osteoblast responses to orthopedic implants: Synergy of surface roughness and chemistry of bioactive ceramic coating.

PubMed

Aniket; Reid, Robert; Hall, Benika; Marriott, Ian; El-Ghannam, Ahmed

2015-06-01

Pro-osteogenic stimulation of bone cells by bioactive ceramic-coated orthopedic implants is influenced by both surface roughness and material chemistry; however, their concomitant impact on osteoblast behavior is not well understood. The aim of this study is to investigate the effects of nano-scale roughness and chemistry of bioactive silica-calcium phosphate nanocomposite (SCPC50) coated Ti-6Al-4V on modulating early bone cell responses. Cell attachment was higher on SCPC50-coated substrates compared to the uncoated controls; however, cells on the uncoated substrate exhibited greater spreading and superior quality of F-actin filaments than cells on the SCPC50-coated substrates. The poor F-actin filament organization on SCPC50-coated substrates is thought to be due to the enhanced calcium uptake by the ceramic surface. Dissolution analyses showed that an increase in surface roughness was accompanied by increased calcium uptake, and increased phosphorous and silicon release, all of which appear to interfere with F-actin assembly and osteoblast morphology. Moreover, cell attachment onto the SCPC50-coated substrates correlated with the known adsorption of fibronectin, and was independent of surface roughness. High-throughput genome sequencing showed enhanced expression of extracellular matrix and cell differentiation related genes. These results demonstrate a synergistic relationship between bioactive ceramic coating roughness and material chemistry resulting in a phenotype that leads to early osteoblast differentiation. © 2014 Wiley Periodicals, Inc.

Strain-induced alignment and phase behavior of blue phase liquid crystals confined to thin films.

PubMed

Bukusoglu, Emre; Martinez-Gonzalez, Jose A; Wang, Xiaoguang; Zhou, Ye; de Pablo, Juan J; Abbott, Nicholas L

2017-12-06

We report on the influence of surface confinement on the phase behavior and strain-induced alignment of thin films of blue phase liquid crystals (BPs). Confining surfaces comprised of bare glass, dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP)-functionalized glass, or polyvinyl alcohol (PVA)-coated glass were used with or without mechanically rubbing to influence the azimuthal anchoring of the BPs. These experiments reveal that confinement can change the phase behavior of the BP films. For example, in experiments performed with rubbed-PVA surfaces, we measured the elastic strain of the BPs to change the isotropic-BPII phase boundary, suppressing formation of BPII for film thicknesses incommensurate with the BPII lattice. In addition, we observed strain-induced alignment of the BPs to exhibit a complex dependence on both the surface chemistry and azimuthal alignment of the BPs. For example, when using bare glass surfaces causing azimuthally degenerate and planar anchoring, BPI oriented with (110) planes of the unit cell parallel to the contacting surfaces for thicknesses below 3 μm but transitioned to an orientation with (200) planes aligned parallel to the contacting surfaces for thicknesses above 4 μm. In contrast, BPI aligned with (110) planes parallel to confining surfaces for all other thicknesses and surface treatments, including bare glass with uniform azimuthal alignment. Complementary simulations based on minimization of the total free energy (Landau-de Gennes formalism) confirmed a thickness-dependent reorientation due to strain of BPI unit cells within a window of surface anchoring energies and in the absence of uniform azimuthal alignment. In contrast to BPI, BPII did not exhibit thickness-dependent orientations but did exhibit orientations that were dependent on the surface chemistry, a result that was also captured in simulations by varying the anchoring energies. Overall, the results in this paper reveal that the orientations assumed by BPs in thin films reflect a complex interplay of surface interactions and elastic energies associated with strain of the BP lattice. The results also provide new principles and methods to control the structure and properties of BP thin films, which may find use in BP-templated material synthesis, and BP-based optical and electronic devices.

Fundamentals of Chemistry at Surfaces and Beyond

DTIC Science & Technology

2013-09-23

results of this research were published in J. Phys. Chem. C.34 B4. Fundamental Theory of Organic/Inorganic Hybrid Solar Cells In the field of...B, 104, 538-547 (2000). 38B. O’Regan, M. Gratzel, “A Low-Cost, High-Efficiency Solar Cell Based on Dye-Sensitized Colloidal TiO2 Films,” Nature...N. Murakami, H. J. Snaith, “Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites,” Sci. Exp., DOI: 10.1126

New Perspectives on Context-Based Chemistry Education: Using a Dialectical Sociocultural Approach to View Teaching and Learning

ERIC Educational Resources Information Center

King, Donna

2012-01-01

Context-based chemistry education aims to improve student interest and motivation in chemistry by connecting canonical chemistry concepts with real-world contexts. Implementation of context-based chemistry programmes began 20 years ago in an attempt to make the learning of chemistry meaningful for students. This paper reviews such programmes…

The role of "inert" surface chemistry in marine biofouling prevention.

PubMed

Rosenhahn, Axel; Schilp, Sören; Kreuzer, Hans Jürgen; Grunze, Michael

2010-05-07

The settlement and colonization of marine organisms on submerged man-made surfaces is a major economic problem for many marine industries. The most apparent detrimental effects of biofouling are increased fuel consumption of ships, clogging of membranes and heat exchangers, disabled underwater sensors, and growth of biofoulers in aquaculture systems. The presently common-but environmentally very problematic-way to deal with marine biofouling is to incorporate biocides, which use biocidal products in the surface coatings to kill the colonizing organisms, into the surface coatings. Since the implementation of the International Maritime Organization Treaty on biocides in 2008, the use of tributyltin (TBT) is restricted and thus environmentally benign but effective surface coatings are required. In this short review, we summarize the different strategies which are pursued in academia and industry to better understand the mechanisms of biofouling and to develop strategies which can be used for industrial products. Our focus will be on chemically "inert" model surface coatings, in particular oligo- and poly(ethylene glycol) (OEG and PEG) functionalized surface films. The reasons for choosing this class of chemistry as an example are three-fold: Firstly, experiments on spore settlement on OEG and PEG coatings help to understand the mechanism of non-fouling of highly hydrated interfaces; secondly, these studies defy the common assumption that surface hydrophilicity-as measured by water contact angles-is an unambiguous and predictive tool to determine the fouling behavior on the surface; and thirdly, choosing this system is a good example for "interfacial systems chemistry": it connects the behavior of unicellular marine organisms with the antifouling properties of a hydrated surface coating with structural and electronic properties as derived from ab initio quantum mechanical calculations using the electronic wave functions of oxygen, hydrogen, and carbon. This short review is written to outline for non-experts the hierarchical structure in length- and timescale of marine biofouling and the role of surface chemistry in fouling prevention. Experts in the field are referred to more specialized recent reviews.

Teaching Two Basic Nanotechnology Concepts in Secondary School by Using a Variety of Teaching Methods

ERIC Educational Resources Information Center

Blonder, Ron; Sakhnini, Sohair

2012-01-01

A nanotechnology module was developed for ninth grade students in the context of teaching chemistry. Two basic concepts in nanotechnology were chosen: (1) size and scale and (2) surface-area-to-volume ratio (SA/V). A wide spectrum of instructional methods (e.g., game-based learning, learning with multimedia, learning with models, project based…

Understanding Thermal Transport in Graded, Layered and Hybrid Materials

DTIC Science & Technology

2014-04-01

interfacial chemistries, including metallic and carbide layers, and; (iv) mimic the observed interface structure on a TDTR specimen by manipulating the...surface carbides , which were extracted from several different composites via acid dissolution of Cu, continued throughout the last 12 months of the...effort. The previously-reported electron probe microanalysis (EPMA) based techniques were employed to estimate the interfacial carbide layer thickness

The influence of surface coating on the properties of water-soluble CdSe and CdSe/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Coto-García, Ana María; Fernández-Argüelles, María T.; Costa-Fernández, José M.; Sanz-Medel, Alfredo; Valledor, Marta; Campo, Juan C.; Ferrero, Francisco J.

2013-01-01

It is well-known that ligands coating the surface of luminescent semiconductor nanocrystals (quantum dots [QDs]) play an important role in the preparation, stability and physical properties of the colloidal QDs in both organic and aqueous media. Here we report on the synthesis and characterization of core (CdSe QDs) and core-shell structured QDs (CdSe/ZnS QDs), both of them stabilized in aqueous medium through different mechanisms of modification of their surface chemistry. The approaches evaluated for QDs transfer to aqueous media were ligand exchange and polymer coating. Experiments were performed using two typical thioalkyl acids as ligands, namely mercaptoacetic acid (QDs-MAA) and 2-mercaptoethanesulphonic acid (QDs-MES), and an amphiphilic polymer (PQDs) based on poly(maleic anhydride) functional groups. The effects of pH (buffer solution), illumination and the presence of ions in the QD environment on the spectroscopic properties of the different synthesized QDs are reported. The stability of the prepared QDs has been comparatively evaluated aimed to elucidate which surface chemistry provides the suitable properties to be employed as fluorescence labels in distinct types of applications. The experimental results and conclusions will be useful for the development of sensitive sensors or assays adopting QDs as fluorescence labels.

The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

NASA Astrophysics Data System (ADS)

Anisimov, M. P.

2016-12-01

One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

PubMed

Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

2016-07-08

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

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

Yao, Juan; Zhou, Yufan; Sui, Xiao

Switchable ionic liquids (SWIL) play an important role in green chemistry. Due to the nature of SWIL chemistry, such as air sensitivity and pressure and temperature dependence, it is difficult to characterize SWIL using vacuum-based surface techniques. The fully CO2 loaded and none-loaded DBU and hexanol mixtures, a SWIL system, were analyzed in situ by time-of-flight secondary ion mass spectrometry (ToF-SIMS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI), respectively. The DBU/Hexanol/CO2 SWIL was injected into the microchannel before liquid SIMS analysis. Bi3+ primary ion beam was used. The positive and negative spectra of the SWILmore » chemical components are presented. The characteristic peaks m/z 153 (reduced DBU) in the positive mode and m/z 101 (oxidized hexanol) in negative mode were observed. In addition, ion pair peaks including m/z 253, 319, 305, 451 in the positive mode and m/z 145, 223, 257 in the negative mode are first observed using this approach. These results demonstrate that the SALVI microfluidic reactor enables the vacuum-based surface technique (i.e., ToF-SIMS) for in situ characterization of challenging liquid samples such as ionic liquids.« less

Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Kessler, Vadim G.

2014-05-01

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

Photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Lee, J.-S.; Stanford, J. A.; Grant, W. K.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Swanberg, E. L.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L. J.; Shah, K.

2013-09-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. Samples of as polished TlBr were treated separately with 2%Br:MeOH, 10%HF, 10%HCl and 96%SOCl2 solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry. Results suggest anion substitution at the surface with subsequent shallow heterojunction formation. Surface chemistry and valence band electronic structure were further correlated with the goal of optimizing the long-term stability and radiation response.

Surface chemistry of gold nanoparticles determines the biocorona composition impacting cellular uptake, toxicity and gene expression profiles in human endothelial cells.

PubMed

Chandran, Parwathy; Riviere, Jim E; Monteiro-Riviere, Nancy A

2017-05-01

This study investigated the role of nanoparticle size and surface chemistry on biocorona composition and its effect on uptake, toxicity and cellular responses in human umbilical vein endothelial cells (HUVEC), employing 40 and 80 nm gold nanoparticles (AuNP) with branched polyethyleneimine (BPEI), lipoic acid (LA) and polyethylene glycol (PEG) coatings. Proteomic analysis identified 59 hard corona proteins among the various AuNP, revealing largely surface chemistry-dependent signature adsorbomes exhibiting human serum albumin (HSA) abundance. Size distribution analysis revealed the relative instability and aggregation inducing potential of bare and corona-bound BPEI-AuNP, over LA- and PEG-AuNP. Circular dichroism analysis showed surface chemistry-dependent conformational changes of proteins binding to AuNP. Time-dependent uptake of bare, plasma corona (PC) and HSA corona-bound AuNP (HSA-AuNP) showed significant reduction in uptake with PC formation. Cell viability studies demonstrated dose-dependent toxicity of BPEI-AuNP. Transcriptional profiling studies revealed 126 genes, from 13 biological pathways, to be differentially regulated by 40 nm bare and PC-bound BPEI-AuNP (PC-BPEI-AuNP). Furthermore, PC formation relieved the toxicity of cationic BPEI-AuNP by modulating expression of genes involved in DNA damage and repair, heat shock response, mitochondrial energy metabolism, oxidative stress and antioxidant response, and ER stress and unfolded protein response cascades, which were aberrantly expressed in bare BPEI-AuNP-treated cells. NP surface chemistry is shown to play the dominant role over size in determining the biocorona composition, which in turn modulates cell uptake, and biological responses, consequently defining the potential safety and efficacy of nanoformulations.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Switchable host-guest systems on surfaces.

PubMed

Yang, Ying-Wei; Sun, Yu-Long; Song, Nan

2014-07-15

CONSPECTUS: For device miniaturization, nanotechnology follows either the "top-down" approach scaling down existing larger-scale devices or the "bottom-up' approach assembling the smallest possible building blocks to functional nanoscale entities. For synthetic nanodevices, self-assembly on surfaces is a superb method to achieve useful functions and enable their interactions with the surrounding world. Consequently, adaptability and responsiveness to external stimuli are other prerequisites for their successful operation. Mechanically interlocked molecules such as rotaxanes and catenanes, and their precursors, that is, molecular switches and supramolecular switches including pseudorotaxanes, are molecular machines or prototypes of machines capable of mechanical motion induced by chemical signals, biological inputs, light or redox processes as the external stimuli. Switching of these functional host-guest systems on surfaces becomes a fundamental requirement for artificial molecular machines to work, mimicking the molecular machines in nature, such as proteins and their assemblies operating at dynamic interfaces such as the surfaces of cell membranes. Current research endeavors in material science and technology are focused on developing either a new class of materials or materials with novel/multiple functionalities by shifting host-guest chemistry from solution phase to surfaces. In this Account, we present our most recent attempts of building monolayers of rotaxanes/pseudorotaxanes on surfaces, providing stimuli-induced macroscopic effects and further understanding on the switchable host-guest systems at interfaces. Biocompatible versions of molecular machines based on synthetic macrocycles, such as cucurbiturils, pillararenes, calixarenes, and cyclodextrins, have been employed to form self-assembled monolayers of gates on the surfaces of mesoporous silica nanoparticles to regulate the controlled release of cargo/drug molecules under a range of external stimuli, such as light, pH variations, competitive binding, and enzyme. Rotaxanes have also been assembled onto the surfaces of gold nanodisks and microcantilevers to realize active molecular plasmonics and synthetic molecular actuators for device fabrication and function. Pillararenes have been successfully used to control and aid the synthesis of gold nanoparticles, semiconducting quantum dots, and magnetic nanoparticles. The resulting organic-inorganic hydrid nanomaterials have been successfully used for controlled self-assembly, herbicide sensing and detection, pesticide removal, and so forth, taking advantage of the selective binding of pillarenes toward target molecules. Cyclodextrins have also been successfully functionalized onto the surface of gold nanoparticles to serve as recycling extractors for C60. Many interesting prototypes of nanodevices based on synthetic macrocycles and their host-guest chemistry have been constructed and served for different potential applications. This Account will be a summary of the efforts made mainly by us, and others, on the host-guest chemistry of synthetic macrocyclic compounds on the surfaces of different solid supports.

Ozone air quality simulations with WRF-Chem (v3.5.1) over Europe: model evaluation and chemical mechanism comparison

NASA Astrophysics Data System (ADS)

Mar, Kathleen A.; Ojha, Narendra; Pozzer, Andrea; Butler, Tim M.

2016-10-01

We present an evaluation of the online regional model WRF-Chem over Europe with a focus on ground-level ozone (O3) and nitrogen oxides (NOx). The model performance is evaluated for two chemical mechanisms, MOZART-4 and RADM2, for year-long simulations. Model-predicted surface meteorological variables (e.g., temperature, wind speed and direction) compared well overall with surface-based observations, consistent with other WRF studies. WRF-Chem simulations employing MOZART-4 as well as RADM2 chemistry were found to reproduce the observed spatial variability in surface ozone over Europe. However, the absolute O3 concentrations predicted by the two chemical mechanisms were found to be quite different, with MOZART-4 predicting O3 concentrations up to 20 µg m-3 greater than RADM2 in summer. Compared to observations, MOZART-4 chemistry overpredicted O3 concentrations for most of Europe in the summer and fall, with a summertime domain-wide mean bias of +10 µg m-3 against observations from the AirBase network. In contrast, RADM2 chemistry generally led to an underestimation of O3 over the European domain in all seasons. We found that the use of the MOZART-4 mechanism, evaluated here for the first time for a European domain, led to lower absolute biases than RADM2 when compared to ground-based observations. The two mechanisms show relatively similar behavior for NOx, with both MOZART-4 and RADM2 resulting in a slight underestimation of NOx compared to surface observations. Further investigation of the differences between the two mechanisms revealed that the net midday photochemical production rate of O3 in summer is higher for MOZART-4 than for RADM2 for most of the domain. The largest differences in O3 production can be seen over Germany, where net O3 production in MOZART-4 is seen to be higher than in RADM2 by 1.8 ppb h-1 (3.6 µg m-3 h-1) or more. We also show that while the two mechanisms exhibit similar NOx sensitivity, RADM2 is approximately twice as sensitive to increases in anthropogenic VOC emissions as MOZART-4. Additionally, we found that differences in reaction rate coefficients for inorganic gas-phase chemistry in MOZART-4 vs. RADM2 accounted for a difference of 8 µg m-3, or 40 % of the summertime difference in O3 predicted by the two mechanisms. Differences in deposition and photolysis schemes explained smaller differences in O3. Our results highlight the strong dependence of modeled surface O3 over Europe on the choice of gas-phase chemical mechanism, which we discuss in the context of overall uncertainties in prediction of ground-level O3 and its associated health impacts (via the health-related metrics MDA8 and SOMO35).

Tuning cell adhesive properties via layer-by-layer assembly of chitosan and alginate

PubMed Central

Silva, Joana M.; García, José R.; Reis, Rui L.; García, Andrés J.; Mano, João F.

2017-01-01

Understanding the mechanisms controlling cell-multilayer film interactions is crucial to the successful engineering of these coatings for biotechnological and biomedical applications. Herein, we present a strategy to tune the cell adhesive properties of multilayers based on marine polysaccharides with and without cross-linking and/or coating with extracellular matrix proteins. Chemical cross-linking of multilayers improved mechanical properties of the coatings but also elicited changes in surface chemistry that alter the adhesion of human umbilical vein endothelial cells. We evaluated a strategy to decouple the mechanical and chemical properties of these films, enabling the transition from cell-adhesive to cell-resistant multilayers. Addition of chitosan/alginate multilayers on top of cross-linked films decreased endothelial cell adhesion, spreading, and proliferation to similar levels as uncross-linked films. Our findings highlight the key role of surface chemistry in cell-multilayer film interactions, and these engineered nanocoatings represent a tunable model of cell adhesive and non-adhesive multilayered films. PMID:28126597

Protons and Hydroxide Ions in Aqueous Systems.

PubMed

Agmon, Noam; Bakker, Huib J; Campen, R Kramer; Henchman, Richard H; Pohl, Peter; Roke, Sylvie; Thämer, Martin; Hassanali, Ali

2016-07-13

Understanding the structure and dynamics of water's constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.

Understanding deviations in lithographic patterns near interfaces: Characterization of bottom anti-reflective coatings (BARC) and the BARC resist interface

NASA Astrophysics Data System (ADS)

Lenhart, Joseph L.; Fischer, Daniel; Sambasivan, Sharadha; Lin, Eric K.; Wu, Wen-Li; Guerrero, Douglas J.; Wang, Yubao; Puligadda, Rama

2007-02-01

Interactions between a bottom anti-reflective coating (BARC) and a photoresist can critically impact lithographic patterns. For example, a lithographic pattern can shrink or spread near a BARC interface, a process called undercutting or footing respectively, due to incompatibility between the two materials. Experiments were conducted on two industrial BARC coatings in an effort to determine the impact of BARC surface chemistry on the footing and undercutting phenomena. The BARC coatings were characterized by near edge X-ray absorption fine structure (NEXAFS), contact angle measurements, and neutron and X-ray reflectivity. Contact angle measurement using a variety of fluids showed that the fluid contact angles were independent of the type of BARC coating or the BARC processing temperature. NEXAFS measurements showed that the surface chemistry of each BARC was also independent of the processing temperature. These results suggest that acid-base interactions at the BARC-resist interface are not the cause of the footing-undercutting phenomena encountered in lithographic patterns.

Proof-of-concept switchable hydrophobic/hydrophilic patterned surfaces from thermo-mechanically tailored acrylate systems

NASA Astrophysics Data System (ADS)

Laursen, Christopher M.

A novel, proof-of-concept, switchable hydrophobic/hydrophilic structured surface targeted to assist in antifouling of materials in aqueous environments was created through the development of a multi-tiered platform. The understructure consists of a thermo-mechanically tailored acrylate based polymer patterned in a pillared array, which was then overlaid with spatially tailored hydrophobic/hydrophilic surface chemistry treatments. Development focused on the synthesis of a ternary acrylate system displaying proper thermo-mechanical behavior in submerged conditions for the understructure, creation of a sufficient soft molding technique, and methods to chemically alter water-surface wetting interactions. The final acrylate based polymer constituents were chosen based on expected low-toxicity and the ability to be photopolymerized, while the final system displayed appropriate mechanical toughness, water absorption, and material stiffness over a select temperature window. This was important as alteration in wettability characteristics relied upon a stark transition in the polymeric materials stiffness within a narrow temperature range. The material qualitatively displayed a more hydrophobic state with the pillared surface structures erect, and a more hydrophilic state with the pillars bent over.

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

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

Griffiths, Natalie A.; Sebestyen, Stephen D.

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

DOE PAGES

Griffiths, Natalie A.; Sebestyen, Stephen D.

2016-10-14

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

Dust evolution, a global view I. Nanoparticles, nascence, nitrogen and natural selection … joining the dots

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

The role and importance of nanoparticles for interstellar chemistry and beyond is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), focusing on their active surface chemistry, the effects of nitrogen doping and the natural selection of interesting nanoparticle sub-structures. Nanoparticle-driven chemistry, and in particular the role of intrinsic epoxide-type structures, could provide a viable route to the observed gas phase OH in tenuous interstellar clouds en route to becoming molecular clouds. The aromatic-rich moieties present in asphaltenes probably provide a viable model for the structures present within aromatic-rich interstellar carbonaceous grains. The observed doping of such nanoparticle structures with nitrogen, if also prevalent in interstellar dust, could perhaps have important and observable consequences for surface chemistry and the formation of precursor pre-biotic species.

Automated Spectral System for Terrain Classification, Mineralogy of Vesta from the Dawn Framing Cameras

NASA Astrophysics Data System (ADS)

Reddy, V.; Le Corre, L.; Nathues, A.; Hall, I.; Gutierrez-Marques, P.; Hoffmann, M.

2011-10-01

The Dawn mission will rendezvous with asteroid (4) Vesta in July 2011. We have developed a set of equations for extracting mean pyroxene chemistry (Ferrosilite and Wollastonite) for classifying terrains on Vesta by using the Dawn Framing Camera (FC) multi-color bands. The Automated Spectral System (ASS) utilizes pseudo-Band I minima to estimate the mean pyroxene chemistry of diogenites, and basaltic eucrites. The mean pyroxene chemistries of cumulate eucrites, and howardites overlap each other on the pyroxene quadrilateral and hence are harder to distinguish. We expect our ASS to carry a bulk of the terrain classification and mineralogy workload utilizing these equations and complement the work of DawnKey (Le Corre et al., 2011, DPS/EPSC 2011). The system will also provide surface mineral chemistry layers that can be used for mapping Vesta's surface.

Correlation between surface chemistry and ion energy dependence of the etch yield in multicomponent oxides etching

NASA Astrophysics Data System (ADS)

Bérubé, P.-M.; Poirier, J.-S.; Margot, J.; Stafford, L.; Ndione, P. F.; Chaker, M.; Morandotti, R.

2009-09-01

The influence of surface chemistry in plasma etching of multicomponent oxides was investigated through measurements of the ion energy dependence of the etch yield. Using pulsed-laser-deposited CaxBa(1-x)Nb2O6 (CBN) and SrTiO3 thin films as examples, it was found that the etching energy threshold shifts toward values larger or smaller than the sputtering threshold depending on whether or not ion-assisted chemical etching is the dominant etching pathway and whether surface chemistry is enhancing or inhibiting desorption of the film atoms. In the case of CBN films etched in an inductively coupled Cl2 plasma, it is found that the chlorine uptake is inhibiting the etching reaction, with the desorption of nonvolatile NbCl2 and BaCl2 compounds being the rate-limiting step.

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

Nelson, A. J.; Voss, L. F.; Beck, P. R.

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

The study of non-fouling and non-specific cellular binding on functionalized surface for mammalian cell identification and manipulation

NASA Astrophysics Data System (ADS)

Zainudin, Nor Syuhada; Hambali, Nor Azura Malini Ahmad; Wahid, Mohamad Halim Abd; Retnasamy, Vithyacharan; Shahimin, Mukhzeer Mohamad

2017-04-01

Surface functionalization has emerged as a powerful tool for mapping limitless surface-cell membrane interaction in diverse biomolecular applications. Inhibition of non-specific biomolecular and cellular adhesion to solid surfaces is critical in improving the performance of some biomedical devices, particularly for in vitro bioassays. Some factors have to be paid particular attention in determining the right surface modification which are the types of surface, the methods and chemical solution that being used during the experimentation and also tools for analyzing the results. Improved surface functionalization technologies that provide better non-fouling performance in conjunction with specific attachment chemistries are sought for these applications. Hence, this paper serves as a review for multiple surface treatment methods including PEG grafting, adsorptive chemistries, self-assembled monolayers (SAMs) and plasma treatments.

Solubility studies of inorganic-organic hybrid nanoparticle photoresists with different surface functional groups

NASA Astrophysics Data System (ADS)

Li, Li; Chakrabarty, Souvik; Jiang, Jing; Zhang, Ben; Ober, Christopher; Giannelis, Emmanuel P.

2016-01-01

The solubility behavior of Hf and Zr based hybrid nanoparticles with different surface ligands in different concentrations of photoacid generator as potential EUV photoresists was investigated in detail. The nanoparticles regardless of core or ligand chemistry have a hydrodynamic diameter of 2-3 nm and a very narrow size distribution in organic solvents. The Hansen solubility parameters for nanoparticles functionalized with IBA and 2MBA have the highest contribution from the dispersion interaction than those with tDMA and MAA, which show more polar character. The nanoparticles functionalized with unsaturated surface ligands showed more apparent solubility changes after exposure to DUV than those with saturated ones. The solubility differences after exposure are more pronounced for films containing a higher amount of photoacid generator. The work reported here provides material selection criteria and processing strategies for the design of high performance EUV photoresists.The solubility behavior of Hf and Zr based hybrid nanoparticles with different surface ligands in different concentrations of photoacid generator as potential EUV photoresists was investigated in detail. The nanoparticles regardless of core or ligand chemistry have a hydrodynamic diameter of 2-3 nm and a very narrow size distribution in organic solvents. The Hansen solubility parameters for nanoparticles functionalized with IBA and 2MBA have the highest contribution from the dispersion interaction than those with tDMA and MAA, which show more polar character. The nanoparticles functionalized with unsaturated surface ligands showed more apparent solubility changes after exposure to DUV than those with saturated ones. The solubility differences after exposure are more pronounced for films containing a higher amount of photoacid generator. The work reported here provides material selection criteria and processing strategies for the design of high performance EUV photoresists. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07334k

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

PubMed

Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

2015-10-14

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

A Monte Carlo Sensitivity Analysis of CF2 and CF Radical Densities in a c-C4F8 Plasma

NASA Technical Reports Server (NTRS)

Bose, Deepak; Rauf, Shahid; Hash, D. B.; Govindan, T. R.; Meyyappan, M.

2004-01-01

A Monte Carlo sensitivity analysis is used to build a plasma chemistry model for octacyclofluorobutane (c-C4F8) which is commonly used in dielectric etch. Experimental data are used both quantitatively and quantitatively to analyze the gas phase and gas surface reactions for neutral radical chemistry. The sensitivity data of the resulting model identifies a few critical gas phase and surface aided reactions that account for most of the uncertainty in the CF2 and CF radical densities. Electron impact dissociation of small radicals (CF2 and CF) and their surface recombination reactions are found to be the rate-limiting steps in the neutral radical chemistry. The relative rates for these electron impact dissociation and surface recombination reactions are also suggested. The resulting mechanism is able to explain the measurements of CF2 and CF densities available in the literature and also their hollow spatial density profiles.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-04-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl2, Br:MeOH, and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p, and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Surface microstructure and chemistry of polyimide by single pulse ablation of picosecond laser

NASA Astrophysics Data System (ADS)

Du, Qifeng; Chen, Ting; Liu, Jianguo; Zeng, Xiaoyan

2018-03-01

Polyimide (PI) surface was ablated by the single pulse of picosecond laser, and the effects of laser wavelength (λ= 355 nm and 1064 nm) and fluence on surface microstructure and chemistry were explored. Scanning electron microscopy (SEM) analysis found that different surface microstructures, i.e., the concave of concentric ring and the convex of porous circular disk, were generated by 355 nm and 1064 nm picosecond laser ablation, respectively. X-ray photoelectron spectroscopy (XPS) characterization indicated that due to the high peak energy density of picosecond laser, oxygen and nitrogen from the ambient were incorporated into the PI surface mainly in the form of Cdbnd O and Csbnd Nsbnd C groups. Thus, both of the O/C and N/C atomic content ratios increased, but the increase caused by 1064 nm wavelength laser was larger. It inferred that the differences of PI surface microstructures and chemistry resulted from different laser parameters were related to different laser-matter interaction effects. For 355 nm picosecond laser, no obvious thermal features were observed and the probable ablation process of PI was mainly governed by photochemical effect; while for 1064 nm picosecond laser, obvious thermal feature appeared and photothermal effect was thought to be dominant.

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Effect of Gold Nanorod Surface Chemistry on Cellular Interactions In Vitro

DTIC Science & Technology

2010-09-01

properties of GNRs on cells. Previous studies on the cytotoxicity of various nanoparticles indicated that surface chemistry has a strong influence on cell...supplemented with 10% fetal bovine serum (FBS, ATCC) and 1% penicillin/streptomycin (pen/strep, Sigma). For nanoparticle exposure, media was supplemented...reagent ( phenazine ethosulfate; PES). Metabolically active cells reduce the MTS compound into a colored formazan product that is soluble in tissue

Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

ERIC Educational Resources Information Center

Martins, Angela; Nunes, Nelson

2015-01-01

In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

PubMed

Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

2015-08-04

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

Label-Free QCM Immunosensor for the Detection of Ochratoxin A

PubMed Central

Ertekin, Özlem; Laguna, Duygu Ercan; Özen, Fehime Şeyma; Öztürk, Zafer Ziya; Öztürk, Selma

2018-01-01

Ochratoxin A (OTA) is a potent mycotoxin that poses a risk in food and feed moieties and subject to worldwide regulation. Laboratory-based analytical methods are traditionally employed for reliable OTA quantification, but these methods cannot provide rapid and on-site analysis, where biosensors fill this gap. In this study a label-free quartz crystal microbalance (QCM)-based immunosensor for the detection of OTA, which is one of the most important small molecule contaminants, was developed by direct immobilization of OTA to amine-bearing sensor surfaces using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-Hydroxysuccinimide (NHS) chemistry. The protein-free sensor surface enabled regeneration of sensor surface with 50 mM NaOH and 1% SDS up to 13 times without loss of performance, which would disrupt a protein-containing sensor surface. We developed a QCM immunosensor using the developed sensor surface with a 17.2–200 ng/mL detection range which can be used for on-site detection of feedstuffs. PMID:29641432

Label-Free QCM Immunosensor for the Detection of Ochratoxin A.

PubMed

Pirinçci, Şerife Şeyda; Ertekin, Özlem; Laguna, Duygu Ercan; Özen, Fehime Şeyma; Öztürk, Zafer Ziya; Öztürk, Selma

2018-04-11

Ochratoxin A (OTA) is a potent mycotoxin that poses a risk in food and feed moieties and subject to worldwide regulation. Laboratory-based analytical methods are traditionally employed for reliable OTA quantification, but these methods cannot provide rapid and on-site analysis, where biosensors fill this gap. In this study a label-free quartz crystal microbalance (QCM)-based immunosensor for the detection of OTA, which is one of the most important small molecule contaminants, was developed by direct immobilization of OTA to amine-bearing sensor surfaces using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-Hydroxysuccinimide (NHS) chemistry. The protein-free sensor surface enabled regeneration of sensor surface with 50 mM NaOH and 1% SDS up to 13 times without loss of performance, which would disrupt a protein-containing sensor surface. We developed a QCM immunosensor using the developed sensor surface with a 17.2-200 ng/mL detection range which can be used for on-site detection of feedstuffs.

Multifunctional Surface Modification of Nanodiamonds Based on Dopamine Polymerization.

PubMed

Zeng, Yun; Liu, Wenyan; Wang, Zheyu; Singamaneni, Srikanth; Wang, Risheng

2018-04-03

Surface functionalization of nanodiamonds (NDs), which is of great interest in advanced material and therapeutic applications, requires the immobilization of functional species, such as nucleic acids, bioprobes, drugs, and metal nanoparticles, onto NDs' surfaces to form stable nanoconjugates. However, it is still challenging to modify the surface of NDs due to the complexity of their surface chemistry and the low density of each functional group on the surfaces of NDs. In this work, we demonstrate a general applicable surface functionalization approach for the preparation of ND-based core-shell nanoconjugates using dopamine polymerization. By taking advantage of the universal adhesion and versatile reactivity of polydopamine, we have effectively conjugated DNA and silver nanoparticles onto NDs. Moreover, the catalytic activity of ND-supported silver nanoparticle was characterized by the reduction of 4-nitrophenol, and the addressability of NDs was tested through DNA hybridization that formed satellite ND-gold nanorod conjugation. This simple and robust method we have presented may significantly improve the capability for attaching various functionalities onto NDs and open up new platforms for applications of NDs.

Seasonal change in precipitation, snowpack, snowmelt, soil water and streamwater chemistry, northern Michigan

USGS Publications Warehouse

Stottlemyer, R.; Toczydlowski, D.

1999-01-01

We have studied weekly precipitation, snowpack, snowmelt, soil water and streamwater chemistry throughout winter for over a decade in a small (176 ha) northern Michigan watershed with high snowfall and vegetated by 60 to 80 year-old northern hardwoods. In this paper, we examine physical, chemical, and biological processes responsible for observed seasonal change in streamwater chemistry based upon intensive study during winter 1996-1997. The objective was to define the contributions made to winter and spring streamwater chemical concentration and flux by processes as snowmelt, over-winter forest floor and surface soil mineralization, immobilization, and exchange, and subsurface flowpath. The forest floor and soil were unfrozen beneath the snowpack which permitted most snowmelt to enter. Over-winter soil mineralization and other biological processes maintain shallow subsurface ion and dissolved organic carbon (DOC) reservoirs. Small, but steady, snowmelt throughout winter removed readily mobilized soil NO3- which resulted in high over-winter streamwater concentrations but little flux. Winter soil water levels and flowpaths were generally deep which increased soil water and streamwater base cation (C(B)), HCO3-, and Si concentrations. Spring snowmelt increased soil water levels and removal of ions and DOC from the biologically active forest floor and shallow soils. The snowpack solute content was a minor component in determining streamwater ion concentration or flux during and following peak snowmelt. Exchangeable ions, weakly adsorbed anions, and DOC in the forest floor and surface soils dominated the chemical concentration and flux in soil water and streamwater. Following peak snowmelt, soil microbial immobilization and rapidly increased plant uptake of limiting nutrients removed nearly all available nitrogen from soil water and streamwater. During the growing season high evapotranspiration increased subsurface flowpath depth which in turn removed weathering products, especially C(B), HCO3-, and Si, from deeper soils. Soil water was a major component in the hydrologic and chemical budgets.We have studied weekly precipitation, snowpack, snowmelt, soil water and streamwater chemistry throughout winter for over a decade in a small (176 ha) northern Michigan watershed with high snowfall and vegetated by 60 to 80 year-old northern hardwoods. In this paper, we examine physical, chemical, and biological processes responsible for observed seasonal change in streamwater chemistry based upon intensive study during winter 1996-1997. The objective was to define the contributions made to winter and spring streamwater chemical concentration and flux by processes as snowmelt, over-winter forest floor and surface soil mineralization, immobilization, and exchange, and subsurface flowpath. The forest floor and soils were unfrozen beneath the snowpack which permitted most snowmelt to enter. Over-winter soil mineralization and other biological processes maintain shallow subsurface ion and dissolved organic carbon (DOC) reservoirs. Small, but steady, snowmelt throughout winter removed readily mobilized soil NO3- which resulted in high over-winter streamwater concentrations but little flux. Winter soil water levels and flowpaths were generally deep which increased soil water and streamwater base cation (CB), HCO3-, and Si concentrations. Spring snowmelt increased soil water levels and removal of ions and DOC from the biologically active forest floor and shallow soils. The snowpack solute content was a minor component in determining streamwater ion concentration or flux during and following peak snowmelt. Exchangeable ions, weakly adsorbed anions, and DOC in the forest floor and surface soils dominated the chemical concentration and flux in soil water and streamwater. Following peak snowmelt, soil microbial immobilization and rapidly increased plant uptake of limiting nutrients removed nearly all available nitrogen from soil water and streamwater. D

Titan: a laboratory for prebiological organic chemistry

NASA Technical Reports Server (NTRS)

Sagan, C.; Thompson, W. R.; Khare, B. N.

1992-01-01

When we examine the atmospheres of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune), the satellites in the outer solar system, comets, and even--through microwave and infrared spectroscopy--the cold dilute gas and grains between the stars, we find a rich organic chemistry, presumably abiological, not only in most of the solar system but throughout the Milky Way galaxy. In part because the composition and surface pressure of the Earth's atmosphere 4 x 10(9) years ago are unknown, laboratory experiments on prebiological organic chemistry are at best suggestive; but we can test our understanding by looking more closely at the observed extraterrestrial organic chemistry. The present Account is restricted to atmospheric organic chemistry, primarily on the large moon of Saturn. Titan is a test of our understanding of the organic chemistry of planetary atmospheres. Its atmospheric bulk composition (N2/CH4) is intermediate between the highly reducing (H2/He/CH4/NH3/H2O) atmospheres of the Jovian planets and the more oxidized (N2/CO2/H2O) atmospheres of the terrestrial planets Mars and Venus. It has long been recognized that Titan's organic chemistry may have some relevance to the events that led to the origin of life on Earth. But with Titan surface temperatures approximately equal to 94 K and pressures approximately equal to 1.6 bar, the oceans of the early Earth have no ready analogue on Titan. Nevertheless, tectonic events in the water ice-rich interior or impact melting and slow re-freezing may lead to an episodic availability of liquid water. Indeed, the latter process is the equivalent of a approximately 10(3)-year-duration shallow aqueous sea over the entire surface of Titan.