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

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.

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.

Saltwater icephobicity: Influence of surface chemistry on saltwater icing

PubMed Central

Carpenter, Katherine; Bahadur, Vaibhav

2015-01-01

Most studies on icephobicity focus on ice formation with pure water. This manuscript presents studies to understand the influence of surfaces on saltwater ice nucleation and propagation. Experiments are conducted to quantify the influence of surface chemistry on saltwater ice nucleation and to understand the utility of superhydrophobic surfaces for saltwater icephobicity. These experiments are conducted with pure water and two sodium chloride solutions, which represent the salinity of seawater and briny produced water. It is seen that the presence of salt slows down the ice front propagation velocity significantly. Saltwater droplet impact dynamics on superhydrophobic surfaces are also different from pure water. Saltwater droplets retract more and a greater fraction of impacting liquid is repelled from the superhydrophobic surface. It is seen that the greater bounciness of saltwater droplets is a result of slower ice nucleation propagation kinetics. These experiments indicate that superhydrophobic surfaces will have better resistance to impact icing with saltwater than pure water and can remain useful at temperatures as low as −40 °C. Overall, this work is a starting point for further studies on heterogeneous nucleation in saltwater and serves as a bridge between the widely studied freshwater icephobic surfaces and saltwater-related applications. PMID:26626958

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.

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

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.

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

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.

Influence of Surface Chemistry on the Release of an Antibacterial Drug from Nanostructured Porous Silicon.

PubMed

Wang, Mengjia; Hartman, Philip S; Loni, Armando; Canham, Leigh T; Bodiford, Nelli; Coffer, Jeffery L

2015-06-09

Nanostructured mesoporous silicon possesses important properties advantageous to drug loading and delivery. For controlled release of the antibacterial drug triclosan, and its associated activity versus Staphylococcus aureus, previous studies investigated the influence of porosity of the silicon matrix. In this work, we focus on the complementary issue of the influence of surface chemistry on such properties, with particular regard to drug loading and release kinetics that can be ideally adjusted by surface modification. Comparison between drug release from as-anodized, hydride-terminated hydrophobic porous silicon and the oxidized hydrophilic counterpart is complicated due to the rapid bioresorption of the former; hence, a hydrophobic interface with long-term biostability is desired, such as can be provided by a relatively long chain octyl moiety. To minimize possible thermal degradation of the surfaces or drug activity during loading of molten drug species, a solution loading method has been investigated. Such studies demonstrate that the ability of porous silicon to act as an effective carrier for sustained delivery of antibacterial agents can be sensitively altered by surface functionalization.

Influence of changing water sources and mineral chemistry on the everglades ecosystem

USGS Publications Warehouse

McCormick, P.V.; Harvey, J.W.; Crawford, E.S.

2011-01-01

Human influences during the previous century increased mineral inputs to the Florida Everglades by changing the sources and chemistry of surface inflows. Biogeochemical responses to this enrichment include changes in the availability of key limiting nutrients such as P, the potential for increased turnover of nutrient pools due to accelerated plant decomposition, and increased rates of mercury methylation associated with sulfate enrichment. Mineral enrichment has also been linked to the loss of sensitive macrophyte species, although dominant Everglades species appear tolerant of a broad range of mineral chemistry. Shifts in periphyton community composition and function provide an especially sensitive indicator of mineral enrichment. Understanding the influence of mineral chemistry on Everglades processes and biota may improve predictions of ecosystem responses to ongoing hydrologic restoration efforts and provide guidelines for protecting remaining mineral-poor areas of this peatland. Copyright ?? 2011 Taylor & Francis Group, LLC.

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.

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...

Mono vs multilayer fibronectin coatings on polar/hydrophobic/ionic polyurethanes: Altering surface interactions with human monocytes.

PubMed

Gossart, Audrey; Battiston, Kyle G; Gand, Adeline; Pauthe, Emmanuel; Santerre, J Paul

2018-01-15

Monocyte interactions with materials that are biofunctionalized with fibronectin (Fn) are of interest because of the documented literature which associates this protein with white blood cell function at implant sites. A degradable-polar hydrophobic ionic polyurethane (D-PHI), has been reported to promote an anti-inflammatory response from human monocytes. The aim of the current work was to study the influence of intrinsic D-PHI material chemistry on Fn adsorption (mono and multi-layer structures), and to investigate the influence of such chemistry on the structural state of the Fn, as well as the latter's influence on the activity of human monocytes on the protein coated substrates. Significant differences in Fn adsorption, surface hydrophobicity and the availability of defined peptide sequences (N terminal, C terminal or Cell Binding Domain) for the Fn in mono vs multilayer structures were observed as a function of the changes in intrinsic material chemistry. A D-PHI-formulated polyurethane substrate with subtle changes in anionic and hydrophobic domain content relative to the polar non-ionic urethane/carbonate groups within the polymer matrix promoted the lowest activation of monocytes, in the presence of multi-layer Fn constructs. These results highlight the importance of chemical heterogeneity as a design parameter for biomaterial surfaces, and establishes a desired strategy for controlling human monocyte activity at the surface of devices, when these are coated with multi-layer Fn structures. The latter is an important step towards functionalizing the materials with multi-layer protein drug carriers as interventional therapeutic agents. The control of the behavior of monocytes, especially migration and activation, is of crucial interest to modulate the inflammatory response at the site of implanted biomaterial. Several studies report the influence of adsorbed serum proteins on the behavior of monocytes on biomaterials. However, few studies show the influence of surface chemical group distribution on the controlled adsorption and the subsequent induced conformation- of mono versus multi-layer assembled structures generated from specific proteins implicated in wound repair. The current research considered the role of Fn adsorption and conformation in thin films while interacting with the intrinsic chemistry of segmented block polyurethanes; and the influence of the former on modulation and activation of human monocytes. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

Indoor chemistry: research opportunities and challenges.

PubMed

Nazaroff, W W; Goldstein, A H

2015-08-01

In this editorial, we have highlighted key research opportunities and challenges in four topical themes for indoor chemistry: human occupants as agents influencing indoor chemistry; oxidative chemistry; surface phenomena; and semivolatile organic compounds. In each case, enough prior work has been done to demonstrate the importance of the theme and to create a foundation for future studies. Extensive achievements and ongoing progress in (outdoor) atmospheric chemistry—both in the analytical methods developed and in the scientific knowledge created—also contribute to a strong foundation from which to achieve rapid research progress in this exciting new domain.

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.

Impact of plasma chemistry versus titanium surface topography on osteoblast orientation.

PubMed

Rebl, Henrike; Finke, Birgit; Lange, Regina; Weltmann, Klaus-Dieter; Nebe, J Barbara

2012-10-01

Topographical and chemical modifications of biomaterial surfaces both influence tissue physiology, but unfortunately little knowledge exists as to their combined effect. There are many indications that rough surfaces positively influence osteoblast behavior. Having determined previously that a positively charged, smooth titanium surface boosts osteoblast adhesion, we wanted to investigate the combined effects of topography and chemistry and elucidate which of these properties is dominant. Polished, machined and corundum-blasted titanium of increasing microroughness was additionally coated with plasma-polymerized allylamine (PPAAm). Collagen I was then immobilized using polyethylene glycol diacid and glutar dialdehyde. On all PPAAm-modified surfaces (i) adhesion of human MG-63 osteoblastic cells increased significantly in combination with roughness, (ii) cells resemble the underlying structure and melt with the surface, and (iii) cells overcome the restrictions of a grooved surface and spread out over a large area as indicated by actin staining. Interestingly, the cellular effects of the plasma-chemical surface modification are predominant over surface topography, especially in the initial phase. Collagen I, although it is the gold standard, does not improve surface adhesion features comparably. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

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.

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.

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.

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.

Transport of E. coli D21g with runoff water under different solution chemistry conditions and surface slopes

USDA-ARS?s Scientific Manuscript database

Tracer and indicator microbe runoff experiments were conducted to investigate the influence of solution chemistry on the transport, retention, and release of Escherichia coli D21g. Experiments were conducted in a chamber (2.25 m long, 0.15 m wide, and 0.16 m high) packed with ultrapure quartz sand (...

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.

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.

The Impact of Chemical Substitutions on Interfacial Properties of REE Orthophosphates (Monazite, Xenotime)

NASA Astrophysics Data System (ADS)

Gamage McEvoy, J.; Thibault, Y.

2016-12-01

Mineral surface properties strongly influence liquid-solid interface behaviour in the presence of various ligands, and can significantly affect processes of natural (ex. fluids, melts) and industrial (ex. oil recovery) relevance. Many Rare Earth Element (REE)-bearing minerals display extensive solid solutions resulting in significant chemical variations which influence their crystal and surface properties and, can consequently impact the interfacial features of their interaction with substances such as organic molecules (i.e. reactivity and sorption). For example, the surface charge properties of some REE orthophosphates show an uncharacteristically wide variation in reported values, where large differences in literature are commonly attributed to compositional differences between samples. However the impact of these chemical substitutions remains largely unknown. As such, the aim of this research was to systematically investigate the influence of mineralogical variation within the compositional space of the REE orthophosphates on their surface chemistry and resulting interaction with organic molecules. To better isolate the chemical, structural, and morphological variables, the synthesis of REE orthophosphate crystals along a number of defined substitutions was conducted, and their surface chemistry characteristics benchmarked against well-characterized natural monazite and xenotime from various localities. The interaction of these crystal surfaces with model organic molecules (long chain carboxylic acids and alkyl hydroxamic acids, respectively) was then studied and characterized via surface (X-ray photoelectron) and near-surface (vibrational) spectroscopic techniques. The implications of crystal surface-organic molecule interactions to mineral processing through flotation were also experimentally investigated.

Nighttime Chemistry in the Polluted Boundary Layer (Invited)

NASA Astrophysics Data System (ADS)

Stutz, J.; Wong, K.; Tsai, C.; Pikelnaya, O.

2009-12-01

Chemistry in the urban nocturnal boundary layer (NBL) has received surprisingly little attention in the past. Surface observations often see low ozone and high NO levels, which lead to low nocturnal radical levels and consequently slow chemistry near the ground. Above the surface, however, ozone and radical levels, for example of NO3, are considerably higher, and more efficient chemical pathways for the removal of gaseous pollutants such as nitrogen oxides, ozone, and hydrocarbons, are active. The influence of nocturnal chemistry on aerosol composition is also largest aloft. These processes are poorly understood due to a lack of observations in the altitude range from 20 - 500m. The strong influence of vertical mixing and transport on the composition of the NBL poses an additional challenge, requiring the measurement of vertical concentration profiles and the use of chemical transport models for their interpretation. In addition, heterogeneous processes on the ground and on aerosol surfaces play an important role in the nocturnal atmosphere. In this presentation we will review our current understanding of nocturnal chemistry in the lowest 300m of the polluted atmosphere, with a focus on nitrogen compounds. A number of field experiments in recent years have given insight into the vertical distribution of some of the most important nocturnal trace gases in urban areas, such as ozone, NO2, NO3, N2O5, and HONO. In particular, two 6-week long experiments in Houston, TX, in 2006 and 2009, have shown the strong and persistent impact of vertical mixing on the distribution of all trace gases, as well as the chemistry in the lowest 300m of the atmosphere. These observations were accompanied by detailed meteorological observations and in-situ measurements of chemical species at 70m above the ground. The observations in Houston were interpreted with a 1D chemical transport model that allows quantification of chemistry and transport at night. Our results identify gaps in our understanding of the polluted nocturnal urban boundary layer will be discussed.

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.

Colloidal characterization of silicon nitride and silicon carbide

NASA Technical Reports Server (NTRS)

Feke, Donald L.

1986-01-01

The colloidal behavior of aqueous ceramic slips strongly affects the forming and sintering behavior and the ultimate mechanical strength of the final ceramic product. The colloidal behavior of these materials, which is dominated by electrical interactions between the particles, is complex due to the strong interaction of the solids with the processing fluids. A surface titration methodology, modified to account for this interaction, was developed and used to provide fundamental insights into the interfacial chemistry of these systems. Various powder pretreatment strategies were explored to differentiate between true surface chemistry and artifacts due to exposure history. The colloidal behavior of both silicon nitride and carbide is dominated by silanol groups on the powder surfaces. However, the colloid chemistry of silicon nitride is apparently influenced by an additional amine group. With the proper powder treatments, silicon nitride and carbide powder can be made to appear colloidally equivalent. The impact of these results on processing control will be discussed.

Real-time single-molecule observations of proteins at the solid-liquid interface

NASA Astrophysics Data System (ADS)

Langdon, Blake Brianna

Non-specific protein adsorption to solid surfaces is pervasive and observed across a broad spectrum of applications including biomaterials, separations, pharmaceuticals, and biosensing. Despite great interest in and considerable literature dedicated to the phenomena, a mechanistic understanding of this complex phenomena is lacking and remains controversial, partially due to the limits of ensemble-averaging techniques used to study it. Single-molecule tracking (SMT) methods allow us to study distinct protein dynamics (e.g. adsorption, desorption, diffusion, and intermolecular associations) on a molecule-by-molecule basis revealing the protein population and spatial heterogeneity inherent in protein interfacial behavior. By employing single-molecule total internal reflection fluorescence microscopy (SM-TIRFM), we have developed SMT methods to directly observe protein interfacial dynamics at the solid-liquid interface to build a better mechanistic understanding of protein adsorption. First, we examined the effects of surface chemistry (e.g. hydrophobicity, hydrogen-bonding capacity), temperature, and electrostatics on isolated protein desorption and interfacial diffusion for fibrinogen (Fg) and bovine serum albumin (BSA). Next, we directly and indirectly probed the effects of protein-protein interactions on interfacial desorption, diffusion, aggregation, and surface spatial heterogeneity on model and polymeric thin films. These studies provided many useful insights into interfacial protein dynamics including the following observations. First, protein adsorption was reversible, with the majority of proteins desorbing from all surface chemistries within seconds. Isolated protein-surface interactions were relatively weak on both hydrophobic and hydrophilic surfaces (apparent desorption activation energies of only a few kBT). However, proteins could dynamically and reversibly associate at the interface, and these interfacial associations led to proteins remaining on the surface for longer time intervals. Surface chemistry and surface spatial heterogeneity (i.e. surface sites with different binding strengths) were shown to influence adsorption, desorption, and interfacial protein-protein associations. For example, faster protein diffusion on hydrophobic surfaces increased protein-protein associations and, at higher protein surface coverage, led to proteins remaining on hydrophobic surfaces longer than on hydrophilic surfaces. Ultimately these studies suggested that surface properties (chemistry, heterogeneity) influence not only protein-surface interactions but also interfacial mobility and protein-protein associations, implying that surfaces that better control protein adsorption can be designed by accounting for these processes.

The Effects of Size, Shape, and Surface Functional Group of Gold Nanostructures on Their Adsorption and Internalization by Cells

PubMed Central

Cho, Eun Chul; Au, Leslie; Zhang, Qiang; Xia, Younan

2010-01-01

In this study, we examined the effects of size, shape, and surface chemistry of gold nanostructures on their uptake (including both adsorption and internalization) by SK-BR-3 breast cancer cells. We used both spherical and cubic Au nanostructures (nanospheres and nanocages, respectively) of two different sizes, and their surface was modified with poly(ethylene glycol) (PEG), antibody anti-HER2, or poly(allyamine hydrochloride) (PAA). Our results showed that the size of the Au nanostructures influenced their uptake by the cells in a similar way regardless of the surface chemistry, while the shape dependency could vary depending on the surface functional group. In addition, the cells preferred to take up the Au nanostructures covered by different surface groups in the following order: PAA>> anti-HER2> PEG. The fraction of Au nanostructures attached to the cell surface was also dependent on the aforementioned parameters. PMID:20029850

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.

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.

The survival and inactivation of enteric viruses on soft surfaces: A systematic review of the literature.

PubMed

Yeargin, Thomas; Buckley, David; Fraser, Angela; Jiang, Xiuping

2016-11-01

Worldwide, enteric viruses are the main cause of acute gastroenteritis. In humans, these viruses spread via person-to-person contact, food, water, and/or the environment. Their survival and inactivation on hard surfaces have been extensively studied; however, nonlaunderable soft surfaces, such as upholstery and carpet, have received little attention. The aim of this systematic review was to determine factors that influence the survival and inactivation of enteric viruses on nonlaunderable soft surfaces. EBSCO and Web of Science were searched for experimental studies published between 1965 and 2015 using Preferred Reporting Items for Systematic Reviews and Meta-Analyses methods. Titles and abstracts were screened using 3 eligibility criteria. The quality of all study methods was also assessed. Our search yielded 12 articles. Viruses survived between 0 hours and 140 days depending on surface and environment conditions. Virus survival was influenced by temperature, relative humidity, organic content, and deposition method. A variety of chemistries were tested across studies and were shown to have a varied effect on enteric viruses. Chlorine, glutaraldehyde, vaporous ozone, and hydrogen peroxide were the most efficacious against enteric viruses (> 3-log reduction). Environmental factors, such as temperature and relative humidity, can influence survival of enteric viruses on nonlaunderable soft surfaces. The efficacy of liquid and vaporous chemistries are associated with surface and virus type. Copyright © 2016 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.

Plant regulation of greenhouse gas emissions and carbon lability in a Neotropical peatland

NASA Astrophysics Data System (ADS)

Girkin, Nicholas; Vane, Christopher; Turner, Benjamin; Ostle, Nicholas; Sjogersten, Sofie

2017-04-01

Tropical peatlands are under significant threat from land use changes but there remains a significant knowledge gap regarding the influences of contrasting plant types on greenhouse gas emissions and belowground carbon dynamics. We investigated differences in surface CO2 and CH4 fluxes and differences in soil organic carbon chemistry under contrasting surface vegetation types, a palm (Raphia taedigera) and a broadleaved evergreen tree (Campnosperma panamensis), in a Neotropical peatland. CO2 and CH4 production differed significantly between species, with higher fluxes measured under R. taedigera. There were significant differences in peat carbon properties under each species as revealed by Rock-Eval pyrolysis. Peat from under each species showed contrasting trends in degradation inside and outside the rooting zone, and strong differences in the presence of the most labile fractions of carbon. These results highlight the strong impacts that surface vegetation can have on surface gas emissions as well as the influences exerted on peat carbon chemistry within a tropical forested peatland, with implications for our understanding of changes in land use type across the tropics.

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

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.

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

Biological Fate of Fe3O4 Core-Shell Mesoporous Silica Nanoparticles Depending on Particle Surface Chemistry

PubMed Central

Rascol, Estelle; Daurat, Morgane; Da Silva, Afitz; Maynadier, Marie; Dorandeu, Christophe; Charnay, Clarence; Garcia, Marcel; Lai-Kee-Him, Joséphine; Bron, Patrick; Auffan, Mélanie; Angeletti, Bernard; Devoisselle, Jean-Marie; Guari, Yannick; Gary-Bobo, Magali; Chopineau, Joël

2017-01-01

The biological fate of nanoparticles (NPs) for biomedical applications is highly dependent of their size and charge, their aggregation state and their surface chemistry. The chemical composition of the NPs surface influences their stability in biological fluids, their interaction with proteins, and their attraction to the cell membranes. In this work, core-shell magnetic mesoporous silica nanoparticles (Fe3O4@MSN), that are considered as potential theranostic candidates, are coated with polyethylene glycol (PEG) or 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. Their biological fate is studied in comparison to the native NPs. The physicochemical properties of these three types of NPs and their suspension behavior in different media are investigated. The attraction to a membrane model is also evaluated using a supported lipid bilayer. The surface composition of NPs strongly influences their dispersion in biological fluids mimics, protein binding and their interaction with cell membrane. While none of these types of NPs is found to be toxic on mice four days after intravenous injection of a dose of 40 mg kg−1 of NPs, their surface coating nature influences the in vivo biodistribution. Importantly, NP coated with DMPC exhibit a strong accumulation in liver and a very low accumulation in lung in comparison with nude or PEG ones. PMID:28665317

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

Sensitivity of biogenic volatile organic compounds to land surface parameterizations and vegetation distributions in California

NASA Astrophysics Data System (ADS)

Zhao, Chun; Huang, Maoyi; Fast, Jerome D.; Berg, Larry K.; Qian, Yun; Guenther, Alex; Gu, Dasa; Shrivastava, Manish; Liu, Ying; Walters, Stacy; Pfister, Gabriele; Jin, Jiming; Shilling, John E.; Warneke, Carsten

2016-05-01

Current climate models still have large uncertainties in estimating biogenic trace gases, which can significantly affect atmospheric chemistry and secondary aerosol formation that ultimately influences air quality and aerosol radiative forcing. These uncertainties result from many factors, including uncertainties in land surface processes and specification of vegetation types, both of which can affect the simulated near-surface fluxes of biogenic volatile organic compounds (BVOCs). In this study, the latest version of Model of Emissions of Gases and Aerosols from Nature (MEGAN v2.1) is coupled within the land surface scheme CLM4 (Community Land Model version 4.0) in the Weather Research and Forecasting model with chemistry (WRF-Chem). In this implementation, MEGAN v2.1 shares a consistent vegetation map with CLM4 for estimating BVOC emissions. This is unlike MEGAN v2.0 in the public version of WRF-Chem that uses a stand-alone vegetation map that differs from what is used by land surface schemes. This improved modeling framework is used to investigate the impact of two land surface schemes, CLM4 and Noah, on BVOCs and examine the sensitivity of BVOCs to vegetation distributions in California. The measurements collected during the Carbonaceous Aerosol and Radiative Effects Study (CARES) and the California Nexus of Air Quality and Climate Experiment (CalNex) conducted in June of 2010 provided an opportunity to evaluate the simulated BVOCs. Sensitivity experiments show that land surface schemes do influence the simulated BVOCs, but the impact is much smaller than that of vegetation distributions. This study indicates that more effort is needed to obtain the most appropriate and accurate land cover data sets for climate and air quality models in terms of simulating BVOCs, oxidant chemistry and, consequently, secondary organic aerosol formation.

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.

The effect of UV radiation from oxygen and argon plasma on the adhesion of organosilicon coatings on polypropylene

NASA Astrophysics Data System (ADS)

Jaritz, M.; Behm, H.; Hopmann, Ch; Kirchheim, D.; Mitschker, F.; Awakowicz, P.; Dahlmann, R.

2017-01-01

The influence of ultraviolet (UV) radiation from oxygen and argon pretreatment plasmas on a plastic substrate has not been fully understood yet. In particular, its influence on the adhesion properties has not been sufficiently researched so far. This paper addresses this issue by comparing the bond strength of a plasmapolymerized silicon organic coating (SiO x C y H z ) on polypropylene (PP) after oxygen and argon plasma pretreatment and pretreatment by UV radiation emitted by the same plasmas. The UV radiation is isolated from the other species from the plasma by means of a magnesium fluoride (MgF2) optical filter. It could be shown that UV radiation originating from an oxygen plasma has a significant impact on both substrate surface chemistry and coating adhesion. The same maximum bond strength enhancement can be reached by pretreating the polypropylene surface either with pulsed oxygen plasma, or with only the UV radiation from this oxygen plasma. Also, similar surface chemistry and topography modifications are induced. For argon plasma no significant influence of its UV radiation on the substrate could be observed in this study.

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.

Duty cycle dependent chemical structure and wettability of RF pulsed plasma copolymers of acrylic acid and octafluorocyclobutane

NASA Astrophysics Data System (ADS)

Muzammil, I.; Li, Y. P.; Li, X. Y.; Lei, M. K.

2018-04-01

Octafluorocyclobutane and acrylic acid (C4F8-co-AA) plasma copolymer coatings are deposited using a pulsed wave (PW) radio frequency (RF) plasma on low density polyethylene (LDPE). The influence of duty cycle in pulsed process with the monomer feed rate on the surface chemistry and wettability of C4F8-co-AA plasma polymer coatings is studied. The concentration of the carboxylic acid (hydrophilic) groups increase, and that of fluorocarbon (hydrophobic) groups decrease by lowering the duty cycle. The combined effect of surface chemistry and surface morphology of the RF pulsed plasma copolymer coatings causes tunable surface wettability and surface adhesion. The gradual emergence of hydrophilic contents leads to surface heterogeneity by lowering duty cycle causing an increased surface adhesion in hydrophobic coatings. The C4F8-co-AA plasma polymer coatings on the nanotextured surfaces are tuned from repulsive superhydrophobicity to adhesive superhydrophobicity, and further to superhydrophilicity by adjusting the duty cycles with the monomer feed rates.

Influence of Collector Surface Composition and Water Chemistry on the Deposition of Cerium Dioxide Nanoparticles: QCM-D and Column Experiment Approaches

EPA Science Inventory

The deposition behavior of cerium dioxide (CeO2) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied ...

Influence of chemistry on wetting dynamics of nanotextured hydrophobic surfaces.

PubMed

Di Mundo, Rosa; Palumbo, Fabio; d'Agostino, Riccardo

2010-04-06

In this work, the role of a chemical parameter, such as the degree of fluorination, on the wetting behavior of nanotextured hydrophobic surfaces is investigated. Texture and chemistry tuning of the surfaces has been accomplished with single batch radiofrequency low-pressure plasma processes. Polystyrene substrates have been textured by CF(4) plasma etching and subsequently covered by thin films with a tunable F-to-C ratio, obtained in discharges fed with C(4)F(8)-C(2)H(4). Measurements of wetting dynamics reveal a regime transition from adhesive-hydrophobic to slippery-superhydrophobic, i.e., from wet to non wet states, as the F-to-C rises at constant topography. Such achievements are strengthened by calculation of the solid fraction of surface water contact area applying Cassie-Baxter advancing and receding equations to water contact angle data of textured and flat reference surfaces.

Dust cloud evolution in sub-stellar atmospheres via plasma deposition and plasma sputtering

NASA Astrophysics Data System (ADS)

Stark, C. R.; Diver, D. A.

2018-04-01

Context. In contemporary sub-stellar model atmospheres, dust growth occurs through neutral gas-phase surface chemistry. Recently, there has been a growing body of theoretical and observational evidence suggesting that ionisation processes can also occur. As a result, atmospheres are populated by regions composed of plasma, gas and dust, and the consequent influence of plasma processes on dust evolution is enhanced. Aim. This paper aims to introduce a new model of dust growth and destruction in sub-stellar atmospheres via plasma deposition and plasma sputtering. Methods: Using example sub-stellar atmospheres from DRIFT-PHOENIX, we have compared plasma deposition and sputtering timescales to those from neutral gas-phase surface chemistry to ascertain their regimes of influence. We calculated the plasma sputtering yield and discuss the circumstances where plasma sputtering dominates over deposition. Results: Within the highest dust density cloud regions, plasma deposition and sputtering dominates over neutral gas-phase surface chemistry if the degree of ionisation is ≳10-4. Loosely bound grains with surface binding energies of the order of 0.1-1 eV are susceptible to destruction through plasma sputtering for feasible degrees of ionisation and electron temperatures; whereas, strong crystalline grains with binding energies of the order 10 eV are resistant to sputtering. Conclusions: The mathematical framework outlined sets the foundation for the inclusion of plasma deposition and plasma sputtering in global dust cloud formation models of sub-stellar atmospheres.

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

Zhao, Chun; Huang, Maoyi; Fast, Jerome D.

Current climate models still have large uncertainties in estimating biogenic trace gases, which can significantly affect atmospheric chemistry and secondary aerosol formation that ultimately influences air quality and aerosol radiative forcing. These uncertainties result from many factors, including uncertainties in land surface processes and specification of vegetation types, both of which can affect the simulated near-surface fluxes of biogenic volatile organic compounds (BVOCs). In this study, the latest version of Model of Emissions of Gases and Aerosols from Nature (MEGAN v2.1) is coupled within the land surface scheme CLM4 (Community Land Model version 4.0) in the Weather Research and Forecasting model withmore » chemistry (WRF-Chem). In this implementation, MEGAN v2.1 shares a consistent vegetation map with CLM4 for estimating BVOC emissions. This is unlike MEGAN v2.0 in the public version of WRF-Chem that uses a stand-alone vegetation map that differs from what is used by land surface schemes. This improved modeling framework is used to investigate the impact of two land surface schemes, CLM4 and Noah, on BVOCs and examine the sensitivity of BVOCs to vegetation distributions in California. The measurements collected during the Carbonaceous Aerosol and Radiative Effects Study (CARES) and the California Nexus of Air Quality and Climate Experiment (CalNex) conducted in June of 2010 provided an opportunity to evaluate the simulated BVOCs. Sensitivity experiments show that land surface schemes do influence the simulated BVOCs, but the impact is much smaller than that of vegetation distributions. This study indicates that more effort is needed to obtain the most appropriate and accurate land cover data sets for climate and air quality models in terms of simulating BVOCs, oxidant chemistry and, consequently, secondary organic aerosol formation.« less

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction

NASA Astrophysics Data System (ADS)

Bonnefille, Eric; Novio, Fernando; Gutmann, Torsten; Poteau, Romuald; Lecante, Pierre; Jumas, Jean-Claude; Philippot, Karine; Chaudret, Bruno

2014-07-01

Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity.Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00791c

Microbiologically Influenced Corrosion: Causative Organisms and Mechanisms

DTIC Science & Technology

2012-01-31

corrosion is both predictable and complex. In aquatic environments and under some atmospheric conditions . microorganisms settle on surfaces and alter the...some atmospheric conditions , microorganisms settle on sin laces and alter the surface chemistry controlling the rates of corrosion or shifting the...pitting corrosion of some allO) S continues under deposits of iron-oxidizing bacteria independent of bacterial activity. Similarly, microbiologicall

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

Quantum Dot Surface Engineering: Toward Inert Fluorophores with Compact Size and Bright, Stable Emission

PubMed Central

Lim, Sung Jun; Ma, Liang; Schleife, André; Smith, Andrew M.

2016-01-01

The surfaces of colloidal nanocrystals are complex interfaces between solid crystals, coordinating ligands, and liquid solutions. For fluorescent quantum dots, the properties of the surface vastly influence the efficiency of light emission, stability, and physical interactions, and thus determine their sensitivity and specificity when they are used to detect and image biological molecules. But after more than 30 years of study, the surfaces of quantum dots remain poorly understood and continue to be an important subject of both experimental and theoretical research. In this article, we review the physics and chemistry of quantum dot surfaces and describe approaches to engineer optimal fluorescent probes for applications in biomolecular imaging and sensing. We describe the structure and electronic properties of crystalline facets, the chemistry of ligand coordination, and the impact of ligands on optical properties. We further describe recent advances in compact coatings that have significantly improved their properties by providing small hydrodynamic size, high stability and fluorescence efficiency, and minimal nonspecific interactions with cells and biological molecules. While major progress has been made in both basic and applied research, many questions remain in the chemistry and physics of quantum dot surfaces that have hindered key breakthroughs to fully optimize their properties. PMID:28344357

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.

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.

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

NASA Astrophysics Data System (ADS)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

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.

The Influence of Nitrogen Oxides on Chlorine Chemistry in Barrow, Alaska

NASA Astrophysics Data System (ADS)

McNamara, S. M.; Raso, A. R. W.; Wang, S.; Thanekar, S.; Fuentes, J. D.; Shepson, P. B.; Pratt, K.

2016-12-01

Active chlorine chemistry in the springtime Arctic boundary layer impacts the fate of atmospheric pollutants and greenhouse gases. Recent field studies have reported high amounts of molecular chlorine (Cl2), up to 400 parts per trillion (ppt), as well as the presence of chlorinated hydrocarbon oxidation products. However, our knowledge of Arctic chlorine chemistry is limited by a paucity of observations. The presence of nitrogen oxides (NOx) may influence the chlorine chemistry in this region. Here, we report chemical ionization mass spectrometry measurements of Cl2, chlorine monoxide (ClO), nitryl chloride (ClNO2), and dinitrogen pentoxide (N2O5), and NOx measurements at Barrow, AK during March-May 2016. To our knowledge, these data represent the first observations of ClNO2 in the Arctic. While the main source of NOx in a pristine Arctic environment is irradiated snow surfaces, anthropogenic sources can significantly enhance local NOx concentrations. The role of NOx in the activation and temporal trends of the reactive chlorine species are examined using a 0-D photochemical model. The prevalence of chlorine chemistry under elevated nitrogen oxide conditions may have significant impacts on the atmospheric composition in an increasingly polluted Arctic.

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.

Role of nanoparticle size, shape and surface chemistry in oral drug delivery.

PubMed

Banerjee, Amrita; Qi, Jianping; Gogoi, Rohan; Wong, Jessica; Mitragotri, Samir

2016-09-28

Nanoparticles find intriguing applications in oral drug delivery since they present a large surface area for interactions with the gastrointestinal tract and can be modified in various ways to address the barriers associated with oral delivery. The size, shape and surface chemistry of nanoparticles can greatly impact cellular uptake and efficacy of the treatment. However, the interplay between particle size, shape and surface chemistry has not been well investigated especially for oral drug delivery. To this end, we prepared sphere-, rod- and disc-shaped nanoparticles and conjugated them with targeting ligands to study the influence of size, shape and surface chemistry on their uptake and transport across intestinal cells. A triple co-culture model of intestinal cells was utilized to more closely mimic the intestinal epithelium. Results demonstrated higher cellular uptake of rod-shaped nanoparticles in the co-culture compared to spheres regardless of the presence of active targeting moieties. Transport of nanorods across the intestinal co-culture was also significantly higher than spheres. The findings indicate that nanoparticle-mediated oral drug delivery can be potentially improved with departure from spherical shape which has been traditionally utilized for the design of nanoparticles. We believe that understanding the role of nanoparticle geometry in intestinal uptake and transport will bring forth a paradigm shift in nanoparticle engineering for oral delivery and non-spherical nanoparticles should be further investigated and considered for oral delivery of therapeutic drugs and diagnostic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

NASA Technical Reports Server (NTRS)

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

PubMed Central

Ghouma, Imen; Limousy, Lionel; Bennici, Simona

2018-01-01

The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD) was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2. PMID:29670008

The surface properties of carbon fibers and their adhesion to organic polymers

NASA Technical Reports Server (NTRS)

Bascom, W. D.; Drzal, L. T.

1987-01-01

The state of knowledge of the surface properties of carbon fibers is reviewed, with emphasis on fiber/matrix adhesion in carbon fiber reinforced plastics. Subjects treated include carbon fiber structure and chemistry, techniques for the study of the fiber surface, polymer/fiber bond strength and its measurement, variations in polymer properties in the interphase, and the influence of fiber matrix adhesion on composite mechanical properties. Critical issues are summarized and search recommendations are made.

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 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

CO2 adhesion on hydrated mineral surfaces.

PubMed

Wang, Shibo; Tao, Zhiyuan; Persily, Sara M; Clarens, Andres F

2013-10-15

Hydrated mineral surfaces in the environment are generally hydrophilic but in certain cases can strongly adhere CO2, which is largely nonpolar. This adhesion can significantly alter the wettability characteristics of the mineral surface and consequently influence capillary/residual trapping and other multiphase flow processes in porous media. Here, the conditions influencing adhesion between CO2 and homogeneous mineral surfaces were studied using static pendant contact angle measurements and captive advancing/receding tests. The prevalence of adhesion was sensitive to both surface roughness and aqueous chemistry. Adhesion was most widely observed on phlogopite mica, silica, and calcite surfaces with roughness on the order of ~10 nm. The incidence of adhesion increased with ionic strength and CO2 partial pressure. Adhesion was very rarely observed on surfaces equilibrated with brines containing strong acid or base. In advancing/receding contact angle measurements, adhesion could increase the contact angle by a factor of 3. These results support an emerging understanding of adhesion of, nonpolar nonaqueous phase fluids on mineral surfaces influenced by the properties of the electrical double layer in the aqueous phase film and surface functional groups between the mineral and CO2.

Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity.

PubMed

Park, Jeong Young; Kim, Sun Mi; Lee, Hyosun; Nedrygailov, Ievgen I

2015-08-18

Energy dissipation at surfaces and interfaces is mediated by excitation of elementary processes, including phonons and electronic excitation, once external energy is deposited to the surface during exothermic chemical processes. Nonadiabatic electronic excitation in exothermic catalytic reactions results in the flow of energetic electrons with an energy of 1-3 eV when chemical energy is converted to electron flow on a short (femtosecond) time scale before atomic vibration adiabatically dissipates the energy (in picoseconds). These energetic electrons that are not in thermal equilibrium with the metal atoms are called "hot electrons". The detection of hot electron flow under atomic or molecular processes and understanding its role in chemical reactions have been major topics in surface chemistry. Recent studies have demonstrated electronic excitation produced during atomic or molecular processes on surfaces, and the influence of hot electrons on atomic and molecular processes. We outline research efforts aimed at identification of the intrinsic relation between the flow of hot electrons and catalytic reactions. We show various strategies for detection and use of hot electrons generated by the energy dissipation processes in surface chemical reactions and photon absorption. A Schottky barrier localized at the metal-oxide interface of either catalytic nanodiodes or hybrid nanocatalysts allows hot electrons to irreversibly transport through the interface. We show that the chemicurrent, composed of hot electrons excited by the surface reaction of CO oxidation or hydrogen oxidation, correlates well with the turnover rate measured separately by gas chromatography. Furthermore, we show that hot electron flows generated on a gold thin film by photon absorption (or internal photoemission) can be amplified by localized surface plasmon resonance. The influence of hot charge carriers on the chemistry at the metal-oxide interface are discussed for the cases of Au, Ag, and Pt nanoparticles on oxide supports and Pt-CdSe-Pt nanodumbbells. We show that the accumulation or depletion of hot electrons on metal nanoparticles, in turn, can also influence catalytic reactions. Mechanisms suggested for hot-electron-induced chemical reactions on a photoexcited plasmonic metal are discussed. We propose that the manipulation of the flow of hot electrons by changing the electrical characteristics of metal-oxide and metal-semiconductor interfaces can give rise to the intriguing capability of tuning the catalytic activity of hybrid nanocatalysts.

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.

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.

Review: Impacts of permafrost degradation on inorganic chemistry of surface fresh water

NASA Astrophysics Data System (ADS)

Colombo, Nicola; Salerno, Franco; Gruber, Stephan; Freppaz, Michele; Williams, Mark; Fratianni, Simona; Giardino, Marco

2018-03-01

Recent studies have shown that climate change is impacting the inorganic chemical characteristics of surface fresh water in permafrost areas and affecting aquatic ecosystems. Concentrations of major ions (e.g., Ca2 +, Mg2 +, SO42 -, NO3-) can increase following permafrost degradation with associated deepening of flow pathways and increased contributions of deep groundwater. In addition, thickening of the active layer and melting of near-surface ground ice can influence inorganic chemical fluxes from permafrost into surface water. Permafrost degradation has also the capability to modify trace element (e.g., Ni, Mn, Al, Hg, Pb) contents in surface water. Although several local and regional modifications of inorganic chemistry of surface fresh water have been attributed to permafrost degradation, a comprehensive review of the observed changes is lacking. The goal of this paper is to distil insight gained across differing permafrost settings through the identification of common patterns in previous studies, at global scale. In this review we focus on three typical permafrost configurations (pervasive permafrost degradation, thermokarst, and thawing rock glaciers) as examples and distinguish impacts on (i) major ions and (ii) trace elements. Consequences of warming climate have caused spatially-distributed progressive increases of major ion and trace element delivery to surface fresh water in both polar and mountain areas following pervasive permafrost degradation. Moreover, localised releases of major ions and trace elements to surface water due to the liberation of soluble materials sequestered in permafrost and ground ice have been found in ice-rich terrains both at high latitude (thermokarst features) and high elevation (rock glaciers). Further release of solutes and related transport to surface fresh water can be expected under warming climatic conditions. However, complex interactions among several factors able to influence the timing and magnitude of the impacts of permafrost degradation on inorganic chemistry of surface fresh water (e.g., permafrost sensitivity to thawing, modes of permafrost degradation, characteristics of watersheds) require further conceptual and mechanistic understanding together with quantitative diagnosis of the involved mechanisms in order to predict future changes with confidence.

Anisotropic wetting of microstructured surfaces as a function of surface chemistry.

PubMed

Neuhaus, Sonja; Spencer, Nicholas D; Padeste, Celestino

2012-01-01

In order to study the influence of surface chemistry on the wetting of structured surfaces, microstructures consisting of grooves or squares were produced via hot embossing of poly(ethylene-alt-tetrafluoroethylene) ETFE substrates. The structured substrates were modified with polymer brushes, thereby changing their surface functionality and wettability. Water droplets were most strongly pinned to the structure when the surface was moderately hydrophilic, as in the case of poly(4-vinylpyridine) (P4VP) or poly(vinyl(N-methyl-2-pyridone) (PVMP) brush-modified substrates. As a result, the droplet shape was determined by the features of the microstructure. The water contact angles (CA) were considerably higher than on flat surfaces and differed, in the most extreme case, by 37° when measured on grooved substrates, parallel and perpendicular to the grooves. On hydrophobic substrates (pristine ETFE), the same effects were observed but were much less pronounced. On very hydrophilic sampes (those modified with poly(N-methyl-vinylpyridinium) (QP4VP)), the microstructure had no influence on the drop shape. These findings are explained by significant differences in apparent and real contact angles at the relatively smooth edges of the embossed structures. Finally, the highly anisotropic grooved microstructure was combined with a gradient in polymer brush composition and wettability. In the case of a parallel alignment of the gradient direction to the grooves, the directed spreading of water droplets could be observed. © 2011 American Chemical Society

Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

DOE PAGES

Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene; ...

2016-04-07

Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces andmore » enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.« less

An in situ investigation of the influence of a controlled burn on the thermophysical properties of a dry soil

Treesearch

W. J. Massman; J. M. Frank

2004-01-01

High soil temperatures associated with fire influence forests and their ability to regenerate after a fire by altering soil properties and soil chemistry and by killing microbes, plant roots, and seeds. Because intense wild fires are an increasingly common component of the landscape (Graham 2003) and because fire is frequently used by land managers to reduce surface...

SAFETY/TOXICITY ASSESSMENT OF CERIA (A MODEL ENGINEERED NP) TO THE BRAIN

EPA Science Inventory

The results will indicate the influence of the size, shape and various surface chemistry properties of ENMs on their entrance into BBB cells and the brain, compared to selected peripheral organs, the effects they produce in the brain, their biopersistence and biotransformation...

Biofilm on dental implants: a review of the literature.

PubMed

Subramani, Karthikeyan; Jung, Ronald E; Molenberg, Aart; Hammerle, Christoph H F

2009-01-01

The aim of this article was to review the current literature with regard to biofilm formation on dental implants and the influence of surface characteristics (chemistry, surface free energy, and roughness) of dental implant and abutment materials and their design features on biofilm formation and its sequelae. An electronic MEDLINE literature search was conducted of studies published between 1966 and June 2007. The following search terms were used: biofilm and dental implants, biofilm formation/plaque bacterial adhesion and implants, plaque/biofilm and surface characteristics/roughness/surface free energy of titanium dental implants, implant-abutment interface and plaque/biofilm, biofilm and supragingival/subgingival plaque microbiology, biofilm/plaque and implant infection, antibacterial/bacteriostatic titanium, titanium nanocoating/nanopatterning, antimicrobial drug/titanium implant. Both in vitro and in vivo studies were included in this review. Fifty-three articles were identified in this review process. The articles were categorized with respect to their context on biofilm formation on teeth and dental implant surfaces and with regard to the influence of surface characteristics of implant biomaterials (especially titanium) and design features of implant and abutment components on biofilm formation. The current state of literature is more descriptive, rather than providing strong data that could be analyzed through meta-analysis. Basic research articles on surface modification of titanium were also included in the review to analyze the applications of such studies on the fabrication of implant surfaces that could possibly decrease early bacterial colonization and biofilm formation. Increase in surface roughness and surface free energy facilitates biofilm formation on dental implant and abutment surfaces, although this conclusion is derived from largely descriptive literature. Surface chemistry and the design features of the implant-abutment configuration also play a significant role in biofilm formation.

Au-thiol interaction chemistry to influence the structural transformation of semiconductor nanocrystals and formation of giant nanostructures.

PubMed

Bose, Riya; Manna, Goutam; Pradhan, Narayan

2014-04-09

Giant nanostructures which are difficult to design by the classical growth process can be fabricated in a facilitated and well programmed surface ligand removal protocol employing the thiol-gold strong interaction chemistry. When thiol capped small ZnSe seed nanocrystals are treated with amine capped gold particles, gold snatches the thiol ligands from ZnSe and forces them to agglomerate leading to the giant crystalline ZnSe nanostructures. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron attachment to molecules in a cluster environment: suppression and enhancement effects

NASA Astrophysics Data System (ADS)

Fabrikant, Ilya I.

2018-05-01

Cluster environments can strongly influence dissociative electron attachment (DEA) processes. These effects are important in many applications, particularly for surface chemistry, radiation damage, and atmospheric physics. We review several mechanisms for DEA suppression and enhancement due to cluster environments, particularly due to microhydration. Long-range electron-molecule and electron-cluster interactions play often a significant role in these effects and can be analysed by using theoretical models. Nevertheless many observations remain unexplained due to complexity of the physics and chemistry of interaction of DEA fragments with the cluster environment.

Ion beam sputter modification of the surface morphology of biological implants

NASA Technical Reports Server (NTRS)

Weigand, A. J.; Banks, B. A.

1976-01-01

The surface chemistry and texture of materials used for biological implants may significantly influence their performance and biocompatibility. Recent interest in the microscopic control of implant surface texture has led to the evaluation of ion beam sputtering as a potentially useful surface roughening technique. Ion sources, similar to electron bombardment ion thrusters designed for propulsive applications, are used to roughen the surfaces of various biocompatible alloys or polymer materials. These materials are typically used for dental implants, orthopedic prostheses, vascular prostheses, and artificial heart components. Masking techniques and resulting surface textures are described along with progress concerning evaluation of the biological response to the ion beam sputtered surfaces.

Ion-beam-sputter modification of the surface morphology of biological implants

NASA Technical Reports Server (NTRS)

Weigand, A. J.; Banks, B. A.

1977-01-01

The surface chemistry and texture of materials used for biological implants may significantly influence their performance and biocompatibility. Recent interest in the microscopic control of implant surface texture has led to the evaluation of ion-beam sputtering as a potentially useful surface roughening technique. Ion sources, similar to electron-bombardment ion thrusters designed for propulsive applications, are used to roughen the surfaces of various biocompatible alloys or polymer materials. These materials are typically used for dental implants, orthopedic prostheses, vascular prostheses, and artificial heart components. Masking techniques and resulting surface textures are described along with progress concerning evaluation of the biological response to the ion-beam-sputtered surfaces.

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.

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.

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.

Influence of Primary Water Chemistry on Oxides Formed on Alloy 600 and Alloy 690

NASA Astrophysics Data System (ADS)

Devine, Thomas M.

The results of in situ SERS investigations of Alloys' 600 and 690 surface films were combined with the results of a number of ex situ studies conducted by other researchers who used a variety of experimental techniques. Comparing the results of different investigations revealed the surface films' composition and microstructure were most sensitive to alloy composition and the concentrations of aqueous metal cations (especially Fe+2).

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.

Influence of ligand chemistry on silver nanoparticles for colorimetric detection of Cr3+ and Hg2+ ions

NASA Astrophysics Data System (ADS)

Kailasa, Suresh Kumar; Chandel, Madhurya; Mehta, Vaibhavkumar N.; Park, Tae Jung

2018-04-01

In this work, we describe the role of ligand chemistry on the surfaces of silver nanoparticles (Ag NPs) for tuning their analytical applications. The citrate and melamine (MA) molecules were used as ligands for the surface modification of Ag NPs. The addition of Cr3+ ion in citrate-Ag NPs (Cit-Ag NPs) and of Hg2+ ion in melamine-Ag NPs (MA-Ag NPs) cause Ag NPs aggregation, and are accompanied by a color change and a red-shift. The resulting distinctly visual readouts are favorable for colorimetric detection of Cr3+ and Hg2+ ions. Under optimal conditions, the linear ranges are observed in the concentration ranges of 1.0-50.0 and of 10.0-100.0 μM, and with detection limit of 0.52 and 1.80 μM for Cr3+ and Hg2+ ions. The simultaneous detection of Cr3+ and Hg2+ ion is driven by the changing the ligand chemistry on the surfaces of Ag NPs that allows to tune their specific interactions with target analytes. Finally, the functionalized Ag NPs were successfully applied to detect Cr3+ and Hg2+ ions in water samples with satisfactory recoveries.

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

USGS Publications Warehouse

Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

2000-01-01

macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

Fullerene ion chemistry: a journey of discovery and achievement

PubMed Central

Böhme, Diethard K.

2016-01-01

An account is provided of the extraordinary features of buckminster fullerene cations and their chemistry that we discovered in our Ion Chemistry Laboratory at York University (Canada) during a ‘golden’ period of research in the early 1990s, just after C60 powder became available. We identified new chemical ways of C60 ionization and tracked novel chemistry of C60n+ as a function of charge state (n=1–3) with some 50 different reagent molecules. We found that multiple charges enhance reaction rates and diversify reaction products and mechanisms. Strong electrostatic interactions with reagent molecules were seen to reduce barriers to carbon surface bonding and charge-separation reactions, while intramolecular Coulomb repulsion appeared to localize charge on the surface or the substituent and so influence higher order chemistry, including ‘spindle’, ‘star’, ‘fuzzy ball’, ‘ball-and-chain’ and dimer ion formation. We introduced the notion of ‘apparent’ gas-phase acidity with measurements of proton-transfer reactions of multiply charged fullerene cations. We also explored the attachment of atomic metal cations to C60 and their subsequent reactions. All these findings were applied to the possible chemistry of fullerene cations in the interstellar medium with a focus on multiply charged fullerene ion formation and the intervention of fullerene cations in fullerene derivatization and molecular synthesis, with a view to their possible future detection. This article is part of the themed issue ‘Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene’. PMID:27501972

Characteristics of biochar: Microchemical properties

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

Amonette, James E.; Joseph, Stephen

2009-03-13

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

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.

Influence of pretreatment on the surface characteristics of PLLA fibers and subsequent hydroxyapatite coating.

PubMed

Peng, F; Olson, J R; Shaw, M T; Wei, M

2009-01-01

A fibrous precursor for bone repair composites was made by coating poly(L-lactide) (PLLA) fibers with hydroxyapatite (HA) using a biomimetic method. To enhance the bonding between the HA coating and the PLLA fiber, PLLA fibers were etched with either sodium hydroxide or sodium hypochlorite to generate carboxyl groups on fiber surfaces. The experiments were designed to determine the influence of etching on the fiber surface morphology and chemistry as well as the subsequent HA coating on the etched fiber surfaces. It was found that the etching pretreatment increased the roughness as well as the hydrophilicity of fibers, indicating that hydrolysis of PLLA chains had taken place on fiber surfaces. The etching pretreatment also promoted HA coating formation by introducing thicker coating on the surface of fibers with a longer etching time, a higher etching concentration, or with NaOCl as the etching agent. A mechanism of surface hydrolysis and oxidation of PLLA was proposed. (c) 2008 Wiley Periodicals, Inc.

Atomistic Structure, Strength, and Kinetic Properties of Intergranular Films in Ceramics

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

Garofalini, Stephen H

2015-01-08

Intergranular films (IGFs) present in polycrystalline oxide and nitride ceramics provide an excellent example of nanoconfined glasses that occupy only a small volume percentage of the bulk ceramic, but can significantly influence various mechanical, thermal, chemical, and optical properties. By employing molecular dynamics computer simulations, we have been able to predict structures and the locations of atoms at the crystal/IGF interface that were subsequently verified with the newest electron microscopies. Modification of the chemistry of the crystal surface in the simulations provided the necessary mechanism for adsorption of specific rare earth ions from the IGF in the liquid state tomore » the crystal surface. Such results had eluded other computational approaches such as ab-initio calculations because of the need to include not only the modified chemistry of the crystal surfaces but also an accurate description of the adjoining glassy IGF. This segregation of certain ions from the IGF to the crystal caused changes in the local chemistry of the IGF that affected fracture behavior in the simulations. Additional work with the rare earth ions La and Lu in the silicon oxynitride IGFs showed the mechanisms for their different affects on crystal growth, even though both types of ions are seen adhering to a bounding crystal surface that would normally imply equivalent affects on grain growth.« less

A Smart Superwetting Surface with Responsivity in Both Surface Chemistry and Microstructure.

PubMed

Zhang, Dongjie; Cheng, Zhongjun; Kang, Hongjun; Yu, Jianxin; Liu, Yuyan; Jiang, Lei

2018-03-26

Recently, smart surfaces with switchable wettability have aroused much attention. However, only single surface chemistry or the microstructure can be changed on these surfaces, which significantly limits their wetting performances, controllability, and applications. A new surface with both tunable surface microstructure and chemistry was prepared by grafting poly(N-isopropylacrylamide) onto the pillar-structured shape memory polymer on which multiple wetting states from superhydrophilicity to superhydrophobicity can be reversibly and precisely controlled by synergistically regulating the surface microstructure and chemistry. Meanwhile, based on the excellent controllability, we also showed the application of the surface as a rewritable platform, and various gradient wettings can be obtained. This work presents for the first time a surface with controllability in both surface chemistry and microstructure, which starts some new ideas for the design of novel superwetting materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Changes in the chemistry of small Irish lakes.

PubMed

Burton, Andrew W; Aherne, Julian

2012-03-01

A re-survey of acid-sensitive lakes in Ireland (initial survey 1997) was carried out during spring 2007 (n = 60). Since 1997, atmospheric emissions of sulfur dioxide and deposition of non-marine sulfate (SO(4) (2-)) in Ireland have decreased by ~63 and 36%, respectively. Comparison of water chemistry between surveys showed significant decreases in the concentration of SO(4) (2-), non-marine SO(4) (2-), and non-marine base cations. In concert, alkalinity increased significantly; however, no change was observed in surface water pH and total aluminum. High inter-annual variability in sea salt inputs and increasing (albeit non-significant) dissolved organic carbon may have influenced the response of pH and total aluminum (as ~70% is organic aluminum). Despite their location on the western periphery of Europe, and dominant influence from Atlantic air masses, the repeat survey suggests that the chemistry of small Irish lakes has shown a significant response to reductions in air pollution driven primarily by the implementation of the Gothenburg Protocol under the UNECE Convention on Long-Range Transboundary Air Pollution.

Element cycling in upland/peatland watersheds Chapter 8.

Treesearch

Noel Urban; Elon S. Verry; Steven Eisenreich; David F. Grigal; Stephen D. Sebestyen

2011-01-01

Studies at the Marcell Experimental Forest (MEF) have measured the pools, cycling, and transport of a variety of elements in both the upland and peatland components of the landscape. Peatlands are important zones of element retention and biogeochemical reactions that greatly influence the chemistry of surface water. In this chapter, we summarize findings on nitrogen (N...

Standardization of fluorine-18 manufacturing processes: new scientific challenges for PET.

PubMed

Hjelstuen, Ole K; Svadberg, Anders; Olberg, Dag E; Rosser, Mark

2011-08-01

In [(18)F]fluoride chemistry, the minute amounts of radioactivity taking part in a radiolabeling reaction are easily outnumbered by other reactants. Surface areas become comparably larger and more influential than in standard fluorine chemistry, while leachables, extractables, and other components that normally are considered small impurities can have a considerable influence on the efficiency of the reaction. A number of techniques exist to give sufficient (18)F-tracer for a study in a pre-clinical or clinical system, but the chemical and pharmaceutical understanding has significant gaps when it comes to scaling up or making the reaction more efficient. Automation and standardization of [(18)F]fluoride PET tracers is a prerequisite for reproducible manufacturing across multiple PET centers. So far, large-scale, multi-site manufacture has been established only for [(18)F]FDG, but several new tracers are emerging. In general terms, this transition from small- to large-scale production has disclosed several scientific challenges that need to be addressed. There are still areas of limited knowledge in the fundamental [(18)F]fluoride chemistry. The role of pharmaceutical factors that could influence the (18)F-radiosynthesis and the gaps in precise chemistry knowledge are discussed in this review based on a normal synthesis pattern. Copyright © 2011 Elsevier B.V. All rights reserved.

Aggregation Kinetics of Diesel Soot Nanoparticles in Wet Environments.

PubMed

Chen, Chengyu; Huang, Weilin

2017-02-21

Soot produced during incomplete combustion consists mainly of carbonaceous nanoparticles (NPs) with severe adverse environmental and health effects, and its environmental fate and transport are largely controlled by aggregation. In this study, we examined the aggregation behavior for diesel soot NPs under aqueous condition in an effort to elucidate the fundamental processes that govern soot particle-particle interactions in wet environments such as rain droplets or surface aquatic systems. The influence of electrolytes and aqueous pH on colloidal stability of these NPs was investigated by measuring their aggregation kinetics in different aqueous solution chemistries. The results showed that the NPs had negatively charged surfaces and exhibited both reaction- and diffusion-limited aggregation regimes with rates depended upon solution chemistry. The aggregation kinetics data were in good agreement with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical coagulation concentrations (CCC) were quantified and the Hamaker constant was derived for the soot (1.4 × 10 -20 J) using the colloidal chemistry approach. The study indicated that, depending upon local aqueous chemistry, single soot NPs could remain stable against self-aggregation in typical freshwater environments and in neutral cloud droplets but are likely to aggregate under salty (e.g., estuaries) or acidic (e.g., acid rain droplets) aquatic conditions or both.

Gold surfaces and nanoparticles are protected by Au(0)-thiyl species and are destroyed when Au(I)-thiolates form.

PubMed

Reimers, Jeffrey R; Ford, Michael J; Halder, Arnab; Ulstrup, Jens; Hush, Noel S

2016-03-15

The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)-thiyl, with Au(I)-thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)-thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s-d hybridization and charge polarization effects that perturbatively mix in some Au(I)-thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)-thiolate involvement. Predictions that Brust-Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)-thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established.

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

PubMed Central

Reimers, Jeffrey R.; Ford, Michael J.; Halder, Arnab; Ulstrup, Jens; Hush, Noel S.

2016-01-01

The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)–thiyl, with Au(I)–thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)–thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s–d hybridization and charge polarization effects that perturbatively mix in some Au(I)–thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)–thiolate involvement. Predictions that Brust–Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)–thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established. PMID:26929334

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.

Chemistry and Photochemistry at the Surface of Urban Road Dust and Photoactive Minerals

NASA Astrophysics Data System (ADS)

Styler, S. A.; Abou-Ghanem, M.; Wickware, B.

2017-12-01

Each year, over a billion tons of dust are released into the atmosphere from arid regions. After its emission, dust can undergo efficient long-range transport to urban centres, where it can interact with local pollution sources. Another source of dust in urban regions is road dust resuspension, which is the largest anthropogenic source of primary particulate matter in both Canada and the United States. Since dust contains light-absorbing components, including iron- and titanium-containing minerals, dust-catalyzed photochemical processes have the potential to influence both the lifetime of pollutants present at the dust surface and the composition of the surrounding atmosphere. To date, most studies of dust photochemistry have focused on TiO2-mediated processes, and no studies have explored trace gas uptake at the surface of road dust. Here, we present first results from aerosol and coated-wall flow tube investigations of ozone uptake at the surface of a suite of titanium-containing minerals and road dust collected in Edmonton, Alberta. Together, this work represents a significant advance in our understanding of chemistry and photochemistry at realistic environmental interfaces.

Influence of Immobilized Biomolecules on Magnetic Bead Plug Formation and Retention in Capillary Electrophoresis

PubMed Central

Henken, Rachel L.; Chantiwas, Rattikan; Gilman, S. Douglass

2012-01-01

Significant changes in the formation and retention of magnetic bead plugs in a capillary during electrophoresis were studied, and it was demonstrated that these effects were due to the type of biological molecule immobilized on the surface of these beads. Three biological molecules, an antibody, an oligonucleotide and alkaline phosphatase, were attached to otherwise identical streptavidin-coated magnetic beads through biotin-avidin binding in order to isolate differences in bead immobilization in a magnetic field resulting from the type of biological molecule immobilized on the bead surface. Alkaline phosphatase also was attached to the magnetic beads using epoxy groups on the bead surfaces (instead of avidin-biotin binding) to study the impact of immobilization chemistry. The formation and retention of magnetic bead plugs were studied quantitatively using light scattering detection of magnetic particles eluting from the bead plugs and qualitatively using microscopy. Both the type of biomolecule immobilized on the magnetic bead surface and the chemistry used to link the biomolecule to the magnetic bead impacted the formation and retention of the bead plugs. PMID:22437880

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.

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Plasma variables and tribological properties of coatings in low pressure (0.1 - 10.0 torr) plasma systems

NASA Technical Reports Server (NTRS)

Avni, R.; Spalvins, T.

1984-01-01

A detailed treatment is presented of the dialog known as plasma surface interactions (PSI) with respect to the coating process and its tribological behavior. Adsorption, morphological changes, defect formation, sputtering, chemical etching, and secondary electron emission are all discussed as promoting and enhancing the surface chemistry, thus influencing the tribological properties of the deposited flux. Phenomenological correlations of rate of deposition, flux composition, microhardness, and wear with the plasma layer variables give an insight to the formation of chemical bonding between the deposited flux and the substrate surface.

Impact of water chemistry on surface charge and aggregation of polystyrene microspheres suspensions.

PubMed

Lu, Songhua; Zhu, Kairuo; Song, Wencheng; Song, Gang; Chen, Diyun; Hayat, Tasawar; Alharbi, Njud S; Chen, Changlun; Sun, Yubing

2018-07-15

The discharge of microplastics into aquatic environment poses the potential threat to the hydrocoles and human health. The fate and transport of microplastics in aqueous solutions are significantly influenced by water chemistry. In this study, the effect of water chemistry (i.e., pH, foreign salts and humic acid) on the surface charge and aggregation of polystyrene microsphere in aqueous solutions was conducted by batch, zeta potentials, hydrodynamic diameters, FT-IR and XPS analysis. Compared to Na + and K + , the lower negative zeta potentials and larger hydrodynamic diameters of polystyrene microspheres after introduction of Mg 2+ were observed within a wide range of pH (2.0-11.0) and ionic strength (IS, 0.01-500mmol/L). No effect of Cl - , HCO 3 - and SO 4 2- on the zeta potentials and hydrodynamic diameters of polystyrene microspheres was observed at low IS concentrations (<5mmol/L), whereas the zeta potentials and hydrodynamic diameters of polystyrene microspheres after addition of SO 4 2- were higher than that of Cl - and HCO 3 - at high IS concentrations (>10mmol/L). The zeta potentials of polystyrene microspheres after HA addition were decreased at pH2.0-11.0, whereas the lower hydrodynamic diameters were observed at pH<4.0. According to FT-IR and XPS analysis, the change in surface properties of polystyrene microspheres after addition of hydrated Mg 2+ and HA was attributed to surface electrostatic and/or steric repulsions. These investigations are crucial for understanding the effect of water chemistry on colloidal stability of microplastics in aquatic environment. Copyright © 2018 Elsevier B.V. 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.

Proteomic Analysis of Serum Opsonins Impacting Biodistribution and Cellular Association of Porous Silicon Microparticles

PubMed Central

Serda, Rita E.; Blanco, Elvin; Mack, Aaron; Stafford, Susan J.; Amra, Sarah; Li, Qingpo; van de Ven, Anne L.; Tanaka, Takemi; Torchilin, Vladimir P.; Wiktorowicz, John E.; Ferrari, Mauro

2014-01-01

Mass transport of drug delivery vehicles is guided by particle properties, such as shape, composition and surface chemistry, as well as biomolecules and serum proteins that adsorb to the particle surface. In an attempt to identify serum proteins influencing cellular associations and biodistribution of intravascularly injected particles, we used two dimensional gel electrophoresis and mass spectrometry to identify proteins eluted from the surface of cationic and anionic silicon microparticles. Cationic microparticles displayed a 25-fold greater abundance of Ig light chain variable region, fibrinogen, and complement component 1 compared to their anionic counterparts. The anionic-surface favored equal accumulation of microparticles in the liver and spleen, while cationic-surfaces favored preferential accumulation in the spleen. Immunohistochemistry supported macrophage internalization of both anionic and cationic silicon microparticles in the liver, as well as evidence of association of cationic microparticles with hepatic endothelial cells. Furthermore, scanning electron micrographs supported cellular competition for cationic microparticles by endothelial cells and macrophages. Despite high macrophage content in the lungs and tumor, microparticle uptake by these cells was minimal, supporting differences in the repertoire of surface receptors expressed by tissue-specific macrophages. In summary, particle surface chemistry drives selective binding of serum components impacting cellular interactions and biodistribution. PMID:21303614

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

Groundwater-surface water interactions and their effects on ecosystem metabolism in a coastal wetland: example from the Florida Everglades

NASA Astrophysics Data System (ADS)

Price, R. M.; Zapata, X.; Koch, G. R.

2013-05-01

Groundwater typically has higher concentrations of salts and nutrients as compared to surface waters in coastal wetlands affected by saltwater intrusion. Discharge of the nutrient-laden brackish groundwater is expected to influence ecosystem function in the overlying surface water. In the coastal Everglades, elevated concentrations of phosphorus have been observed in the underlying groundwater due to water-rock interactions occurring as seawater intrudes into the coastal carbonate aquifer. The objective of this research was to determine the timing and amount of brackish groundwater discharge to the coastal wetlands of the Everglades and to evaluate the effects of the groundwater discharge on the surface water chemistry and ecosystem metabolism. The timing of groundwater discharge was determined by four techniques including a water balance, hydraulic gradient, temperature, and geochemical tracers. Groundwater discharge rates were quantified from well data using Darcy's Law. Ecosystem metabolism was estimated as daily rates of gross primary production (GPP), ecosystem respiration (R) and net ecosystem production (NEP) from free-water, diel changes in dissolved oxygen. Over 2 years, all four groundwater discharge techniques converged as to the timing of groundwater discharge which was greatest between May and July. Surface water chemistry was fresh from September through February, but became brackish to hypersaline between March and July, concurrent with the times of highest brackish groundwater discharge. Phosphorus concentrations as well as GPP and R were observed to spike in the surface water during the times of greatest groundwater discharge. The results of this research support the conclusions that brackish groundwater discharge effects surface water chemistry and ecosystem function in the coastal Everglades.

Design of Microstructured Conducting Polymer Films for Enhanced Trace Explosives Detection

NASA Astrophysics Data System (ADS)

Laster, Jennifer S.

The detection of trace amounts of explosive material is critical to national security. Ion mobility spectrometer (IMS)-based contact sampling continues to be a common method employed for the detection of explosives in high security checkpoint applications, such as airport security. In this process a surface of interest, such as a passenger's hands or luggage, is probed by a swab or particle trap to collect and transfer residue to an IMS for analysis. The collection of residue on a sampling swab has been shown to be a limiting step in this detection process. As such, there is significant need to develop new materials with increased adhesion to explosive analytes and with superior particle removal abilities. Here, the design of novel sampling swabs is presented for the enhanced collection of trace explosive residue from surfaces. First, the influence of the swab microstructure on the ability to remove particles from representative substrates is demonstrated. Free-standing microstructured polypyrrole (PPy) films of a variety of dimensions and form factors are fabricated using a templated electropolymerization process. The removal of polystyrene fluorescent particles from an aluminum substrate of varying surface roughness is examined as a function of the polymer microstructure. PPy microstructured films display enhanced particle removal abilities compared to PPy non-structured and current commercial films. This increase in particle removal is attributed to the increased particle-swab contact from the microstructured films. Next, the influence of the surface chemistry of sampling swabs on the collection of a representative explosive analyte, trinitrotoluene (TNT) is explored. The surface chemistry of PPy films is modified by electropolymerizaton of an N-substituted pyrrole monomer. The surface chemistries examined include a methyl, carboxylic acid, and amino-phenyl functionality. The vapor deposition of TNT on the surface of the functionalized PPy films is quantified through ultraviolet-visible (UV-vis) absorption and compared to commercial swabbing materials of varying chemistry and surface roughness. The PPy modified films with potential sites for hydrogen bonding display the highest deposition of TNT, while the Teflon coated commercial films display the lowest interaction with TNT. Finally, the desorption and release of TNT from sampling swabs is studied as an effect of temperature and of applied bias. For successful analyte detection within an IMS, the residue collected on a sampling swab must be released from the swab, typically through a thermal desorption process. In this work the release of TNT from sampling swabs is determined through solid-phase microextraction-gas chromatography mass spectrometry (SPME-GCMS). The results of this thesis provide important information on the design considerations for the development of novel particle sampling swabs with increased performance.

Chemistry of throughfall under douglas fir and Rocky Mountain juniper. [Pseudotsuga menziesii var. glauca; Juniperus scopulorum

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

Hart, G.E.; Parent, D.R.

1974-01-01

Concentrations of sodium, calcium, magnesium, potassium, phosphorus and nitrate were measured in throughfall under isolated douglas fir (Pseudotsuga menziesii var. glauca) and Rocky Mountain juniper (Juniperus scopulorum) trees in northern Utah for 39 storms in 1970 and 1971. Concentrations were 3-16 times greater under the trees than in the open. Throughfall under douglas fir invariably had higher concentrations than that under juniper. Since most of the chemical input occurs as dry fallout between storms, surface area and form of the canopy are believed to be the prime factors influencing throughfall chemistry in this region. 15 references, 2 figures, 5 tables.

Chemistry in interstellar space. [environment characteristics influencing reaction dynamics

NASA Technical Reports Server (NTRS)

Donn, B.

1973-01-01

The particular characteristics of chemistry in interstellar space are determined by the unique environmental conditions involved. Interstellar matter is present at extremely low densities. Large deviations from thermodynamic equilibrium are, therefore, to be expected. A relatively intense ultraviolet radiation is present in many regions. The temperatures are in the range from 5 to 200 K. Data concerning the inhibiting effect of small activation energies in interstellar clouds are presented in a table. A summary of measured activation energies or barrier heights for exothermic exchange reactions is also provided. Problems of molecule formation are discussed, taking into account gas phase reactions and surface catalyzed processes.

An evaluation of effects of groundwater exchange on nearshore habitats and water quality of western Lake Erie

USGS Publications Warehouse

Haack, Sheridan K.; Neff, Brian P.; Rosenberry, Donald O.; Savino, Jacqueline F.; Lundstrom, Scott C.

2005-01-01

Historically, the high potentiometric surface of groundwater in the Silurian/Devonian carbonate aquifer in Monroe County, MI resulted in discharge of highly mineralized, SO4-rich groundwater to the Lake Erie shoreline near both Erie State Game Area (ESGA) and Pointe Mouillee State Game Area (PMSGA). Recently, regional groundwater levels near PMSGA have been drawn down as much as 45 m below lake level in apparent response to quarry dewatering. From August to November of 2003, we conducted preliminary studies of groundwater flow dynamics and chemistry, shallow lake water chemistry, and fish and invertebrate communities at both sites. Consistent with regional observations, groundwater flow direction in the nearshore at ESGA was upward, or toward Lake Erie, and shallow nearshore groundwater chemistry was influenced by regional groundwater chemistry. In contrast, at PMSGA, the groundwater flow potential was downward and lake water, influenced by quarry discharge seeping downward into nearshore sediments, produced a different lake and shallow groundwater chemistry than at ESGA. Although the invertebrate and young fish community was similar at the two sites, taxonomic groups tolerant of degraded water quality were more prevalent at PMSGA. Sensitive taxa were more prevalent at ESGA. We propose a conceptual model, based on well-described models of groundwater/seawater interaction along coastal margins, to describe the interconnection among geologic, hydrologic, chemical, and biological processes in the different nearshore habitats of Lake Erie, and we identify processes that warrant further detailed study in the Great Lakes.

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

NASA Astrophysics Data System (ADS)

Leff, L.

2005-05-01

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

Molecular Grafting of Fluorinated and Nonfluorinated Alkylsiloxanes on Various Ceramic Membrane Surfaces for the Removal of Volatile Organic Compounds Applying Vacuum Membrane Distillation.

PubMed

Kujawa, Joanna; Al-Gharabli, Samer; Kujawski, Wojciech; Knozowska, Katarzyna

2017-02-22

Four main tasks were presented: (i) ceramic membrane functionalization (TiO 2 5 kDa and 300 kDa), (ii) extended material characterization (physicochemistry and tribology) of pristine and modified ceramic samples, (iii) evaluation of chemical and mechanical stability, and finally (iv) assessment of membrane efficiency in vacuum membrane distillation applied for volatile organic compounds (VOCs) removal from water. Highly efficient molecular grafting with four types of perfluoroalkylsilanes and one nonfluorinated agent was developed. Materials with controllable tribological and physicochemical properties were achieved. The most meaningful finding is associated with the applicability of fluorinated and nonfluorinated grafting agents. The results of contact angle, hysteresis of contact angle, sliding angle, and critical surface tension as well as Young's modulus, nanohardness, and adhesion force for grafting by these two modifiers are comparable. This provides insight into the potential applicability of environmental friendly hydrophobic and superhydrophobic surfaces. The achieved hydrophobic membranes were very effective in the removal of VOCs (butanol, methyl-tert-butyl ether, and ethyl acetate) from binary aqueous solutions in vacuum membrane distillation. The correlation between membrane effectiveness and separated solvent polarity was compared in terms of material properties and resistance to the wetting (kinetics of wetting and in-depth liquid penetration). Material properties were interpreted considering Zisman theory and using Kao diagram. The significant influence of surface chemistry on the membrane performance was noticed (5 kDa, influence of hydrophobic nanolayer and separation controlled by solution-diffusion model; 300 kDa, no impact of surface chemistry and separation controlled by liquid-vapor equilibrium).

Shape control VO2 nanorods prepared by soft chemistry and electrochemical method

NASA Astrophysics Data System (ADS)

Simo, A.; Sibanyoni, J.; Fuku, X.; Numan, N.; Omorogbe, S.; Maaza, M.

2018-07-01

"Bottom up" approach is of primary interest for chemistry and materials science because the fundamental building blocks are atoms. Thus colloidal chemical synthetic methods can be utilized to prepare uniform nanocrystals with controlled particle size. In the following work of study, thermochromic VO2 nanostructures were prepared by hydrothermal technique soft chemistry. We concentrate on solution phase synthetic methods that enable a proper shape and size control of metal oxide nanocrystals. Their structural properties were studied by Scanning Electron Microscopy (SEM), Fourier Transform IR (FTIR) and Differential Scanning Calorimetry (DSC). It is demonstrated that the surfactant assistance (NaOH) has great influence on the morphology-control of the material. Electrochemical properties of the nanospheres show good stability after 20 cycles and the surface diffusion coefficient was calculated to be 5 × 10-6 cm2 s-1.

When the Sun's Away, N2O5 Comes Out to Play: An Updated Analysis of Ambient N2O5 Heterogeneous Chemistry

NASA Astrophysics Data System (ADS)

McDuffie, E. E.; Brown, S. S.

2017-12-01

The heterogeneous chemistry of N2O5 impacts the budget of tropospheric oxidants, which directly controls air quality at Earth's surface. The reaction between gas-phase N2O5 and aerosol particles occurs largely at night, and is therefore more important during the less-intensively-studied winter season. Though N2O5-aerosol interactions are vital for the accurate understanding and simulation of tropospheric chemistry and air quality, many uncertainties persist in our understanding of how various environmental factors influence the reaction rate and probability. Quantitative and accurate evaluation of these factors directly improves the predictive capabilities of atmospheric models, used to inform mitigation strategies for wintertime air pollution. In an update to last year's presentation, The Wintertime Fate of N2O5: Observations and Box Model Analysis for the 2015 WINTER Aircraft Campaign, this presentation will focus on recent field results regarding new information about N2O5 heterogeneous chemistry and future research directions.

Estimating natural background groundwater chemistry, Questa molybdenum mine, New Mexico

USGS Publications Warehouse

Verplanck, Phillip L.; Nordstrom, D. Kirk; Plumlee, Geoffrey S.; Walker, Bruce M.; Morgan, Lisa A.; Quane, Steven L.

2010-01-01

This 2 1/2 day field trip will present an overview of a U.S. Geological Survey (USGS) project whose objective was to estimate pre-mining groundwater chemistry at the Questa molybdenum mine, New Mexico. Because of intense debate among stakeholders regarding pre-mining groundwater chemistry standards, the New Mexico Environment Department and Chevron Mining Inc. (formerly Molycorp) agreed that the USGS should determine pre-mining groundwater quality at the site. In 2001, the USGS began a 5-year, multidisciplinary investigation to estimate pre-mining groundwater chemistry utilizing a detailed assessment of a proximal natural analog site and applied an interdisciplinary approach to infer pre-mining conditions. The trip will include a surface tour of the Questa mine and key locations in the erosion scar areas and along the Red River. The trip will provide participants with a detailed understanding of geochemical processes that influence pre-mining environmental baselines in mineralized areas and estimation techniques for determining pre-mining baseline conditions.

Effect of surface topological structure and chemical modification of flame sprayed aluminum coatings on the colonization of Cylindrotheca closterium on their surfaces

NASA Astrophysics Data System (ADS)

Chen, Xiuyong; He, Xiaoyan; Suo, Xinkun; Huang, Jing; Gong, Yongfeng; Liu, Yi; Li, Hua

2016-12-01

Biofouling is one of the major problems for the coatings used for protecting marine infrastructures during their long-term services. Regulation in surface structure and local chemistry is usually the key for adjusting antifouling performances of the coatings. In this study, flame sprayed multi-layered aluminum coatings with micropatterned surfaces were constructed and the effects of their surface structure and chemistry on the settlement of typical marine diatoms were investigated. Micropatterned topographical morphology of the coatings was constructed by employing steel mesh as a shielding plate during the coating deposition. A silicone elastomer layer for sealing and interconnection was further brush-coated on the micropatterned coatings. Additional surface modification was made using zwitterionic molecules via DOPA linkage. The surface-modified coatings resist effectively colonization of Cylindrotheca closterium. This is explained by the quantitative examination of a simplified conditioning layer that deteriorated adsorption of bovine calf serum proteins on the zwitterionic molecule-treated samples is revealed. The colonization behaviors of the marine diatoms are markedly influenced by the micropatterned topographical morphology. Either the surface micropatterning or the surface modification by zwitterionic molecules enhances antimicrobial ability of the coatings. However, the combined micropatterned structure and zwitterionic modification do not show synergistic effect. The results give insight into anti-corrosion/fouling applications of the modified aluminum coatings in the marine environment.

Performance of high temperature heat flux plates and soil moisture probes during controlled surface fires

Treesearch

W. J. Massman; J. M. Frank; S. M. Massman; W. D. Shepperd

2003-01-01

Natural and prescribed fires play an important role in managing and maintaining most ecosystems in the western United States. The high soil temperatures associated with fire influence forests and their ability to regenerate after a fire by altering soil properties and soil chemistry and by killing microbes, plant roots, and seeds. Because prescribed fire is frequently...

Influences of N-fixing and non-N-fixing vegetation and invasive fish on water chemistry of Hawaiian anchialine ponds

Treesearch

B. D. Dudley; Richard MacKenzie; T. S. Sakihara; H. Dulaiova; C. A. Waters; Flint Hughes; R. Ostertag

2014-01-01

In coastal waters, it remains unclear how terrestrial invasive species might alter nutrient availability and thus affect bottom-up control of primary production. Anchialine ponds are tidal- and groundwater-fed coastal water bodies without surface connections that provide convenient model systems in which to examine terrestrial to aquatic nutrient flow. To investigate...

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

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.

Carbon Nanotube Web with Carboxylated Polythiophene "Assist" for High-Performance Battery Electrodes.

PubMed

Kwon, Yo Han; Park, Jung Jin; Housel, Lisa M; Minnici, Krysten; Zhang, Guoyan; Lee, Sujin R; Lee, Seung Woo; Chen, Zhongming; Noda, Suguru; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C; Reichmanis, Elsa

2018-04-24

A carbon nanotube (CNT) web electrode comprising magnetite spheres and few-walled carbon nanotubes (FWNTs) linked by the carboxylated conjugated polymer, poly[3-(potassium-4-butanoate) thiophene] (PPBT), was designed to demonstrate benefits derived from the rational consideration of electron/ion transport coupled with the surface chemistry of the electrode materials components. To maximize transport properties, the approach introduces monodispersed spherical Fe 3 O 4 (sFe 3 O 4 ) for uniform Li + diffusion and a FWNT web electrode frame that affords characteristics of long-ranged electronic pathways and porous networks. The sFe 3 O 4 particles were used as a model high-capacity energy active material, owing to their well-defined chemistry with surface hydroxyl (-OH) functionalities that provide for facile detection of molecular interactions. PPBT, having a π-conjugated backbone and alkyl side chains substituted with carboxylate moieties, interacted with the FWNT π-electron-rich and hydroxylated sFe 3 O 4 surfaces, which enabled the formation of effective electrical bridges between the respective components, contributing to efficient electron transport and electrode stability. To further induce interactions between PPBT and the metal hydroxide surface, polyethylene glycol was coated onto the sFe 3 O 4 particles, allowing for facile materials dispersion and connectivity. Additionally, the introduction of carbon particles into the web electrode minimized sFe 3 O 4 aggregation and afforded more porous FWNT networks. As a consequence, the design of composite electrodes with rigorous consideration of specific molecular interactions induced by the surface chemistries favorably influenced electrochemical kinetics and electrode resistance, which afforded high-performance electrodes for battery applications.

Influence of stripping and cooling atmospheres on surface properties and corrosion of zinc galvanizing coatings

NASA Astrophysics Data System (ADS)

Yasakau, K. A.; Giner, I.; Vree, C.; Ozcan, O.; Grothe, R.; Oliveira, A.; Grundmeier, G.; Ferreira, M. G. S.; Zheludkevich, M. L.

2016-12-01

In this work the influence of stripping/cooling atmospheres used after withdrawal of steel sheet from Zn or Zn-alloy melt on surface properties of Zn (Z) and Zn-Al-Mg (ZM) hot-dip galvanizing coatings has been studied. The aim was to understand how the atmosphere (composed by nitrogen (N2) or air) affects adhesion strength to model adhesive and corrosive behaviour of the galvanized substrates. It was shown that the surface chemical composition and Volta potential of the galvanizing coatings prepared under the air or nitrogen atmosphere are strongly influenced by the atmosphere. The surface chemistry Z and ZM surfaces prepared under N2 contained a higher content of metal atoms and a richer hydroxide density than the specimens prepared under air atmosphere as assessed by X-ray photoelectron spectroscopy (XPS). The induced differences on the microstructure of the galvanized coatings played a key role on the local corrosion induced defects as observed by means of in situ Atomic force microscopy (AFM). Peel force tests performed on the substrates coated by model adhesive films indicate a higher adhesive strength to the surfaces prepared under nitrogen atmosphere. The obtained results have been discussed in terms of the microstructure and surface chemical composition of the galvanizing coatings.

Numerical Prediction of the Influence of Process Parameters on Large Area Diamond Deposition by DC Arcjet with ARC Roots Rotating and Operating at Gas Recycling Mode

NASA Astrophysics Data System (ADS)

Lu, F. X.; Huang, T. B.; Tang, W. Z.; Song, J. H.; Tong, Y. M.

A computer model have been set up for simulation of the flow and temperature field, and the radial distribution of atomic hydrogen and active carbonaceous species over a large area substrate surface for a new type dc arc plasma torch with rotating arc roots and operating at gas recycling mode A gas recycling radio of 90% was assumed. In numerical calculation of plasma chemistry, the Thermal-Calc program and a powerful thermodynamic database were employed. Numerical calculations to the computer model were performed using boundary conditions close to the experimental setup for large area diamond films deposition. The results showed that the flow and temperature field over substrate surface of Φ60-100mm were smooth and uniform. Calculations were also made with plasma of the same geometry but no arc roots rotation. It was clearly demonstrated that the design of rotating arc roots was advantageous for high quality uniform deposition of large area diamond films. Theoretical predictions on growth rate and film quality as well as their radial uniformity, and the influence of process parameters on large area diamond deposition were discussed in detail based on the spatial distribution of atomic hydrogen and the carbonaceous species in the plasma over the substrate surface obtained from thermodynamic calculations of plasma chemistry, and were compared with experimental observations.

The influence of surface chemistry and topography on the contact guidance of MG63 osteoblast cells.

PubMed

Ismail, F S Magdon; Rohanizadeh, R; Atwa, S; Mason, R S; Ruys, A J; Martin, P J; Bendavid, A

2007-05-01

The purpose of the present study was to determine in vitro the effects of different surface topographies and chemistries of commercially pure titanium (cpTi) and diamond-like carbon (DLC) surfaces on osteoblast growth and attachment. Microgrooves (widths of 2, 4, 8 and 10 microm and a depth of 1.5-2 microm) were patterned onto silicon (Si) substrates using microlithography and reactive ion etching. The Si substrates were subsequently vapor coated with either cpTi or DLC coatings. All surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Using the MG63 Osteoblast-Like cell line, we determined cell viability, adhesion, and morphology on different substrates over a 3 day culture period. The results showed cpTi surfaces to be significantly more hydrophilic than DLC for groove sizes larger than 2 microm. Cell contact guidance was observed for all grooved samples in comparison to the unpatterned controls. The cell viability tests indicated a significantly greater cell number for 8 and 10 microm grooves on cpTi surfaces compared to other groove sizes. The cell adhesion study showed that the smaller groove sizes, as well as the unpatterned control groups, displayed better cell adhesion to the substrate.

Chemically active colloids near osmotic-responsive walls with surface-chemistry gradients

NASA Astrophysics Data System (ADS)

Popescu, M. N.; Uspal, W. E.; Dietrich, S.

2017-04-01

Chemically active colloids move by creating gradients in the composition of the surrounding solution and by exploiting the differences in their interactions with the various molecular species in solution. If such particles move near boundaries, e.g. the walls of the container confining the suspension, gradients in the composition of the solution are also created along the wall. This give rise to chemi-osmosis (via the interactions of the wall with the molecular species forming the solution), which drives flows coupling back to the colloid and thus influences its motility. Employing an approximate ‘point-particle’ analysis, we show analytically that—owing to this kind of induced active response (chemi-osmosis) of the wall—such chemically active colloids can align with, and follow, gradients in the surface chemistry of the wall. In this sense, these artificial ‘swimmers’ exhibit a primitive form of thigmotaxis with the meaning of sensing the proximity of a (not necessarily discontinuous) physical change in the environment. We show that the alignment with the surface-chemistry gradient is generic for chemically active colloids as long as they exhibit motility in an unbounded fluid, i.e. this phenomenon does not depend on the exact details of the propulsion mechanism. The results are discussed in the context of simple models of chemical activity, corresponding to Janus particles with ‘source’ chemical reactions on one half of the surface and either ‘inert’ or ‘sink’ reactions over the other half.

Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Shigaki, H.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

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

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

PubMed

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

2017-06-01

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

Electrofluidic gating of a chemically reactive surface.

PubMed

Jiang, Zhijun; Stein, Derek

2010-06-01

We consider the influence of an electric field applied normal to the electric double layer at a chemically reactive surface. Our goal is to elucidate how surface chemistry affects the potential for field-effect control over micro- and nanofluidic systems, which we call electrofluidic gating. The charging of a metal-oxide-electrolyte (MOE) capacitor is first modeled analytically. We apply the Poisson-Boltzmann description of the double layer and impose chemical equilibrium between the ionizable surface groups and the solution at the solid-liquid interface. The chemically reactive surface is predicted to behave as a buffer, regulating the charge in the double layer by either protonating or deprotonating in response to the applied field. We present the dependence of the charge density and the electrochemical potential of the double layer on the applied field, the density, and the dissociation constants of ionizable surface groups and the ionic strength and the pH of the electrolyte. We simulate the responses of SiO(2) and Al(2)O(3), two widely used oxide insulators with different surface chemistries. We also consider the limits to electrofluidic gating imposed by the nonlinear behavior of the double layer and the dielectric strength of oxide materials, which were measured for SiO(2) and Al(2)O(3) films in MOE configurations. Our results clarify the response of chemically reactive surfaces to applied fields, which is crucial to understanding electrofluidic effects in real devices.

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.

Influence of Natural Convection and Thermal Radiation Multi-Component Transport in MOCVD Reactors

NASA Technical Reports Server (NTRS)

Lowry, S.; Krishnan, A.; Clark, I.

1999-01-01

The influence of Grashof and Reynolds number in Metal Organic Chemical Vapor (MOCVD) reactors is being investigated under a combined empirical/numerical study. As part of that research, the deposition of Indium Phosphide in an MOCVD reactor is modeled using the computational code CFD-ACE. The model includes the effects of convection, conduction, and radiation as well as multi-component diffusion and multi-step surface/gas phase chemistry. The results of the prediction are compared with experimental data for a commercial reactor and analyzed with respect to the model accuracy.

The Impacts of Urbanization on Meteorology and Air Quality in the Los Angeles Basin

NASA Astrophysics Data System (ADS)

Li, Y.; Zhang, J.; Sailor, D.; Ban-Weiss, G. A.

2017-12-01

Urbanization has a profound influence on regional meteorology in mega cities like Los Angeles. This influence is driven by changes in land surface physical properties and urban processes, and their corresponding influence on surface-atmosphere coupling. Changes in meteorology from urbanization in turn influences air quality through weather-dependent chemical reaction, pollutant dispersion, etc. Hence, a real-world representation of the urban land surface properties and urban processes should be accurately resolved in regional climate-chemistry models for better understanding the role of urbanization on changing urban meteorology and associated pollutant dynamics. By incorporating high-resolution land surface data, previous research has improved model-observation comparisons of meteorology in urban areas including the Los Angeles basin, and indicated that historical urbanization has increased urban temperatures and altered wind flows significantly. However, the impact of urban expansion on air quality has been less studied. Thus, in this study, we aim to evaluate the effectiveness of resolving high-resolution heterogeneity in urban land surface properties and processes for regional weather and pollutant concentration predictions. We coupled the Weather Research and Forecasting model with Chemistry to the single-layer Urban Canopy Model to simulate a typical summer period in year 2012 for Southern California. Land cover type and urban fraction were determined from National Land Cover Data. MODIS observations were used to determine satellite-derived albedo, green vegetation fraction, and leaf area index. Urban morphology was determined from GIS datasets of 3D building geometries. An urban irrigation scheme was also implemented in the model. Our results show that the improved model captures the diurnal cycle of 2m air temperature (T2) and Ozone (O3) concentrations. However, it tends to overestimate wind speed and underestimate T2, which leads to an underestimation of O3 and fine particulate matter concentrations. By comparing simulations assuming current land cover of the Los Angeles basin versus pre-urbanization land cover, we find that land cover change through urbanization has led to important shifts in regional air pollution via the aforementioned physical and chemical mechanisms.

Real-time and post-plasma studies of influence of low levels of tungsten on carbon erosion and surface evolution behaviour in D2 plasma

NASA Astrophysics Data System (ADS)

Weilnboeck, F.; Fox-Lyon, N.; Oehrlein, G. S.; Doerner, R. P.

2010-02-01

A profound influence of monolayer tungsten coverage of hard carbon films on the evolution of carbon surface erosion behaviour, surface chemistry and morphology in D2 plasma has been established by real-time ellipsometry, x-ray photoelectron spectroscopy and atomic force microscopy measurements. The erosion of tungsten-covered carbon showed two distinct stages of plasma material interactions: rapid tungsten removal during the initial erosion period and steady-state amorphous carbon removal accompanied by large-scale surface roughness development. The initial removal of tungsten takes place at a rate that significantly exceeds typical sputter yields at the ion energies used here and is attributed to elimination of weakly bonded tungsten from the surface. The tungsten remaining on the a-C : H film surface causes surface roughness development of the eroding carbon surface by a masking effect, and simultaneously leads to a seven fold reduction of the steady-state carbon erosion rate for long plasma surface interaction times (~100 s). Results presented are of direct relevance for material transport and re-deposition, and the interaction of those films with plasma in the divertor region and on mirror surfaces of fusion devices.

Influence of intermittent water releases on groundwater chemistry at the lower reaches of the Tarim River, China.

PubMed

Chen, Yong-jin; Chen, Ya-ning; Liu, Jia-zhen; Zhang, Er-xun

2009-11-01

Based on the data of the depths and the chemical properties of groundwater, salinity in the soil profile, and the basic information on each delivery of water collected from the years 2000 to 2006, the varied character of groundwater chemistry and related factors were studied. The results confirmed the three stages of the variations in groundwater chemistry influenced by the intermittent water deliveries. The factors that had close relations to the variations in groundwater chemistry were the distances of monitoring wells from the water channel, the depths of the groundwater, water flux in watercourse, and the salinities in soils. The relations between chemical variation and groundwater depths indicated that the water quality was the best with the groundwater varying from 5 to 6 m. In addition, the constructive species in the study area can survive well with the depth of groundwater varying from 5 to 6 m, so the rational depth of groundwater in the lower reaches of the Tarim River should be 5 m or so. The redistribution of salts in the soil profile and its relations to the chemical properties and depths of groundwater revealed the linear water delivery at present combining with surface water supply in proper sections would promote water quality optimized and speed up the pace of ecological restoration in the study area.

Surface chemistry of InP ridge structures etched in Cl{sub 2}-based plasma analyzed with angular XPS

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

Bouchoule, Sophie, E-mail: sophie.bouchoule@lpn.cnrs.fr; Cambril, Edmond; Guilet, Stephane

2015-09-15

Two x-ray photoelectron spectroscopy configurations are proposed to analyze the surface chemistry of micron-scale InP ridge structures etched in chlorine-based inductively coupled plasma (ICP). Either a classical or a grazing configuration allows to retrieve information about the surface chemistry of the bottom surface and sidewalls of the etched features. The procedure is used to study the stoichiometry of the etched surface as a function of ridge aspect ratio for Cl{sub 2}/Ar and Cl{sub 2}/H{sub 2} plasma chemistries. The results show that the bottom surface and the etched sidewalls are P-rich, and indicate that the P-enrichment mechanism is rather chemically driven.more » Results also evidence that adding H{sub 2} to Cl{sub 2} does not necessarily leads to a more balanced surface stoichiometry. This is in contrast with recent experimental results obtained with the HBr ICP chemistry for which fairly stoichiometric surfaces have been obtained.« less

Headwater Influences on Downstream Water Quality

PubMed Central

Oakes, Robert M.

2007-01-01

We investigated the influence of riparian and whole watershed land use as a function of stream size on surface water chemistry and assessed regional variation in these relationships. Sixty-eight watersheds in four level III U.S. EPA ecoregions in eastern Kansas were selected as study sites. Riparian land cover and watershed land use were quantified for the entire watershed, and by Strahler order. Multiple regression analyses using riparian land cover classifications as independent variables explained among-site variation in water chemistry parameters, particularly total nitrogen (41%), nitrate (61%), and total phosphorus (63%) concentrations. Whole watershed land use explained slightly less variance, but riparian and whole watershed land use were so tightly correlated that it was difficult to separate their effects. Water chemistry parameters sampled in downstream reaches were most closely correlated with riparian land cover adjacent to the smallest (first-order) streams of watersheds or land use in the entire watershed, with riparian zones immediately upstream of sampling sites offering less explanatory power as stream size increased. Interestingly, headwater effects were evident even at times when these small streams were unlikely to be flowing. Relationships were similar among ecoregions, indicating that land use characteristics were most responsible for water quality variation among watersheds. These findings suggest that nonpoint pollution control strategies should consider the influence of small upland streams and protection of downstream riparian zones alone is not sufficient to protect water quality. PMID:17999108

Impact of surface chemistry

PubMed Central

Somorjai, Gabor A.; Li, Yimin

2011-01-01

The applications of molecular surface chemistry in heterogeneous catalyst technology, semiconductor-based technology, medical technology, anticorrosion and lubricant technology, and nanotechnology are highlighted in this perspective. The evolution of surface chemistry at the molecular level is reviewed, and the key roles of surface instrumentation developments for in situ studies of the gas–solid, liquid–solid, and solid–solid interfaces under reaction conditions are emphasized. PMID:20880833

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

Climate Impacts on Tropospheric Ozone and Hydroxyl

NASA Technical Reports Server (NTRS)

Shindell, Drew T.; Bell, N.; Faluvegi, G.

2003-01-01

Climate change may influence tropospheric ozone and OH via several main pathways: (1) altering chemistry via temperature and humidity changes, (2) changing ozone and precursor sources via surface emissions, stratosphere-troposphere exchange, and light- ning, and (3) affecting trace gas sinks via the hydrological cycle and dry deposition. We report results from a set of coupled chemistry-climate model simulations designed to systematically study these effects. We compare the various effects with one another and with past and projected future changes in anthropogenic and natural emissions of ozone precursors. We find that white the overall impact of climate on ozone is probably small compared to emission changes, some significant seasonal and regional effects are apparent. The global effect on hydroxyl is quite large, however, similar in size to the effect of emission changes. Additionally, we show that many of the chemistry-climate links that are not yet adequately modeled are potentially important.

Kinetics of dodecanoic acid adsorption from caustic solution by activated carbon.

PubMed

Pendleton, Phillip; Wu, Sophie Hua

2003-10-15

This study examines the influences of adsorbent porosity and surface chemistry and of carbon dosage on dodecanoic acid adsorption kinetics from aqueous and 2 M NaOH solutions as batch adsorption processes. Both adsorbents are steam-activated carbons prepared from either coconut or coal precursors. Prior to use the adsorbents were washed in deionized water or 2 M NaOH. Mass transfer coefficients and effective overall diffusion coefficients indicate a minor contribution from adsorbent porosity. In contrast, high surface oxygen content impedes transport to and into the adsorbent structure. Carbon dosage shows a proportional increase in transport coefficients with increasing mass; these coefficients are constant when normalized per unit mass. Neither water nor NaOH treatment of the adsorbents has a significant influence on dodecanoic acid adsorption kinetics. Molecular and Knudsen diffusion coefficients are defined to demonstrate that the overall effective diffusion coefficient values and the diffusion process are controlled by surface diffusion.

The influence of an extensive dust event on snow chemistry in the southern Rocky Mountains

Treesearch

Charles Rhoades; Kelly Elder; E. Greene

2010-01-01

In mid-February 2006, windstorms in Arizona, Utah, and western Colorado generated a dust cloud that distributed a layer of dust across the surface of the snowpack throughout much of the Colorado Rockies; it remained visible throughout the winter. We compared the chemical composition of snowfall and snowpack collected during and after the dust deposition event with pre-...

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.

Student academic achievement in college chemistry

NASA Astrophysics Data System (ADS)

Tabibzadeh, Kiana S.

General Chemistry is required for variety of baccalaureate degrees, including all medical related fields, engineering, and science majors. Depending on the institution, the prerequisite requirement for college level General Chemistry varies. The success rate for this course is low. The purpose of this study is to examine the factors influencing student academic achievement and retention in General Chemistry at the college level. In this study student achievement is defined by those students who earned grades of "C" or better. The dissertation contains in-depth studies on influence of Intermediate Algebra as a prerequisite compared to Fundamental Chemistry for student academic achievement and student retention in college General Chemistry. In addition the study examined the extent and manner in which student self-efficacy influences student academic achievement in college level General Chemistry. The sample for this part of the study is 144 students enrolled in first semester college level General Chemistry. Student surveys determined student self-efficacy level. The statistical analyses of study demonstrated that Fundamental Chemistry is a better prerequisite for student academic achievement and student retention. The study also found that student self-efficacy has no influence on student academic achievement. The significance of this study will be to provide data for the purpose of establishing a uniform and most suitable prerequisite for college level General Chemistry. Finally the variables identified to influence student academic achievement and enhance student retention will support educators' mission to maximize the students' ability to complete their educational goal at institutions of higher education.

Influence of three-dimensional hyaluronic acid microenvironments on mesenchymal stem cell chondrogenesis.

PubMed

Chung, Cindy; Burdick, Jason A

2009-02-01

Mesenchymal stem cells (MSCs) are multipotent progenitor cells whose plasticity and self-renewal capacity have generated significant interest for applications in tissue engineering. The objective of this study was to investigate MSC chondrogenesis in photo-cross-linked hyaluronic acid (HA) hydrogels. Because HA is a native component of cartilage, and MSCs may interact with HA via cell surface receptors, these hydrogels could influence stem cell differentiation. In vitro and in vivo cultures of MSC-laden HA hydrogels permitted chondrogenesis, measured by the early gene expression and production of cartilage-specific matrix proteins. For in vivo culture, MSCs were encapsulated with and without transforming growth factor beta-3 (TGF-beta3) or pre-cultured for 2 weeks in chondrogenic medium before implantation. Up-regulation of type II collagen, aggrecan, and sox 9 was observed for all groups over MSCs at the time of encapsulation, and the addition of TGF-beta3 further enhanced the expression of these genes. To assess the influence of scaffold chemistry on chondrogenesis, HA hydrogels were compared with relatively inert poly(ethylene glycol) (PEG) hydrogels and showed enhanced expression of cartilage-specific markers. Differences between HA and PEG hydrogels in vivo were most noticeable for MSCs and polymer alone, indicating that hydrogel chemistry influences the commitment of MSCs to undergo chondrogenesis (e.g., approximately 43-fold up-regulation of type II collagen of MSCs in HA over PEG hydrogels). Although this study investigated only early markers of tissue regeneration, these results emphasize the importance of material cues in MSC differentiation microenvironments, potentially through interactions between scaffold materials and cell surface receptors.

Tuning Wettability and Adhesion of Structured Surfaces

NASA Astrophysics Data System (ADS)

Badge, Ila

Structured surfaces with feature size ranging from a few micrometers down to nanometers are of great interest in the applications such as design of anti-wetting surfaces, tissue engineering, microfluidics, filtration, microelectronic devices, anti-reflective coatings and reversible adhesives. A specific surface property demands particular roughness geometry along with suitable surface chemistry. Plasma Enhanced Chemical Vapor Deposition (PECVD) is a technique that offers control over surface chemistry without significantly affecting the roughness and thus, provides a flexibility to alter surface chemistry selectively for a given structured surface. In this study, we have used PECVD to fine tune wetting and adhesion properties. The research presented focuses on material design aspects as well as the fundamental understanding of wetting and adhesion phenomena of structured surfaces. In order to study the effect of surface roughness and surface chemistry on the surface wettability independently, we developed a model surface by combination of colloidal lithography and PECVD. A systematically controlled hierarchical roughness using spherical colloidal particles and surface chemistry allowed for quantitative prediction of contact angles corresponding to metastable and stable wetting states. A well-defined roughness and chemical composition of the surface enabled establishing a correlation between theory predictions and experimental measurements. We developed an extremely robust superhydrophobic surface based on Carbon-Nanotubes (CNT) mats. The surface of CNTs forming a nano-porous mesh was modified using PECVD to deposit a layer of hydrophobic coating (PCNT). The PCNT surface thus formed is superhydrophobic with almost zero contact angle hysteresis. We demonstrated that the PCNT surface is not wetted under steam condensation even after prolonged exposure and also continues to retain its superhydrophobicity after multiple frosting-defrosting cycles. The anti-wetting behavior of PCNT surface is consistent with our model predictions, derived based on thermodynamic theory of wetting. The surface of gecko feet is a very unique natural structured surface. The hierarchical surface structure of a Gecko toe pad is responsible for its reversible adhesive properties and superhydrophobicity. van der Waals interactions is known to be the key mechanism behind Gecko adhesion. However, we found that the wettability, thus the surface chemistry plays a significant role in Gecko adhesion mechanism, especially in the case of underwater adhesion. We used PECVD process to deposit a layer of coating with known chemistry on the surface of sheds of gecko toes to study the effect that wettability of the toe surface has on its adhesion. In summary, we demonstrated that PECVD can be effectively used as means of surface chemistry control for tunable structure-property relationship of three types of structured surfaces; each having unique surface features.

Dynamic development of the protein corona on silica nanoparticles: composition and role in toxicity

NASA Astrophysics Data System (ADS)

Mortensen, Ninell P.; Hurst, Gregory B.; Wang, Wei; Foster, Carmen M.; Nallathamby, Prakash D.; Retterer, Scott T.

2013-06-01

The formation and composition of the protein corona on silica (SiO2) nanoparticles (NP) with different surface chemistries was evaluated over time. Native SiO2, amine (-NH2) and carboxy (-COO-) modified NP were examined following incubation in mammalian growth media containing fetal bovine serum (FBS) for 1, 4, 24 and 48 hours. The protein corona transition from its early dynamic state to the later more stable corona was evaluated using mass spectrometry. The NP diameter was 22.4 +/- 2.2 nm measured by scanning transmission electron microscopy (STEM). Changes in hydrodynamic diameter and agglomeration kinetics were studied using dynamic light scattering (DLS). The initial surface chemistry of the NP played an important role in the development and final composition of the protein corona, impacting agglomeration kinetics and NP toxicity. Particle toxicity, indicated by changes in membrane integrity and mitochondrial activity, was measured by lactate dehydrogenase (LDH) release and tetrazolium reduction (MTT), respectively, in mouse alveolar macrophages (RAW264.7) and mouse lung epithelial cells (C10). SiO2-COO- NP had a slower agglomeration rate, formed smaller aggregates, and exhibited lower cytotoxicity compared to SiO2 and SiO2-NH2. Composition of the protein corona for each of the three NP was unique, indicating a strong dependence of corona development on NP surface chemistry. This work underscores the need to understand all aspects of NP toxicity, particularly the influence of agglomeration on effective dose and particle size. Furthermore, the interplay between materials and local biological environment is emphasized and highlights the need to conduct toxicity profiling under physiologically relevant conditions that provide an appropriate estimation of material modifications that occur during exposure in natural environments.The formation and composition of the protein corona on silica (SiO2) nanoparticles (NP) with different surface chemistries was evaluated over time. Native SiO2, amine (-NH2) and carboxy (-COO-) modified NP were examined following incubation in mammalian growth media containing fetal bovine serum (FBS) for 1, 4, 24 and 48 hours. The protein corona transition from its early dynamic state to the later more stable corona was evaluated using mass spectrometry. The NP diameter was 22.4 +/- 2.2 nm measured by scanning transmission electron microscopy (STEM). Changes in hydrodynamic diameter and agglomeration kinetics were studied using dynamic light scattering (DLS). The initial surface chemistry of the NP played an important role in the development and final composition of the protein corona, impacting agglomeration kinetics and NP toxicity. Particle toxicity, indicated by changes in membrane integrity and mitochondrial activity, was measured by lactate dehydrogenase (LDH) release and tetrazolium reduction (MTT), respectively, in mouse alveolar macrophages (RAW264.7) and mouse lung epithelial cells (C10). SiO2-COO- NP had a slower agglomeration rate, formed smaller aggregates, and exhibited lower cytotoxicity compared to SiO2 and SiO2-NH2. Composition of the protein corona for each of the three NP was unique, indicating a strong dependence of corona development on NP surface chemistry. This work underscores the need to understand all aspects of NP toxicity, particularly the influence of agglomeration on effective dose and particle size. Furthermore, the interplay between materials and local biological environment is emphasized and highlights the need to conduct toxicity profiling under physiologically relevant conditions that provide an appropriate estimation of material modifications that occur during exposure in natural environments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33280b

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

Filtration Efficiency of Functionalized Ceramic Foam Filters for Aluminum Melt Filtration

NASA Astrophysics Data System (ADS)

Voigt, Claudia; Jäckel, Eva; Taina, Fabio; Zienert, Tilo; Salomon, Anton; Wolf, Gotthard; Aneziris, Christos G.; Le Brun, Pierre

2017-02-01

The influence of filter surface chemistry on the filtration efficiency of cast aluminum alloys was evaluated for four different filter coating compositions (Al2O3—alumina, MgAl2O4—spinel, 3Al2O3·2SiO2—mullite, and TiO2—rutile). The tests were conducted on a laboratory scale with a filtration pilot plant, which facilitates long-term filtration tests (40 to 76 minutes). This test set-up allows the simultaneous use of two LiMCAs (before and after the filter) for the determination of the efficiency of inclusion removal. The four tested filter surface chemistries exhibited good thermal stability and mechanical robustness after 750 kg of molten aluminum had been cast. All four filter types exhibited a mean filtration efficiency of at least 80 pct. However, differences were also observed. The highest filtration efficiencies were obtained with alumina- and spinel-coated filter surfaces (>90 pct), and the complete removal of the largest inclusions (>90 µm) was observed. The efficiency was slightly lower with mullite- and rutile-coated filter surfaces, in particular for large inclusions. These observations are discussed in relation to the properties of the filters, in particular in terms of, for example, the surface roughness.

Influence of surface oxides on the adsorption of naphthalene onto multiwalled carbon nanotubes.

PubMed

Cho, Hyun-Hee; Smith, Billy A; Wnuk, Joshua D; Fairbrother, D Howard; Ball, William P

2008-04-15

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs.

A study of the factors affecting the attitudes of young female students toward chemistry at the high school level

NASA Astrophysics Data System (ADS)

Banya, Santonino K.

Chemistry is a human endeavor that relies on basic human qualities like creativity, insights, reasoning, and skills. It depends on habits of the mind: skepticism, tolerance of ambiguity, openness to new ideas, intellectual honesty, curiosity, and communication. Young female students begin studying chemistry curiosity; however, when unconvinced, they become skeptical. Researches focused on gender studies have indicated that attitudes toward science education differ between males and females. A declining interest in chemistry and the under representation of females in the chemical science was found (Jacobs, 2000). This study investigated whether self-confidence toward chemistry, the influence of role models, and knowledge about the usefulness of chemistry were affecting the attitudes toward chemistry, of 183 high school young females across the United States. The young female students surveyed, had studied chemistry for at least one year prior to participating in the study during the fall semester of 2003. The schools were randomly selected represented diverse economic backgrounds and geographical locations. Data were obtained using Chemistry Attitude Influencing Factors (CAIF) instrument and from interviews with a focus group of three young female students about the effect of self-confidence toward chemistry, the influence of role models, and knowledge about the usefulness of chemistry on their decision to study chemistry. The CAIF instrument consisted of a 12-items self-confidence questionnaire (ConfiS), 12-items each of the influence of role models (RoMoS) and knowledge about usefulness of chemistry (US) questionnaire. ConfiS was adopted (with permission) from CAEQ (Coll & Dalgety, 2001), and both RoMoS and US were modified from TOSRA (Fraser, 1978), public domain document. The three young female students interviewed, gave detailed responses about their opinions regarding self-confidence toward chemistry, the influence of role models, and knowledge about the usefulness of chemistry on their attitudes toward the study of chemistry. Both quantitative (a Likert-type Scale questionnaire) and qualitative (open-ended questions) items were used to investigate the views of young female students. Results of the survey were analysed using a correlation test. Significant differences were found in the Likert-type scale scores, providing evidences supporting literature that suggests, self-confidence toward chemistry, the influence of role models, and knowledge about the usefulness of chemistry affect the decision of young female students about the study of chemistry. Interview responses corroborated the results from the survey. Strategies for addressing the problems and recommendations for further studies have been suggested.

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.

Inorganic Nanoparticle Induced Morphological Transition for Confined Self-Assembly of Block Copolymers within Emulsion Droplets.

PubMed

Zhang, Yan; He, Yun; Yan, Nan; Zhu, Yutian; Hu, Yuexin

2017-09-07

Recently, it has been reported that the incorporation of functional inorganic nanoparticles (NPs) into the three-dimensional (3D) confined self-assembly of block copolymers (BCPs) creates the unique nanostructured hybrid composites, which can not only introduce new functions to BCPs but also induce some interesting morphological transitions of BCPs. In the current study, we systematically investigate the cooperative self-assembly of a series of size-controlled and surface chemistry-tunable gold nanoparticles (AuNPs) and polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer within the emulsion droplets. The influences of the size, content, and surface chemistry of the AuNPs on the coassembled nanostructures as well as the spatial distribution of AuNPs in the hybrid particles are examined. It is found that the size and content of the AuNPs are related to the entropic interaction, while the surface chemistry of AuNPs is related to the enthalpic interaction, which can be utilized to tailor the self-assembled morphologies of block copolymer confined in the emulsion droplets. As the content of PS-coated AuNPs increases, the morphology of the resulting AuNPs/PS-b-P2VP hybrid particles changes from the pupa-like particles to the bud-like particles and then to the onion-like particles. However, a unique morphological transition from the pupa-like particles to the mushroom-like particles is observed as the content of P4VP-coated AuNPs increases. More interestingly, it is observed that the large AuNPs are expelled to the surface of the BCP particles to reduce the loss in the conformational entropy of the block segment, which can arrange into the strings of necklaces on the surfaces of the hybrid particles.

Physicochemical controls on absorbed water film thickness in unsaturated geological media

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

Tokunaga, T.

2011-06-14

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here, the problem of adsorbed water film thickness is examined through combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses, and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable, and showed that pendular ringsmore » within drained porous media retain most of the 'residual' water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (< 10 mol m{sup -3}) on surfaces with higher magnitude electrostatic potentials (more negative than - 50 mV). Adsorbed water films are predicted to usually range in thickness from 1 to 20 nm in drained pores and fractures of unsaturated environments.« less

Physicochemical controls on adsorbed water film thickness in unsaturated geological media

NASA Astrophysics Data System (ADS)

Tokunaga, Tetsu K.

2011-08-01

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here the problem of adsorbed water film thickness is examined by combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable and showed that pendular rings within drained porous media retain most of the "residual" water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double-layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double-layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (<10 mol m-3) on surfaces with higher-magnitude electrostatic potentials (more negative than ≈-50 mV). Adsorbed water films are predicted to usually range in thickness from ≈1 to 20 nm in drained pores and fractures of unsaturated environments.

Impact of finite rate chemistry on the hydrodynamic stability of shear flows in turbulent lean premixed combustion

NASA Astrophysics Data System (ADS)

Dagan, Yuval; Ghoniem, Ahmed

2017-11-01

Recent experimental observations show that the dynamic response of a reactive flow is strongly impacted by the fuel chemistry. In order to gain insight into some of the underlying mechanisms we formulate a new linear stability model that incorporates the impact of finite rate chemistry on the hydrodynamic stability of shear flows. Contrary to previous studies which typically assume that the velocity field is independent of the kinetic rates, the velocity field in our study is coupled with the temperature field. Using this formulation, we reproduce previous results, e.g., most unstable global modes, obtained for non-reacting shear flow. Moreover, we show that these modes are significantly altered in frequency and gain by the presence of a reaction region within the shear layer. This qualitatively agrees with results of our recent experimental and numerical studies, which show that the flame surface location relative to the shear layer influences the stability characteristics in combustion tunnels. This study suggests a physical explanation for the observed impact of finite rate chemistry on shear flow stability.

Nano-scaling law: geometric foundation of thiolated gold nanomolecules.

PubMed

Dass, Amala

2012-04-07

Thiolated gold nanomolecules show a power correlation between the number of gold atoms and the thiolate ligands with a 2/3 scaling similar to Platonic and Archimedean solids. Nanomolecule stability is influenced by a universal geometric factor that is foundational to its stability through the Euclidean surface rule, in addition to the electronic shell closing factor and staple motif requirements. This journal is © The Royal Society of Chemistry 2012

Multiscale Simulations of ALD in Cross Flow Reactors

DOE PAGES

Yanguas-Gil, Angel; Libera, Joseph A.; Elam, Jeffrey W.

2014-08-13

In this study, we have developed a multiscale simulation code that allows us to study the impact of surface chemistry on the coating of large area substrates with high surface area/high aspect-ratio features. Our code, based on open-source libraries, takes advantage of the ALD surface chemistry to achieve an extremely efficient two-way coupling between reactor and feature length scales, and it can provide simulated quartz crystal microbalance and mass spectrometry data at any point of the reactor. By combining experimental surface characterization with simple analysis of growth profiles in a tubular cross flow reactor, we are able to extract amore » minimal set of reactions to effectively model the surface chemistry, including the presence of spurious CVD, to evaluate the impact of surface chemistry on the coating of large, high surface area substrates.« less

A force sensor using nanowire arrays to understand biofilm formation (Conference Presentation)

NASA Astrophysics Data System (ADS)

Sahoo, Prasana K.; Cavalli, Alessandro; Pelegati, Vitor B.; Murillo, Duber M.; Souza, Alessandra A.; Cesar, Carlos L.; Bakkers, Erik P. A. M.; Cotta, Monica A.

2016-03-01

Understanding the cellular signaling and function at the nano-bio interface can pave the way towards developing next-generation smart diagnostic tools. From this perspective, limited reports detail so far the cellular and subcellular forces exerted by bacterial cells during the interaction with abiotic materials. Nanowire arrays with high aspect ratio have been used to detect such small forces. In this regard, live force measurements were performed ex-vivo during the interaction of Xylella fastidiosa bacterial cells with InP nanowire arrays. The influence of nanowire array topography and surface chemistry on the response and motion of bacterial cells was studied in detail. The nanowire arrays were also functionalized with different cell adhesive promoters, such as amines and XadA1, an afimbrial protein of X.fastidiosa. By employing the well-defined InP nanowire arrays platform, and single cell confocal imaging system, we were able to trace the bacterial growth pattern, and show that their initial attachment locations are strongly influenced by the surface chemistry and nanoscale surface topography. In addition, we measure the cellular forces down to few nanonewton range using these nanowire arrays. In case of nanowire functionalized with XadA1, the force exerted by vertically and horizontally attached single bacteria on the nanowire is in average 14% and 26% higher than for the pristine array, respectively. These results provide an excellent basis for live-cell force measurements as well as unravel the range of forces involved during the early stages of bacterial adhesion and biofilm formation.

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.

Is Nitrogen Deposition Altering the Nitrogen Status of Northeastern Forests?

NASA Astrophysics Data System (ADS)

Aber, J. D.; Goodale, C. L.; Ollinger, S. V.; Smith, M.; Magill, A. H.; Martin, M. E.; Hallett, R. A.; Stoddard, J. L.; Participants, N.

2002-05-01

The nitrogen saturation hypothesis suggests that foliar and soil N concentration, nitrification rate, and nitrate leaching loss should all increase in response to increased N deposition. We tested this hypothesis with a major new synthesis of foliar (362 plots), soil (251 plots), and surface water (354 lakes and streams) chemistry from the northeastern U.S. Nitrogen deposition decreases across the Northeast from ~ 10-12 kg ha-1 yr-1 in the Mid-Atlantic region to ~ 4 kg ha-1 yr-1 in northern Maine. Foliar chemistry (%N and lignin:N ratio) of red spruce and sugar maple correlated more strongly with elevation than with N deposition, although these factors covary. Forest floor C:N ratio decreased with N deposition for both conifers and hardwoods although correlations were not strong (R2 < 0.20). Regardless of forest type or soil horizon, percent nitrification (as a fraction of N mineralization) increased as soil C:N decreased below ~25, and increased weakly with N deposition in hardwood stands. Across the Northeast, surface water seasonal nitrate concentrations and N export during the mid- to late-1990s increased with N deposition (R2 = 0.30-0.56), with two important patterns emerging: 1) nitrate rarely exceeded 1 μ mol/L in watersheds receiving <8-10 kg ha-1 yr-1; and 2) high nitrate concentrations occurred only in lakes and streams receiving relatively high N inputs. This pattern resembles that for European forests. Factors such as species composition, forest history, climate, and hydrology may affect foliar, soil, and stream chemistry at different spatial and temporal scales. Foliar and soil chemistry may be more strongly influenced by local heterogeneity, whereas surface water samples integrate over much larger areas. Using surface waters as the most comprehensive indicator of N saturation, it appears that N deposition is altering the N status of forests in the northeastern U.S.

Physicochemical modifications accompanying UV laser induced surface structures on poly(ethylene terephthalate) and their effect on adhesion of mesenchymal cells.

PubMed

Rebollar, Esther; Pérez, Susana; Hernández, Margarita; Domingo, Concepción; Martín, Margarita; Ezquerra, Tiberio A; García-Ruiz, Josefa P; Castillejo, Marta

2014-09-07

This work reports on the formation of different types of structures on the surface of polymer films upon UV laser irradiation. Poly(ethylene terephthalate) was irradiated with nanosecond UV pulses at 193 and 266 nm. The polarization of the laser beam and the irradiation angle of incidence were varied, giving rise to laser induced surface structures with different shapes and periodicities. The irradiated surfaces were topographically characterized by atomic force microscopy and the chemical modifications induced by laser irradiation were inspected via micro-Raman and fluorescence spectroscopies. Contact angle measurements were performed with different liquids, and the results evaluated in terms of surface free energy components. Finally, in order to test the influence of surface properties for a potential application, the modified surfaces were used for mesenchymal stem cell culture assays and the effect of nanostructure and surface chemistry on cell adhesion was evaluated.

Surface energy of talc and chlorite: Comparison between electronegativity calculation and immersion results.

PubMed

Douillard, Jean-Marc; Salles, Fabrice; Henry, Marc; Malandrini, Harold; Clauss, Frédéric

2007-01-15

The surface energies of talc and chlorite is computed using a simple model, which uses the calculation of the electrostatic energy of the crystal. It is necessary to calculate the atomic charges. We have chosen to follow Henry's model of determination of partial charges using scales of electronegativity and hardness. The results are in correct agreement with a determination of the surface energy obtained from an analysis of the heat of immersion data. Both results indicate that the surface energy of talc is lower than the surface energy of chlorite, in agreement with observed behavior of wettability. The influence of Al and Fe on this phenomenon is discussed. Surface energy of this type of solids seems to depend more strongly on the geometry of the crystal than on the type of atoms pointing out of the surface; i.e., the surface energy depends more on the physics of the system than on its chemistry.

A fundamental review of the friction and wear behavior of ceramics

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1972-01-01

The basic concepts associated with the friction and wear of materials are discussed as they relate to ceramics. Properties of ceramics such as crystal structure, crystallographic orientation, mechanical deformation, and surface chemistry are reviewed as they influence friction and wear. Both adhesive and abrasive wear of ceramics are discussed. The friction and wear of ceramics are examined in contact with themselves and when in contact with metals. The influences of environmental constituents such as water and hydrocarbons on friction and wear are reviewed. Materials discussed, by way of example, include aluminum oxide, rutile, calcium fluoride, and lithium fluoride.

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

PubMed Central

Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

2014-01-01

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70–90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties. PMID:25323067

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

NASA Astrophysics Data System (ADS)

Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

2014-10-01

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

Surface chemical properties of eutectic and frozen NaCl solutions probed by XPS and NEXAFS.

PubMed

Křepelová, Adéla; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

2010-12-17

We study the surface of sodium chloride-water mixtures above, at, and below the eutectic temperature using X-ray photoelectron spectroscopy (XPS) and electron-yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NaCl frozen solutions are mimicking sea-salt deposits in ice or snow. Sea-salt particles emitted from the oceans are a major contributor to the global aerosol burden and can act as a catalyst for heterogeneous chemistry or as cloud condensation nuclei. The nature of halogen ions at ice surfaces and their influence on surface melting of ice are of significant current interest. We found that the surface of the frozen solution, depending on the temperature, consists of ice and different NaCl phases, that is, NaCl, NaCl·2H(2)O, and surface-adsorbed water.

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

Rajachidambaram, Meena Suhanya; Pandey, Archana; Vilayur Ganapathy, Subramanian

The role of back channel surface chemistry on amorphous zinc tin oxide (ZTO) bottom gate thin film transistors (TFT) have been characterized by positive bias-stress measurements and x-ray photoelectron spectroscopy. Positive bias-stress turn-on voltage shifts for ZTO-TFTs were significantly reduced by passivation of back channel surfaces with self-assembled monolayers of n-hexylphosphonic acid (n-HPA) when compared to ZTO-TFTs with no passivation. These results indicate that adsorption of molecular species on exposed back channel of ZTO-TFTs strongly influence observed turn-on voltage shifts, as opposed to charge injection into the dielectric or trapping due to oxygen vacancies.

Predictive model for ice formation on superhydrophobic surfaces.

PubMed

Bahadur, Vaibhav; Mishchenko, Lidiya; Hatton, Benjamin; Taylor, J Ashley; Aizenberg, Joanna; Krupenkin, Tom

2011-12-06

The prevention and control of ice accumulation has important applications in aviation, building construction, and energy conversion devices. One area of active research concerns the use of superhydrophobic surfaces for preventing ice formation. The present work develops a physics-based modeling framework to predict ice formation on cooled superhydrophobic surfaces resulting from the impact of supercooled water droplets. This modeling approach analyzes the multiple phenomena influencing ice formation on superhydrophobic surfaces through the development of submodels describing droplet impact dynamics, heat transfer, and heterogeneous ice nucleation. These models are then integrated together to achieve a comprehensive understanding of ice formation upon impact of liquid droplets at freezing conditions. The accuracy of this model is validated by its successful prediction of the experimental findings that demonstrate that superhydrophobic surfaces can fully prevent the freezing of impacting water droplets down to surface temperatures of as low as -20 to -25 °C. The model can be used to study the influence of surface morphology, surface chemistry, and fluid and thermal properties on dynamic ice formation and identify parameters critical to achieving icephobic surfaces. The framework of the present work is the first detailed modeling tool developed for the design and analysis of surfaces for various ice prevention/reduction strategies. © 2011 American Chemical Society

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

Nanometer-scale water- and proton-diffusion heterogeneities across water channels in polymer electrolyte membranes.

PubMed

Song, Jinsuk; Han, Oc Hee; Han, Songi

2015-03-16

Nafion, the most widely used polymer for electrolyte membranes (PEMs) in fuel cells, consists of a fluorocarbon backbone and acidic groups that, upon hydration, swell to form percolated channels through which water and ions diffuse. Although the effects of the channel structures and the acidic groups on water/ion transport have been studied before, the surface chemistry or the spatially heterogeneous diffusivity across water channels has never been shown to directly influence water/ion transport. By the use of molecular spin probes that are selectively partitioned into heterogeneous regions of the PEM and Overhauser dynamic nuclear polarization relaxometry, this study reveals that both water and proton diffusivity are significantly faster near the fluorocarbon and the acidic groups lining the water channels than within the water channels. The concept that surface chemistry at the (sub)nanometer scale dictates water and proton diffusivity invokes a new design principle for PEMs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

How does Interactive Chemistry Influence the Representation of Stratosphere-Troposphere Coupling in a Climate Model?

NASA Astrophysics Data System (ADS)

Haase, S.; Matthes, K. B.

2017-12-01

Changes in stratospheric ozone can trigger tropospheric circulation changes. In the Southern hemisphere (SH), the observed shift of the Southern Annular Mode was attributed to the observed trend in lower stratospheric ozone. In the Northern Hemisphere (NH), a recent study showed that extremely low stratospheric ozone conditions during spring produce robust anomalies in the troposphere (zonal wind, temperature and precipitation). This could only be reproduced in a coupled chemistry climate model indicating that chemical-dynamical feedbacks are also important on the NH. To further investigate the importance of interactive chemistry for surface climate, we conducted a set of experiments using NCAR's Community Earth System Model (CESM1) with the Whole Atmosphere Community Climate Model (WACCM) as the atmosphere component. WACCM contains a fully interactive stratospheric chemistry module in its standard configuration. It also allows for an alternative configuration, referred to as SC-WACCM, in which the chemistry (O3, NO, O, O2, CO2 and chemical and shortwave heating rates) is specified as a 2D field in the radiation code. A comparison of the interactive vs. the specified chemistry version enables us to evaluate the relative importance of interactive chemistry by systematically inhibiting the feedbacks between chemistry and dynamics. To diminish the effect of temporal interpolation when prescribing ozone, we use daily resolved zonal mean ozone fields for the specified chemistry run. Here, we investigate the differences in stratosphere-troposphere coupling between the interactive and specified chemistry simulations for the mainly chemically driven SH as well as for the mainly dynamically driven NH. We will especially consider years that are characterized by extremely low stratospheric ozone on the one hand and by large dynamical disturbances, i.e. Sudden Stratospheric Warmings, on the other hand.

Weathering of a carbon nanotube/epoxy nanocomposite under UV light and in water bath: impact on abraded particles

NASA Astrophysics Data System (ADS)

Schlagenhauf, Lukas; Kianfar, Bahareh; Buerki-Thurnherr, Tina; Kuo, Yu-Ying; Wichser, Adrian; Nüesch, Frank; Wick, Peter; Wang, Jing

2015-11-01

Weathering processes can influence the surface properties of composites with incorporated nanoparticles. These changes may affect the release behavior of nanoparticles when an abrasion process is applied. Therefore, the influence of two different weathering processes, immersion in water and exposure to UV light, on the properties of abraded particles from a carbon nanotube (CNT)/epoxy nanocomposite was investigated. The investigation included the measurement of the weathering impact on the surface chemistry of the exposed samples, the particle size of abraded particles, the quantity of exposed CNTs in the respirable part of the abraded particles, and the toxicity of abraded particles, measured by in vitro toxicity tests using the THP-1 monocyte-derived macrophages. The results showed that weathering by immersion in water had no influence on the properties of abraded particles. The exposure to UV light caused a degradation of the epoxy on the surface, followed by delamination of an approx. 2.5 μm thick layer. An increased quantity of exposed CNTs in abraded particles was not found; on the contrary, longer UV exposure times decreased the released fraction of CNTs from 0.6% to 0.4%. The toxicity tests revealed that abraded particles from the nanocomposites did not induce additional acute cytotoxic effects compared to particles from the neat epoxy.Weathering processes can influence the surface properties of composites with incorporated nanoparticles. These changes may affect the release behavior of nanoparticles when an abrasion process is applied. Therefore, the influence of two different weathering processes, immersion in water and exposure to UV light, on the properties of abraded particles from a carbon nanotube (CNT)/epoxy nanocomposite was investigated. The investigation included the measurement of the weathering impact on the surface chemistry of the exposed samples, the particle size of abraded particles, the quantity of exposed CNTs in the respirable part of the abraded particles, and the toxicity of abraded particles, measured by in vitro toxicity tests using the THP-1 monocyte-derived macrophages. The results showed that weathering by immersion in water had no influence on the properties of abraded particles. The exposure to UV light caused a degradation of the epoxy on the surface, followed by delamination of an approx. 2.5 μm thick layer. An increased quantity of exposed CNTs in abraded particles was not found; on the contrary, longer UV exposure times decreased the released fraction of CNTs from 0.6% to 0.4%. The toxicity tests revealed that abraded particles from the nanocomposites did not induce additional acute cytotoxic effects compared to particles from the neat epoxy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05387k

Planning, Implementation, and Scientific Goals of the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) Field Missions

NASA Technical Reports Server (NTRS)

Toon, Owen B.; Maring, Hal; Dibb, Jack; Ferrare, Richard A.; Jacob, Daniel J.; Jensen, Eric J.; Luo, Z. Johnny; Mace, Gerald G.; Pan, Laura L.; Pfister, Leonhard;

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

2017-02-17

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry, but are challenging to probe experimentally with atomic-scale understanding. Here we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO surface is more reactive toward water, forming hydroxyl species andmore » adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight into the design of catalyst materials.« less

Future Effects of Southern Hemisphere Stratospheric Zonal Asymmetries on Climate

NASA Astrophysics Data System (ADS)

Stone, K.; Solomon, S.; Kinnison, D. E.; Fyfe, J. C.

2017-12-01

Stratospheric zonal asymmetries in the Southern Hemisphere have been shown to have significant influences on both stratospheric and tropospheric dynamics and climate. Accurate representation of stratospheric ozone in particular is important for realistic simulation of the polar vortex strength and temperature trends. This is therefore also important for stratospheric ozone change's effect on the troposphere, both through modulation of the Southern Annular Mode (SAM), and more localized climate. Here, we characterization the impact of future changes in Southern Hemisphere zonal asymmetry on tropospheric climate, including changes to future tropospheric temperature, and precipitation. The separate impacts of increasing GHGs and ozone recovery on the zonal asymmetric influence on the surface are also investigated. For this purpose, we use a variety of models, including Chemistry Climate Model Initiative simulations from the Community Earth System Model, version 1, with the Whole Atmosphere Community Climate Model (CESM1(WACCM)) and the Australian Community Climate and Earth System Simulator-Chemistry Climate Model (ACCESS-CCM). These models have interactive chemistry and can therefore more accurately represent the zonally asymmetric nature of the stratosphere. The CESM1(WACCM) and ACCESS-CCM models are also compared to simulations from the Canadian Can2ESM model and CESM-Large Ensemble Project (LENS) that have prescribed ozone to further investigate the importance of simulating stratospheric zonal asymmetry.

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.

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters.

PubMed

Yin, Yongguang; Yang, Xiaoya; Zhou, Xiaoxia; Wang, Weidong; Yu, Sujuan; Liu, Jingfu; Jiang, Guibin

2015-08-01

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV-visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV-visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca(2+) and Mg(2+)) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments. Copyright © 2015. Published by Elsevier B.V.

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

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less

Heterogeneous nucleation and growth of nanoparticles at environmental interfaces

DOE PAGES

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

2016-08-11

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less

Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

PubMed

Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W

2016-09-20

Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.

Efforts to control radiation build-up in Ringhals

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

Egner, K.; Aronsson, P.O.; Erixon, O.

1995-03-01

It is well known that good control of the primary chemistry in a PWR is essential in order to minimize material problems and fuel damages. It has also been well established that the water chemistry has a great influence on accumulation of corrosion products on the fuel and the radiation build-up on primary system surfaces. Ringhals was one of the pioneers to increase operating pH in order to reduce radiation build-up and has now been operating for ten years with pH at 7.4 or (in later years) 7.2. Our experience is favourable and includes low radiation levels in the newmore » (1989) steam generators of Ringhals 2. Ringhals 4 has operated almost its whole life at pH 7.2 or higher and it remains one of the cleanest PWRs of its vintage. In addition to strict adherence to a stable operating chemistry, Ringhals is now working on a program with the aim to find optimum shut-down and start-up chemistry to reduce activity levels in the primary systems. A particular goal is to use the shut-down and start-up chemistry at the 1994 outage in Ringhals 3 in order to reduce doserates in preparation for the planned steam generator replacement in 1995. The paper summarizes the experience to date of the established operating chemistry, on-going tests with modified shut-down and start-up chemistry and other measures to limit or reduce the activity build-up.« less

Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

PubMed

Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

2018-03-07

Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Discovering Factors that Influence the Decision to Pursue a Chemistry-Related Career: A Comparative Analysis of the Experiences of Non Scientist Adults and Chemistry Teachers in Greece

ERIC Educational Resources Information Center

Salta, Katerina; Gekos, Michael; Petsimeri, Irene; Koulougliotis, Dionysios

2012-01-01

This study aims at identifying factors that influence students' choice not to pursue a chemistry-related career by analyzing the experiences of secondary education chemistry teachers in Greece and of Greek adults who have not pursued studies related to science. Data collection was done with the method of individual structured interviews. The…

Chemistry, the Terminal Science? The Impact of the High School Science Order on the Development of U.S. Chemistry Education

ERIC Educational Resources Information Center

Sheppard, Keith; Robbins, Dennis M.

2006-01-01

This is a follow-up to a previous article about the historical development of the biology-chemistry-physics order of science courses in U.S. high schools. The ideas and influences behind the development of the order and some of the original arguments about the grade placement of chemistry are presented. The influence of a leading chemistry…

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.

Urban-Related Environmental Variables and Their Relation with Patterns in Biological Community Structure in the Fountain Creek Basin, Colorado, 2003-2005

USGS Publications Warehouse

Zuellig, Robert E.; Bruce, James F.; Evans, Erin E.; Stogner, Sr., Robert W.

2007-01-01

In 2003, the U.S. Geological Survey, in cooperation with Colorado Springs City Engineering, began a study to evaluate the influence of urbanization on stream ecosystems. To accomplish this task, invertebrate, fish, stream discharge, habitat, water-chemistry, and land-use data were collected from 13 sites in the Fountain Creek basin from 2003 to 2005. The Hydrologic Index Tool was used to calculate hydrologic indices known to be related to urbanization. Response of stream hydrology to urbanization was evident among hydrologic variables that described stormflow. These indices included one measurement of high-flow magnitude, two measurements of high-flow frequency, and one measurement of stream flashiness. Habitat and selected nonstormflow water chemistry were characterized at each site. Land-use data were converted to estimates of impervious surface cover and used as the measure of urbanization annually. Correlation analysis (Spearman?s rho) was used to identify a suite of nonredundant streamflow, habitat, and water-chemistry variables that were strongly associated (rho > 0.6) with impervious surface cover but not strongly related to elevation (rho < 0.60). An exploratory multivariate analysis (BIO-ENV, PRIMER ver 6.1, Plymouth, UK) was used to create subsets of eight urban-related environmental variables that described patterns in biological community structure. The strongest and most parsimonious subset of variables describing patterns in invertebrate community structure included high flood pulse count, lower bank capacity, and nutrients. Several other combinations of environmental variables resulted in competing subsets, but these subsets always included the three variables found in the most parsimonious list. This study found that patterns in invertebrate community structure from 2003 to 2005 in the Fountain Creek basin were associated with a variety of environmental characteristics influenced by urbanization. These patterns were explained by a combination of hydrologic, habitat, and water-chemistry variables. Fish community structure showed weaker links between urban-related environmental variables and biological patterns. A conceptual model was developed that showed the influence of urban-related environmental variables and their relation to fish and invertebrate assemblages. This model should prove helpful in guiding future studies on the impacts of urbanization on aquatic systems. Long-term monitoring efforts may be needed in other drainages along the Front Range of Colorado to link urban-related variables to aquatic communities in transition zone streams.

Chemical studies of elements with Z ⩾ 104 in gas phase

NASA Astrophysics Data System (ADS)

Türler, Andreas; Eichler, Robert; Yakushev, Alexander

2015-12-01

Chemical investigations of superheavy elements in the gas-phase, i.e. elements with Z ≥ 104, allow assessing the influence of relativistic effects on their chemical properties. Furthermore, for some superheavy elements and their compounds quite unique gas-phase chemical properties were predicted. The experimental verification of these properties yields supporting evidence for a firm assignment of the atomic number. Prominent examples are the high volatility observed for HsO4 or the very weak interaction of Cn with gold surfaces. The unique properties of HsO4 were exploited to discover the doubly-magic even-even nucleus 270Hs and the new isotope 271Hs. The combination of kinematic pre-separation and gas-phase chemistry allowed gaining access to a new class of relatively fragile compounds, the carbonyl complexes of elements Sg through Mt. A not yet resolved issue concerns the interaction of Fl with gold surfaces. While competing experiments agree on the fact that Fl is a volatile element, there are discrepancies concerning its adsorption on gold surfaces with respect to its daughter Cn. The elucidation of these and other questions amounts to the fascination that gas-phase chemical investigations exert on current research at the extreme limits of chemistry today.

Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

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

Roldin, P.; Eriksson, A. C.; Nordin, E. Z.

2014-08-11

We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3)more » and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.« less

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

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.

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

The Influence of Web-Based Chemistry Learning on Students' Perceptions, Attitudes, and Achievements

ERIC Educational Resources Information Center

Frailich, Marcel; Kesner, Miri; Hofstein, Avi

2007-01-01

The goal of this study was to investigate whether integrating a website into chemistry teaching influences 10th-grade students' perceptions of the classroom learning environment, their attitudes regarding the relevance of chemistry, and their understanding of the concept of chemical bonding. Two groups participated in this study: an experimental…

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.

Plasma protein adsorption to zwitterionic poly (carboxybetaine methacrylate) modified surfaces: chain chemistry and end-group effects on protein adsorption kinetics, adsorbed amounts and immunoblots.

PubMed

Abraham, Sinoj; Bahniuk, Markian S; Unsworth, Larry D

2012-12-01

Protein-surface interactions are crucial to the overall biocompatability of biomaterials, and are thought to be the impetus towards the adverse host responses such as blood coagulation and complement activation. Only a few studies hint at the ultra-low fouling potential of zwitterionic poly(carboxybetaine methacrylate) (PCBMA) grafted surfaces and, of those, very few systematically investigate their non-fouling behavior. In this work, single protein adsorption studies as well as protein adsorption from complex solutions (i.e. human plasma) were used to evaluate the non-fouling potential of PCBMA grafted silica wafers prepared by nitroxide-mediated free radical polymerization. PCBMAs used for surface grafting varied in charge separating spacer groups that influence the overall surface charges, and chain end-groups that influence the overall hydrophilicity, thereby, allows a better understanding of these effects towards the protein adsorption for these materials. In situ ellipsometry was used to quantify the adsorbed layer thickness and adsorption kinetics for the adsorption of four proteins from single protein buffer solutions, viz, lysozyme, α-lactalbumin, human serum albumin and fibrinogen. Total amount of protein adsorbed on surfaces differed as a function of surface properties and protein characteristics. Finally, immunoblots results showed that human plasma protein adsorption to these surfaces resulted, primarily, in the adsorption of human serum albumin, with total protein adsorbed amounts being the lowest for PCBMA-3 (TEMPO). It was apparent that surface charge and chain hydrophilicity directly influenced protein adsorption behavior of PCBMA systems and are promising materials for biomedical applications.

Reduced Gas Cycling in Microbial Mats: Implications for Early Earth

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Bebout, Brad M.; DesMarais, David J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

For more than half the history of life on Earth, biological productivity was dominated by photosynthetic microbial mats. During this time, mats served as the preeminent biological influence on earth's surface and atmospheric chemistry and also as the primary crucible for microbial evolution. We find that modern analogs of these ancient mat communities generate substantial quantities of hydrogen, carbon monoxide, and methane. Escape of these gases from the biosphere would contribute strongly to atmospheric evolution and potentially to the net oxidation of earth's surface; sequestration within the biosphere carries equally important implications for the structure, function, and evolution of anaerobic microbial communities within the context of mat biology.

Turbulent Mixing Chemistry in Disks

NASA Astrophysics Data System (ADS)

Semenov, D.; Wiebe, D.

2006-11-01

A gas-grain chemical model with surface reaction and 1D/2D turbulent mixing is available for protoplanetary disks and molecular clouds. Current version is based on the updated UMIST'95 database with gas-grain interactions (accretion, desorption, photoevaporation, etc.) and modified rate equation approach to surface chemistry (see also abstract for the static chemistry code).

The role of chemistry and pH of solid surfaces for specific adsorption of biomolecules in solution--accurate computational models and experiment.

PubMed

Heinz, Hendrik

2014-06-18

Adsorption of biomolecules and polymers to inorganic nanostructures plays a major role in the design of novel materials and therapeutics. The behavior of flexible molecules on solid surfaces at a scale of 1-1000 nm remains difficult and expensive to monitor using current laboratory techniques, while playing a critical role in energy conversion and composite materials as well as in understanding the origin of diseases. Approaches to implement key surface features and pH in molecular models of solids are explained, and distinct mechanisms of peptide recognition on metal nanostructures, silica and apatite surfaces in solution are described as illustrative examples. The influence of surface energies, specific surface features and protonation states on the structure of aqueous interfaces and selective biomolecular adsorption is found to be critical, comparable to the well-known influence of the charge state and pH of proteins and surfactants on their conformations and assembly. The representation of such details in molecular models according to experimental data and available chemical knowledge enables accurate simulations of unknown complex interfaces in atomic resolution in quantitative agreement with independent experimental measurements. In this context, the benefits of a uniform force field for all material classes and of a mineral surface structure database are discussed.

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.

An examination of past and present influences on university chemistry education

NASA Astrophysics Data System (ADS)

Soliman, William Atef

This study examined the historical influences that have contributed to past and present-day university level chemistry education. The study was organized into three sections: First, by analyzing the academic genealogy, education origins of prominent chemists, Nobel Prize winners in chemistry and scientific patents awarded by countries; the major historical contributors to chemical education during the 19th century were identified; Secondly, by analyzing the educational backgrounds of current chemistry professors (n=12,120) in 407 universities in 40 countries around the world and six chemical education indicators for 25 countries; and finally the relationship, if any, between a country's chemical, biotechnology, defense, and petroleum industries to its level of chemistry education was investigated utilizing a multiple regression analysis between the monetary value of the industries and the extent of chemical education within each country. The findings indicated that the U.S., Britain, Germany, and France were major influencers of 19th century chemical education while the major present-day influencers of university chemical education are the U.S., Germany, Britain, France, Italy, and Japan. Pearson correlation coefficients indicated that the value of the chemical industry for a country was significantly related to (a) the number of chemistry doctorates awarded (p=.05), (b) chemistry Nobel awards (p=.001), (c) the number of chemistry publications (p=.001), and (d) prominence of the country in the chemical literature (p=.05). Multiple regression analysis indicated that the value of the biotechnology industry was significantly related to the number of Nobel awards (p=.007) and the number of chemistry publications (p=.001). The value of the defense industry was significantly related to chemistry doctorates (p=.002), chemistry Nobel awards (p=.001), the number of chemistry publications (p=.001), and prominence in the literature (p=.001). The value of the petroleum industry was not significantly related to any education variables. The findings suggest that university chemical education is influenced by a select group of countries and that chemical, biotechnology, and defense industry values are significantly related to the level of a country's chemical education. These findings may be valuable to those interested in the industrial and societal applications of chemical education.

Geochemical Analyses of Surface and Shallow Gas Flux and Composition Over a Proposed Carbon Sequestration Site in Eastern Kentucky

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

Thomas Parris; Michael Solis; Kathryn Takacs

2009-12-31

Using soil gas chemistry to detect leakage from underground reservoirs (i.e. microseepage) requires that the natural range of soil gas flux and chemistry be fully characterized. To meet this need, soil gas flux (CO{sub 2}, CH{sub 4}) and the bulk (CO{sub 2}, CH{sub 4}) and isotopic chemistry ({delta}{sup 13}C-CO2) of shallow soil gases (<1 m, 3.3 ft) were measured at 25 locations distributed among two active oil and gas fields, an active strip mine, and a relatively undisturbed research forest in eastern Kentucky. The measurements apportion the biologic, atmospheric, and geologic influences on soil gas composition under varying degrees ofmore » human surface disturbance. The measurements also highlight potential challenges in using soil gas chemistry as a monitoring tool where the surface cover consists of reclaimed mine land or is underlain by shallow coals. For example, enrichment of ({delta}{sup 13}C-CO2) and high CH{sub 4} concentrations in soils have been historically used as indicators of microseepage, but in the reclaimed mine lands similar soil chemistry characteristics likely result from dissolution of carbonate cement in siliciclastic clasts having {delta}{sup 13}C values close to 0{per_thousand} and degassing of coal fragments. The gases accumulate in the reclaimed mine land soils because intense compaction reduces soil permeability, thereby impeding equilibration with the atmosphere. Consequently, the reclaimed mine lands provide a false microseepage anomaly. Further potential challenges arise from low permeability zones associated with compacted soils in reclaimed mine lands and shallow coals in undisturbed areas that might impede upward gas migration. To investigate the effect of these materials on gas migration and composition, four 10 m (33 ft) deep monitoring wells were drilled in reclaimed mine material and in undisturbed soils with and without coals. The wells, configured with sampling zones at discrete intervals, show the persistence of some of the aforementioned anomalies at depth. Moreover, high CO{sub 2} concentrations associated with coals in the vadose zone suggest a strong affinity for adsorbing CO{sub 2}. Overall, the low permeability of reclaimed mine lands and coals and CO2 adsorption by the latter is likely to reduce the ability of surface geochemistry tools to detect a microseepage signal.« less

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)

Inquiry Teaching in High School Chemistry Classrooms: The Role of Knowledge and Beliefs

NASA Astrophysics Data System (ADS)

Roehrig, Gillian H.; Luft, Julie A.

2004-10-01

"Science as inquiry" is a key content standard in the National Science Education Standards, yet implementation of inquiry-based teaching is rare in secondary chemistry classrooms. This paper is the result of a study conducted to understand factors that effect the inquiry-based instruction of ten novice secondary chemistry teachers. The study focused on the influence of teaching beliefs and content knowledge on the instructional practices of these ten teachers. Case and cross-case comparisons revealed that chemistry teachers' intentions to implement inquiry teaching were strongly influenced by their teaching beliefs rather than their knowledge of chemistry. The quality of inquiry lessons, however, was found to depend on the teachers' knowledge of chemistry content. This study reinforces the need for chemistry-focused inservice training for beginning chemistry teachers that focuses on both inquiry teaching strategies and teaching beliefs.

A functionalized poly(ethylene glycol)-based bioassay surface chemistry that facilitates bio-immobilization and inhibits non-specific protein, bacterial, and mammalian cell adhesion

PubMed Central

Harbers, Gregory M.; Emoto, Kazunori; Greef, Charles; Metzger, Steven W.; Woodward, Heather N.; Mascali, James J.; Grainger, David W.; Lochhead, Michael J.

2008-01-01

This paper describes a new bioassay surface chemistry that effectively inhibits non-specific biomolecular and cell binding interactions, while providing a capacity for specific immobilization of desired biomolecules. Poly(ethylene glycol) (PEG) as the primary component in nonfouling film chemistry is well-established, but the multicomponent formulation described here is unique in that it (1) is applied in a single, reproducible, solution-based coating step; (2) can be applied to diverse substrate materials without the use of special primers; and (3) is readily functionalized to provide specific attachment chemistries. Surface analysis data are presented, detailing surface roughness, polymer film thickness, and film chemistry. Protein non-specific binding assays demonstrate significant inhibition of serum, fibrinogen, and lysozyme adsorption to coated glass, indium tin oxide, and tissue culture polystyrene dishes. Inhibition of S. aureus and K. pneumoniae microbial adhesion in a microfluidic flow cell, and inhibition of fibroblast cell adhesion from serum-based cell culture is shown. Effective functionalization of the coating is demonstrated by directing fibroblast adhesion to polymer surfaces activated with an RGD peptide. Batch-to-batch reproducibility data are included. The in situ cross-linked PEG-based coating chemistry is unique in its formulation, and its surface properties are attractive for a broad range of in vitro bioassay applications. PMID:18815622

Influence of ammonia and carbon dioxide on the sorption of a basic organic pollutant to carpet and latex-painted gypsum board.

PubMed

Ongwandee, Maneerat; Morrison, Glenn C

2008-08-01

Sorptive interactions with indoor surfaces strongly influence indoor exposure to organic pollutants. Adsorption itself may be influenced by indoor levels of common indoor gases such as CO2, NH3, and H2O. We quantified sorption characteristics of trimethylamine (TMA) on carpet and painted wallboard, while challenging the surface with gas-phase CO2, NH3 and H2O. We show that the capacity of the carpet to sorb TMA, doubles when the CO2 mixing ratio is increased from 0 to 1000 ppm CO2 at 90% relative humidity. In contrast, NH3 decreases the surface capacity of both carpet and latex paint. Sorption of TMA to these indoor materials is primarily caused by interactions at one or more interfaces. Dissolution of TMA and aqueous acid-base chemistry appear to also contribute to the overall sorptive capacity of carpet at high relative humidity. The reduction in the distribution coefficient, k(e), in the presence of NH3 is explained by competition between TMA and NH3 molecules for sites on the substrates at low-to-medium relative humidity conditions.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces.

PubMed

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

2014-01-01

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

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

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

Wilmsmeyer, Amanda R.; Morris, John R.; Gordon, Wesley O.

2014-01-15

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

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.

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.

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.

Photochemical oxidant processes in the presence of dust: An evaluation of the impact of dust on particulate nitrate and ozone formation

NASA Technical Reports Server (NTRS)

Zhang, Yang; Sunwoo, Young; Kotamarthi, Veerabhadra; Carmichael, Gregory R.

1994-01-01

The influence of dust on the tropospheric photochemical oxidant cycle is studied through the use of a detailed coupled aerosol and gas-phase chemistry model. Dust is a significant component of the troposphere throughout Asia and provides a surface for a variety of heterogeneous reactions. Dust is found to be an important surface for particulate nitrate formation. For dust loading and ambient concentrations representative of conditions in East Asia, particulate nitrate levels of 1.5-11.5 micrograms/cubic meter are predicted, consistent with measured levels in this region. Dust is also found to reduce NO(x) levels by up to 50%, HO2 concentrations by 20%-80%, and ozone production rates by up to 25%. The magnitude of the influence of dust is sensitive to mass concentration of the aerosol, relative humidity, and the value of the accommodation coefficient.

Surface changes of biopolymers PHB and PLLA induced by Ar+ plasma treatment and wet etching

NASA Astrophysics Data System (ADS)

Slepičková Kasálková, N.; Slepička, P.; Sajdl, P.; Švorčík, V.

2014-08-01

Polymers, especially group of biopolymers find potential application in a wide range of disciplines due to their biodegradability. In biomedical applications these materials can be used as a scaffold or matrix. In this work, the influence of the Ar+ plasma treatment and subsequent wet etching (acetone/water) on the surface properties of polymers were studied. Two biopolymers - polyhydroxybutyrate with 8% polyhydroxyvalerate (PHB) and poly-L-lactic acid (PLLA) were used in these experiments. Modified surface layers were analyzed by different methods. Surface wettability was characterized by determination of water contact angle. Changes in elemental composition of modified surfaces were performed by X-ray Photoelectron Spectroscopy (XPS). Surface morphology and roughness was examined using Atomic Force Microscopy (AFM). Gravimetry method was used to study the mass loss. It was found that the modification from both with plasma and wet etching leads to dramatic changes of surface properties (surface chemistry, morphology and roughness). Rate of changes of these features strongly depends on the modification parameters.

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.

The influence of surface chemistry and size of nanoscale graphene oxide on photothermal therapy of cancer using ultra-low laser power.

PubMed

Yang, Kai; Wan, Jianmei; Zhang, Shuai; Tian, Bo; Zhang, Youjiu; Liu, Zhuang

2012-03-01

Photothermal therapy as a physical treatment approach to destruct cancer has emerged as an alternative of currently used cancer therapies. Previously we have shown that polyethylene glycol (PEG) functionalized nano-graphene oxide (nGO-PEG) with strong optical absorption in the near-infrared (NIR) region was a powerful photothermal agent for in vivo cancer treatment. In this work, by using ultra-small reduced graphene oxide (nRGO) with non-covalent PEG coating, we study how sizes and surface chemistry affect the in vivo behaviors of graphene, and remarkably improve the performance of graphene-based in vivo photothermal cancer treatment. Owing to the enhanced NIR absorbance and highly efficient tumor passive targeting of nRGO-PEG, excellent in vivo treatment efficacy with 100% of tumor elimination is observed after intravenous injection of nRGO-PEG and the followed 808 nm laser irradiation, the power density (0.15 W/cm(2), 5 min) of which is an order of magnitude lower than that usually applied for in vivo tumor ablation using many other nanomaterials. All mice after treatment survive over a period of 100 days without a single death or any obvious sign of side effect. Our results highlight that both surface chemistry and sizes are critical to the in vivo performance of graphene, and show the promise of using optimized nano-graphene for ultra-effective photothermal treatment, which may potentially be combined with other therapeutic approaches to assist our fight against cancer. Copyright © 2011 Elsevier Ltd. All rights reserved.

Impact of Asian Dust on Global Surface Air Quality and Radiation Budget

NASA Technical Reports Server (NTRS)

Chin, Mian; Diehl, Thomas; Yu, Hongbin; Ginoux, Paul

2006-01-01

Dust originating from Asian deserts and desertification areas can be transported regionally and globally to affect surface air quality, visibility, and radiation budget not only at immediate downwind locations (e.g., eastern Asia) but also regions far away from the sources (e.g., North America). Deposition of Asian dust to the North Pacific Ocean basin influences the ocean productivity. In this study, we will use the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model, remote sensing data form satellite and from the ground-based network, and in-situ data from aircraft and surface observations to address the following questions: - What are the effects of Asian dust on the surface air quality and visibility over Asia and North America? - What are the seasonal and spatial variations of dust deposition to the North Pacific Ocean? How does the Asian dust affect surface radiation budget?

Laser surface texturing of polymers for biomedical applications

NASA Astrophysics Data System (ADS)

Riveiro, Antonio; Maçon, Anthony L. B.; del Val, Jesus; Comesaña, Rafael; Pou, Juan

2018-02-01

Polymers are materials widely used in biomedical science because of their biocompatibility, and good mechanical properties (which, in some cases, are similar to those of human tissues); however, these materials are, in general, chemically and biologically inert. Surface characteristics, such as topography (at the macro-, micro, and nanoscale), surface chemistry, surface energy, charge or wettability are interrelated properties, and they cooperatively influence the biological performance of materials when used for biomedical applications. They regulate the biological response at the implant/tissue interface (e.g., influencing the cell adhesion, cell orientation, cell motility, etc.). Several surface processing techniques have been explored to modulate these properties for biomedical applications. Despite their potentials, these methods have limitations that prevent their applicability. In this regard, laser-based methods, in particular laser surface texturing (LST), can be an interesting alternative. Different works have showed the potentiality of this technique to control the surface properties of biomedical polymers and enhance their biological performance; however, more research is needed to obtain the desired biological response. This work provides a general overview of the basics and applications of LST for the surface modification of polymers currently used in the clinical practice (e.g. PEEK, UHMWPE, PP, etc.). The modification of roughness, wettability, and their impact on the biological response is addressed to offer new insights on the surface modification of biomedical polymers.

Lights, Camera, Reaction! The Influence of Interfacial Chemistry on Nanoparticle Photoreactivity

NASA Astrophysics Data System (ADS)

Farner Budarz, Jeffrey Michael

The ability of photocatalytic nanoparticles (NPs) to produce reactive oxygen species (ROS) has inspired research into several new applications and technologies, including water purification, contaminant remediation, and self-cleaning surface coatings. As a result, NPs continue to be incorporated into a wide variety of increasingly complex products. With the increased use of NPs and nano-enabled products and their subsequent disposal, NPs will make their way into the environment. Currently, many unanswered questions remain concerning how changes to the NP surface chemistry that occur in natural waters will impact reactivity. This work seeks to investigate potential influences on photoreactivity - specifically the impact of functionalization, the influence of anions, and interactions with biological objects - so that ROS generation in natural aquatic environments may be better understood. To this aim, titanium dioxide nanoparticles (TiO2) and fullerene nanoparticles (FNPs) were studied in terms of their reactive endpoints: ROS generation measured through the use of fluorescent or spectroscopic probe compounds, virus and bacterial inactivation, and contaminant degradation. Physical characterization of NPs included light scattering, electron microscopy and electrophoretic mobility. These systematic investigations into the effect of functionalization, sorption, and aggregation on NP aggregate structure, size, and reactivity improve our understanding of trends that impact nanoparticle reactivity. Engineered functionalization of FNPs was shown to impact NP aggregation, ROS generation, and viral affinity. Fullerene cage derivatization can lead to a greater affinity for the aqueous phase, smaller mean aggregate size, and a more open aggregate structure, favoring greater rates of ROS production. At the same time however, fullerene derivatization also decreases the 1O2 quantum yield and may either increase or decrease the affinity for a biological surface. These results suggest that the biological impact of fullerenes will be influenced by changes in the type of surface functionalization and extent of cage derivatization, potentially increasing the ROS generation rate and facilitating closer association with biological targets. Investigations into anion sorption onto the surface of TiO2 indicate that reactivity will be strongly influenced by the waters they are introduced into. The type and concentration of anion impacted both aggregate state and reactivity to varying degrees. Specific interactions due to inner sphere ligand exchange with phosphate and carbonate have been shown to stabilize NPs. As a result, waters containing chloride or nitrate may have little impact on inherent reactivity but will reduce NP transport via aggregation, while waters containing even low levels of phosphate and carbonate may decrease "acute" reactivity but stabilize NPs such that their lifetime in the water column is increased. Finally, ROS delivery in a multicomponent system was studied under the paradigm of pesticide degradation. The presence of bacteria or chlorpyrifos in solution significantly decreased bulk ROS measurements, with almost no •OH detected when both were present. However, the presence of bacteria had no observable impact on the rate of chlorpyrifos degradation, nor chlorpyrifos on bacterial inactivation. These results imply that investigating reactivity in simplified systems may significantly over or underestimate photocatalytic efficiency in realistic environments, depending on the surface affinity of a given target. This dissertation demonstrates that the reactivity of a system is largely determined by NP surface chemistry. Altering the NP surface, either intentionally or incidentally, produces significant changes in reactivity and aggregate characteristics. Additionally, the photocatalytic impact of the ROS generated by a NP depends on the characteristics of potential targets as well as on the characteristics of the NP itself. These are complicating factors, and the myriad potential exposure conditions, endpoints, and environmental systems to be considered for even a single NP highlight the need for functional assays that employ environmentally relevant conditions if risk assessments for engineered NPs are to be made in a timely fashion so as not to be outpaced by, or impede, technological advances.

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

PubMed

Rao, Archana N; Grainger, David W

2014-04-01

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

BIOPHYSICAL PROPERTIES OF NUCLEIC ACIDS AT SURFACES RELEVANT TO MICROARRAY PERFORMANCE

PubMed Central

Rao, Archana N.; Grainger, David W.

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

Garrod, Robin

2015-08-01

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

Carbon nanotube-poly(methyl methacrylate) hybrid films: preparation using diazonium salt chemistry and mechanical properties.

PubMed

Mammeri, Fayna; Teyssandier, Joan; Darche-Dugaret, Clément; Debacker, Sabine; Le Bourhis, Eric; Chehimi, Mohamed Mehdi

2014-11-01

The poor miscibility of carbon nanotubes (CNTs) in common organic solvents and organic monomers requires their modification by suitable functional (reactive or not) groups prior to their incorporation in thermoplastic polymers. Dispersion behavior of carbon nanotubes and mechanical properties of various CNT-poly(methylmethacrylate) (PMMA) nanocomposites were investigated. We studied the influence of the surface chemistry through the use of diazonium salts as an elegant and environmentally friendly platform to provide a suitable sidewall functionalization by methyl methacrylate functions. We used either a molecular size functional group through the grafting of methacryloxypropyltrimethoxysilane or a macromolecular size one, consisting in PMMA brushes grown by SI-ATRP in order to study the influence of the length of methacrylate function on the dispersion of CNT in PMMA. The hardness and the elastic indentation modulus of all hybrid films were obtained through nanoindentation measurements and found to increase, using ATRP-modified CNTs, suggesting a better dispersion of CNTs in PMMA due to optimal inorganic-organic interactions promoted by the short chains of PMMA. Copyright © 2014 Elsevier Inc. All rights reserved.

Fogwater Chemistry and Air Quality in the Texas-Louisiana Gulf Coast Corridor

NASA Astrophysics Data System (ADS)

Kommalapati, R. R.; Raja, S.; Ravikrishna, R.; Murugesan, K.; Collett, J. L.; Valsaraj, K.

2007-05-01

The presence of fog water in polluted atmosphere can influence atmospheric chemistry and air quality. The study of interactions between fog water and atmospheric gases and aerosols are very important in understanding the atmospheric fate of the pollutants. In this Study several air samples and fogwater samples were collected in the heavily industrialized area of Gulf Coast corridor( Houston, TX and Baton Rouge, LA). A total of 32 fogwater samples were collected, comprising of nine fog events in Baton Rouge (Nov 2004 to Feb 2005) and two fog events in Houston (Feb, 2006), during the fog sampling campaigns. These samples were analyzed for pH, total and dissolved carbon, major inorganic ions, organic acids, and aromatics, aldehydes, VOCs, and linear alkanes organic compounds. Fogwater samples collected in Houston show clear influence of marine and anthropogenic environment, while Baton Rouge samples reveal a relatively less polluted environment. Also, a time series observation of air samples indicated that fog event at the monitoring site impacted the air concentrations of the pollutants. This is attributed to presence of surface active organic matter in fog water.

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment.

PubMed

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy.

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment

PubMed Central

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy. PMID:29202036

Influence of ozone, precipitation chemistry, and soil type on red spruce (Picea rubens)

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

Taylor, G.E. Jr.; Norby, R.J.; McLaughlin, S.B.

1986-04-01

The response of growth processes in red spruce to ozone, mist chemistry, rain chemistry, and soil type (singly and in combination) was investigated over a four-month period. Precipitation and ozone exposures were based on air chemistry/deposition in high elevation forests of eastern North America. The two soils were from Camels Hump in the Green Mountains of Vermont and Acadia National Park on the Maine coast. Growth was evaluated through analysis of relative growth rates (RGR) and biomass partitioning to root, stem, and needle fractions. The only main treatments that consistently influenced seedling growth were soil type and rain chemistry. Seedlingsmore » grown in Camels Hump soil had significantly less needle, stem, and root biomass and lower RGR. The only influence of precipitation chemistry was greater root and shoot biomass in seedlings experiencing the more acidic rain. It is hypothesized that the physiological mechanism underlying the growth responses of P. rubens is whole-plant allocation of carbon resources.« less

Interaction of acidic trace gases with ice from a surface science perspective

NASA Astrophysics Data System (ADS)

Waldner, A.; Kong, X.; Ammann, M.; Orlando, F.; Birrer, M.; Artiglia, L.; Bartels-Rausch, T.

2016-12-01

Acidic trace gases, such as HCOOH, HCl and HONO, play important roles in atmospheric chemistry. The presence of ice is known to have the capability to modify this chemistry (Neu et al. 2012). The molecular level processes of the interaction of acidic trace gases with ice are still a matter of debate and a quantification of the uptake is difficult (Dash et al. 2006, Bartels-Rausch et al. 2014, Huthwelker et al. 2006). This hampers a proper inclusion of ice as a substrate in models of various scales as for example in global chemistry climate models that would among others allow predicting large-scale effects of ice clouds. So far, direct observations of the ice surface and of the interaction with trace gases at temperatures and concentrations relevant to the environment are very limited. In this study, we take advantage of the surface and analytical sensitivity as well as the chemical selectivity of photoemission and absorption spectroscopy performed at ambient pressure using the near ambient pressure photoemission endstation (NAPP) at Swiss Light Source to overcome this limitation in environmental science (Orlando et al. 2016). Specifically, ambient pressure X-ray Photoelectron Spectroscopy (XPS) allows us to get information about chemical state and concentration depth profiles of dopants. The combination of XPS with auger electron yield Near-Edge X-ray Absorption Fine Structure (NEXAFS) enables us to locate the dopant and analyse wheather the interaction leads to enhanced surface disorder and to what extent different disorders influences the uptake of the trace gas. For the first time, this study looks directly at the interaction of HCOOH, the strongest organic acid, with ice at 2 different temperatures (233 and 253 K) relevant for environmental science by means of electron spectroscopy. XPS depth profiles indicate that the HCOOH basically remains within the topmost ice layers and O K-edge NEXAFS analysis show that the interaction ice-HCOOH does not lead to enhanced surface disorder at environmentally relevant conditions.

Ozone budgets from the Dynamics and Chemistry of Marine Stratocumulus experiment

NASA Technical Reports Server (NTRS)

Kawa, S. R.; Pearson, R., Jr.

1989-01-01

Measurements from the Dynamics and Chemistry of marine Stratocumulus experiment have been used to study components of the regional ozone budget. The surface destruction rate is determined by eddy correlation of ozone and vertical velocity measured by a low-flying aircraft. Significant variability is found in the measured surface resistance; it is partially correlated with friction velocity but appears to have other controlling influences as well. The mean resistance is 4190 s/m which is higher (slower destruction) than most previous estimates for seawater. Flux and mean measurements throughout the marine boundary layer are used to estimate the net rate of in situ photochemical production/destruction of ozone. Averaged over the flights, ozone concentration is found to be near steady state, and a net of photochemical destruction of 0.02-0.07 ng/cu m per sec is diagnosed. This is an important confirmation of photochemical model results for the remote marine boundary layer. Ozone vertical distributions above the boundary layer show a strongly layered structure with very sharp gradients. These distributions are possibly related to the stratospheric ozone source.

Photocatalytic degradation using design of experiments: a review and example of the Congo red degradation.

PubMed

Sakkas, Vasilios A; Islam, Md Azharul; Stalikas, Constantine; Albanis, Triantafyllos A

2010-03-15

The use of chemometric methods such as response surface methodology (RSM) based on statistical design of experiments (DOEs) is becoming increasingly widespread in several sciences such as analytical chemistry, engineering and environmental chemistry. Applied catalysis, is certainly not the exception. It is clear that photocatalytic processes mated with chemometric experimental design play a crucial role in the ability of reaching the optimum of the catalytic reactions. The present article reviews the major applications of RSM in modern experimental design combined with photocatalytic degradation processes. Moreover, the theoretical principles and designs that enable to obtain a polynomial regression equation, which expresses the influence of process parameters on the response are thoroughly discussed. An original experimental work, the photocatalytic degradation of the dye Congo red (CR) using TiO(2) suspensions and H(2)O(2), in natural surface water (river water) is comprehensively described as a case study, in order to provide sufficient guidelines to deal with this subject, in a rational and integrated way. (c) 2009 Elsevier B.V. All rights reserved.

Atmospheric Processing of Perovskite Solar Cells Using Intense Pulsed Light Sintering

NASA Astrophysics Data System (ADS)

Ankireddy, Krishnamraju; Lavery, Brandon W.; Druffel, Thad

2018-02-01

Atmospheric processing of metal-organic halide perovskite materials is highly desirable for large-scale manufacturing of solar cells. Atmospheric deposition and thermal processing of perovskite thin films for photovoltaic applications facilitated via rapid intense pulsed light (IPL) processing have been carried out. The interplay between the deposition chemistry, process, and IPL parameters to produce a functional photoactive thin film is discussed. Further addition of polyvinylpyrrolidone (PVP) as functional surfactant is explored to influence grain growth during the IPL process. Structural analysis by x-ray diffraction revealed formation of mixed-phase perovskite crystals from methylammonium chloride and lead iodide precursors. Ultraviolet-visible (UV-Vis) spectroscopy indicated that the light absorption by the perovskite films lay within a narrow band of the visible spectrum with bandgap of 2.9 eV. Scanning electron microscopy characterization of the surface morphology of the perovskite films revealed that addition of PVP to the ink chemistry assisted the IPL process in forming a fully covered surface with clearly defined grains. Functional devices with perovskite thin film processed by IPL under fully atmospheric conditions were demonstrated.

The differential regulation of osteoblast and osteoclast activity by surface topography of hydroxyapatite coatings.

PubMed

Costa, Daniel O; Prowse, Paul D H; Chrones, Tom; Sims, Stephen M; Hamilton, Douglas W; Rizkalla, Amin S; Dixon, S Jeffrey

2013-10-01

The behavior of bone cells is influenced by the surface chemistry and topography of implants and scaffolds. Our purpose was to investigate how the topography of biomimetic hydroxyapatite (HA) coatings influences the attachment and differentiation of osteoblasts, and the resorptive activity of osteoclasts. Using strategies reported previously, we directly controlled the surface topography of HA coatings on polycaprolactone discs. Osteoblasts and osteoclasts were incubated on HA coatings having distinct isotropic topographies with submicrometer and micro-scale features. Osteoblast attachment and differentiation were greater on more complex, micro-rough HA surfaces (Ra ~2 μm) than on smoother topographies (Ra ~1 μm). In contrast, activity of the osteoclast marker tartrate-resistant acid phosphatase was greater on smoother than on micro-rough surfaces. Furthermore, scanning electron microscopy revealed the presence of resorption lacunae exclusively on smoother HA coatings. Inhibition of resorption on micro-rough surfaces was associated with disruption of filamentous actin sealing zones. In conclusion, HA coatings can be prepared with distinct topographies, which differentially regulate responses of osteoblasts, as well as osteoclastic activity and hence susceptibility to resorption. Thus, it may be possible to design HA coatings that induce optimal rates of bone formation and degradation specifically tailored for different applications in orthopedics and dentistry. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of biocompatible metal ions (Ag, Fe, Y) on the surface chemistry, corrosion behavior and cytocompatibility of Mg-1Ca alloy treated with MEVVA.

PubMed

Liu, Yang; Bian, Dong; Wu, Yuanhao; Li, Nan; Qiu, Kejin; Zheng, Yufeng; Han, Yong

2015-09-01

Mg-1Ca samples were implanted with biocompatible alloy ions Ag, Fe and Y respectively with a dose of 2×10(17)ionscm(-2) by metal vapor vacuum arc technique (MEVVA). The surface morphologies and surface chemistry were investigated by SEM, AES and XPS. Surface changes were observed after all three kinds of elemental ion implantation. The results revealed that the modified layer was composed of two sublayers, including an outer oxidized layer with mixture of oxides and an inner implanted layer, after Ag and Fe ion implantation. Y ion implantation induced an Mg/Ca-deficient outer oxidized layer and the distribution of Y along with depth was more homogeneous. Both electrochemical test and immersion test revealed accelerated corrosion rate of Ag-implanted Mg-1Ca and Fe-implanted Mg-1Ca, whereas Y ion implantation showed a short period of protection since enhanced corrosion resistance was obtained by electrochemical test, but accelerated corrosion rate was found by long period immersion test. Indirect cytotoxicity assay indicated good cytocompatibility of Y-implanted Mg-1Ca. Moreover, the corresponding corrosion mechanisms involving implanting ions into magnesium alloys were proposed, which might provide guidance for further application of plasma ion implantation to biodegradable Mg alloys. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

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

Bruhn, Thomas; Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Albert-Einstein-Str.9, 12489 Berlin; Fimland, Bjørn-Ove

We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. Onmore » the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.« less

Prominent Chemists Team Up to Review Frontiers in Chemistry.

ERIC Educational Resources Information Center

Baum, Rudy M.

1989-01-01

Discusses a symposium which focused on the influence of inorganic chemistry on organic synthesis, the impact of organic chemistry on biochemistry and vice versa, chemical reaction dynamics, and advances in inorganic chemistry. Explains the purpose of the symposium was to illustrate the intellectual dynamism of modern chemistry. (MVL)

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…

Perspective on nanoparticle technology for biomedical use

PubMed Central

Raliya, Ramesh; Chadha, Tandeep Singh; Hadad, Kelsey; Biswas, Pratim

2016-01-01

This review gives a short overview on the widespread use of nanostructured and nanocomposite materials for disease diagnostics, drug delivery, imaging and biomedical sensing applications. Nanoparticle interaction with a biological matrix/entity is greatly influenced by its morphology, crystal phase, surface chemistry, functionalization, physicochemical and electronic properties of the particle. Various nanoparticle synthesis routes, characteristization, and functionalization methodologies to be used for biomedical applications ranging from drug delivery to molecular probing of underlying mechanisms and concepts are described with several examples (150 references). PMID:26951098

Limitations of using Raman microscopy for the analysis of high-content-carbon-filled ethylene propylene diene monomer rubber.

PubMed

Ghanbari-Siahkali, Afshin; Almdal, Kristoffer; Kingshott, Peter

2003-12-01

The effects of laser irradiation on changes to the surface chemistry and structure of a commercially available ethylene propylene diene monomer (EPDM) rubber sample after Raman microscopy analysis was investigated. The Raman measurements were carried out with different levels of laser power on the sample, ranging from 4.55 mW to 0.09 mW. The surface of the EPDM was analyzed before and after laser exposure using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The techniques have surface probe depths of approximately < or = 10 nm and 1 microm, respectively. Both sets of analysis show that ingredients of the blended EPDM rubber "bloom" to the surface as a result of local heating that takes place due to the absorption of laser by carbon black during the Raman analysis. Scanning electron microscopy (SEM) analysis was also performed on the Raman analyzed areas to visually illustrate the effects created due to laser light exposure (i.e., burning marks). The change in surface chemistry also occurs in regions a few millimeters from the exposed sites, indicating that the effect is quite long range. However, this phenomenon has no major influence, as far as XPS or ATR-FTIR results disclose, on the backbone structure of the rubber sample. The results indicate that precautions should be taken when analyzing complex blended polymer samples using Raman spectroscopy.

Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO2 catalysts

PubMed Central

Wolfbeisser, Astrid; Klötzer, Bernhard; Mayr, Lukas; Rameshan, Raffael; Zemlyanov, Dmitry; Bernardi, Johannes; Rupprechter, Günther

2015-01-01

The surface chemistry of methane on Ni–ZrO2 and bimetallic CuNi–ZrO2 catalysts and the stability of the CuNi alloy under reaction conditions of methane decomposition were investigated by combining reactivity measurements and in situ synchrotron-based near-ambient pressure XPS. Cu was selected as an exemplary promoter for modifying the reactivity of Ni and enhancing the resistance against coke formation. We observed an activation process occurring in methane between 650 and 735 K with the exact temperature depending on the composition which resulted in an irreversible modification of the catalytic performance of the bimetallic catalysts towards a Ni-like behaviour. The sudden increase in catalytic activity could be explained by an increase in the concentration of reduced Ni atoms at the catalyst surface in the active state, likely as a consequence of the interaction with methane. Cu addition to Ni improved the desired resistance against carbon deposition by lowering the amount of coke formed. As a key conclusion, the CuNi alloy shows limited stability under relevant reaction conditions. This system is stable only in a limited range of temperature up to ~700 K in methane. Beyond this temperature, segregation of Ni species causes a fast increase in methane decomposition rate. In view of the applicability of this system, a detailed understanding of the stability and surface composition of the bimetallic phases present and the influence of the Cu promoter on the surface chemistry under relevant reaction conditions are essential. PMID:25815163

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.

Mapping Distant Continental Influences in the Remote Pacific Atmosphere; Simulations of CO Relevant to the Photochemistry of Oxidants

NASA Technical Reports Server (NTRS)

Chatfield Robert B.; Guo, Z.; Sachse, G.; Singh, H.; Hipskind, R. Stephen (Technical Monitor)

2000-01-01

An animated sequence of maps of simulated carbon monoxide concentrations graphically portrays the extent of residual continental influence upon the tropical Pacific Ocean as studied by NASA aircraft during the PEM-Tropics B intensive sampling campaign. We used the MM5 at a 90 km resolution in a globally wrapped grid to simulate the meteorology of transport, and our GRACES model to follow the basic chemistry. The CO we simulate derives from different sources, and so we distinguish anthropogenic, natural terpenoid oxidation, biomass burning, and pervasive CH4-oxidation influences. "Influence" is always judged with an implicit timescale, and these maps describe influence on the 15-45 day timescale appropriate for CO oxidation. In consequence, the maps are useful in assessing the origins of slowly reacting compounds like acetone, methanol, and the lightest hydrocarbons. At 8 km altitude, The Eastern South Pacific to ca. 130 W (eastern Polynesia) was frequently affected by continental influences but NASA's DC-8's flight path did not happen to take it into these regions very often. Near the surface, continentally influenced air crossed into t he Western South Pacific, in the region northwest of the Southern Pacific Convergence Zone but south of the Intertropical Convergence Zone. This air originated from the NE Pacific, and partly from North America. Comparisons are made to CO and other compounds measured aboard the DC-8 and the P-3 aircraft. We will also use tracers to describe the influence of marine convection in the upper troposphere. As time allows, we will discuss the "age" of ozone within the very cleanest region sampled in portions of the near-equatorial Western South Pacific, using a simple chemical mechanism for ozone levels. These simulations describe the chemistry of an atmosphere with very low ozone.

Effects of Accelerated Deglaciation on Chemical Characteristics of Sub-arctic Lakes and Rivers in South and West Iceland

NASA Astrophysics Data System (ADS)

Ritter, M.; Strock, K.; Edwards, B. R.

2017-12-01

Glaciers and their associated paraglacial landscapes have changed rapidly over the past century, and may see increased rates of melt as temperatures increase in high latitude environments. As glaciers recede, glacial meltwater subsidies increase to inland freshwater systems, influencing their structure and function. Evidence suggests melting ice influences the chemical characteristics of systems by providing nutrient subsidies, while inputs of glacial flour influence their physical structure by affecting temperature, reducing water clarity and increasing turbidity. Together, changes in physical and chemical structure of these systems have subsequent effects on biota, with the potential to lower taxonomic richness. This study characterized the chemistry of rivers and lakes fed by glacial meltwater in sub-arctic environments of Iceland, where there is limited limnological data. The survey characterized nutrient chemistry, dissolved organic carbon, and ion chemistry. We surveyed glacial meltwater from six glaciers in south and west Iceland, using the drainage basin of Gigjökull glacier along the southern coast as a detailed study area to examine the interactions between groundwater and surface runoff. The southern systems, within the Eastern Volcanic Zone, have minimal soil development and active volcanoes produce ash input to lakes. Lakes in the Western Volcanic Zone were more diverse, located in older bedrock with more extensively weathered soil. Key differences were observed between aquatic environments subsidized with glacial meltwater and those without. This included physical effects, such as lower temperatures and chemical effects such as lower conductivity and higher pH in glacially fed systems. In the drainage basin of Gigjökull glacier, lakes formed after the former lagoon was emptied and then partly refilled with debris from jokulhlaups during the 2010 Eyjafjallajökull eruption. These newly formed lakes resembled non-glacial melt systems despite receiving glacial melt via indirect pathways. The effects of changing glacial inputs to inland freshwater systems are complex, and will be felt over a wide range of time scales. The systems in Gigjökull basin suggest once systems no longer receive glacial surface water melt, they will experience rapid shifts in physical and chemical structure.

Placing prairie pothole wetlands along spatial and temporal continua to improve integration of wetland function in ecological investigations

USGS Publications Warehouse

Euliss, Ned H.; Mushet, David M.; Newton, Wesley E.; Otto, Clint R.V.; Nelson, Richard D.; LaBaugh, James W.; Scherff, Eric J.; Rosenberry, Donald O.

2014-01-01

We evaluated the efficacy of using chemical characteristics to rank wetland relation to surface and groundwater along a hydrologic continuum ranging from groundwater recharge to groundwater discharge. We used 27 years (1974–2002) of water chemistry data from 15 prairie pothole wetlands and known hydrologic connections of these wetlands to groundwater to evaluate spatial and temporal patterns in chemical characteristics that correspond to the unique ecosystem functions each wetland performed. Due to the mineral content and the low permeability rate of glacial till and soils, salinity of wetland waters increased along a continuum of wetland relation to groundwater recharge, flow-through or discharge. Mean inter-annual specific conductance (a proxy for salinity) increased along this continuum from wetlands that recharge groundwater being fresh to wetlands that receive groundwater discharge being the most saline, and wetlands that both recharge and discharge to groundwater (i.e., groundwater flow-through wetlands) being of intermediate salinity. The primary axis from a principal component analysis revealed that specific conductance (and major ions affecting conductance) explained 71% of the variation in wetland chemistry over the 27 years of this investigation. We found that long-term averages from this axis were useful to identify a wetland’s long-term relation to surface and groundwater. Yearly or seasonal measurements of specific conductance can be less definitive because of highly dynamic inter- and intra-annual climate cycles that affect water volumes and the interaction of groundwater and geologic materials, and thereby influence the chemical composition of wetland waters. The influence of wetland relation to surface and groundwater on water chemistry has application in many scientific disciplines and is especially needed to improve ecological understanding in wetland investigations. We suggest ways that monitoring in situ wetland conditions could be linked with evolving remote sensing technology to improve our ability to better inform decisions affecting wetland sustainability and provide periodic inventories of wetland ecosystem services to document temporal trends in wetland function and how they respond to contemporary land-use change.

A facile route to steady redox-modulated nitroxide spin-labeled surfaces based on diazonium chemistry.

PubMed

Cougnon, Charles; Boisard, Séverine; Cador, Olivier; Dias, Marylène; Levillain, Eric; Breton, Tony

2013-05-18

A TEMPO derivative was covalently grafted onto carbon and gold surfaces via the diazonium chemistry. The acid-dependent redox properties of the nitroxyl group were exploited to elaborate electro-switchable magnetic surfaces. ESR characterization demonstrated the reversible and permanent magnetic character of the material.

Dynamic electrophoretic fingerprinting of the HIV-1 envelope glycoprotein

PubMed Central

2013-01-01

Background Interactions between the HIV-1 envelope glycoprotein (Env) and its primary receptor CD4 are influenced by the physiological setting in which these events take place. In this study, we explored the surface chemistry of HIV-1 Env constructs at a range of pH and salinities relevant to mucosal and systemic compartments through electrophoretic mobility (EM) measurements. Sexual transmission events provide a more acidic environment for HIV-1 compared to dissemination and spread of infection occurring in blood or lymph node. We hypothesize functional, trimeric Env behaves differently than monomeric forms. Results The dynamic electrophoretic fingerprint of trimeric gp140 revealed a change in EM from strongly negative to strongly positive as pH increased from that of the lower female genital tract (pHx) to that of the blood (pHy). Similar findings were observed using a trimeric influenza Haemagglutinin (HA) glycoprotein, indicating that this may be a general attribute of trimeric viral envelope glycoproteins. These findings were supported by computationally modeling the surface charge of various gp120 and HA crystal structures. To identify the behavior of the infectious agent and its target cells, EM measurements were made on purified whole HIV-1 virions and primary T-lymphocytes. Viral particles had a largely negative surface charge, and lacked the regions of positivity near neutral pH that were observed with trimeric Env. T cells changed their surface chemistry as a function of activation state, becoming more negative over a wider range of pH after activation. Soluble recombinant CD4 (sCD4) was found to be positively charged under a wide range of conditions. Binding studies between sCD4 and gp140 show that the affinity of CD4-gp140 interactions depends on pH. Conclusions Taken together, these findings allow a more complete model of the electrochemical forces involved in HIV-1 Env functionality. These results indicate that the influence of the localized environment on the interactions of HIV with target cells are more pronounced than previously appreciated. There is differential chemistry of trimeric, but not monomeric, Env under conditions which mimic the mucosa compared to those found systemically. This should be taken into consideration during design of immunogens which targets virus at mucosal portals of entry. PMID:23514633

Protein adsorption on tailored substrates: long-range forces and conformational changes

NASA Astrophysics Data System (ADS)

Bellion, M.; Santen, L.; Mantz, H.; Hähl, H.; Quinn, A.; Nagel, A.; Gilow, C.; Weitenberg, C.; Schmitt, Y.; Jacobs, K.

2008-10-01

Adsorption of proteins onto solid surfaces is an everyday phenomenon that is not yet fully understood. To further the current understanding, we have performed in situ ellipsometry studies to reveal the adsorption kinetics of three different proteins, lysozyme, α-amylase and bovine serum albumin. As substrates we offer Si wafers with a controlled Si oxide layer thickness and a hydrophilic or hydrophobic surface functionalization, allowing the tailoring of the influence of short- and long-range interactions. Our studies show that not only the surface chemistry determines the properties of an adsorbed protein layer but also the van der Waals contributions of a composite substrate. We compare the experimental findings to results of a colloidal Monte Carlo approach that includes conformational changes of the adsorbed proteins induced by density fluctuations.

Theoretical study of sum-frequency vibrational spectroscopy on limonene surface

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

Zheng, Ren-Hui, E-mail: zrh@iccas.ac.cn; Liu, Hao; Jing, Yuan-Yuan

2014-03-14

By combining molecule dynamics (MD) simulation and quantum chemistry computation, we calculate the surface sum-frequency vibrational spectroscopy (SFVS) of R-limonene molecules at the gas-liquid interface for SSP, PPP, and SPS polarization combinations. The distributions of the Euler angles are obtained using MD simulation, the ψ-distribution is between isotropic and Gaussian. Instead of the MD distributions, different analytical distributions such as the δ-function, Gaussian and isotropic distributions are applied to simulate surface SFVS. We find that different distributions significantly affect the absolute SFVS intensity and also influence on relative SFVS intensity, and the δ-function distribution should be used with caution whenmore » the orientation distribution is broad. Furthermore, the reason that the SPS signal is weak in reflected arrangement is discussed.« less

Consequences of plasma oxidation and vacuum annealing on the chemical properties and electron accumulation of In2O3 surfaces

NASA Astrophysics Data System (ADS)

Berthold, Theresa; Rombach, Julius; Stauden, Thomas; Polyakov, Vladimir; Cimalla, Volker; Krischok, Stefan; Bierwagen, Oliver; Himmerlich, Marcel

2016-12-01

The influence of oxygen plasma treatments on the surface chemistry and electronic properties of unintentionally doped and Mg-doped In2O3(111) films grown by plasma-assisted molecular beam epitaxy or metal-organic chemical vapor deposition is studied by photoelectron spectroscopy. We evaluate the impact of semiconductor processing technology relevant treatments by an inductively coupled oxygen plasma on the electronic surface properties. In order to determine the underlying reaction processes and chemical changes during film surface-oxygen plasma interaction and to identify reasons for the induced electron depletion, in situ characterization was performed implementing a dielectric barrier discharge oxygen plasma as well as vacuum annealing. The strong depletion of the initial surface electron accumulation layer is identified to be caused by adsorption of reactive oxygen species, which induce an electron transfer from the semiconductor to localized adsorbate states. The chemical modification is found to be restricted to the topmost surface and adsorbate layers. The change in band bending mainly depends on the amount of attached oxygen adatoms and the film bulk electron concentration as confirmed by calculations of the influence of surface state density on the electron concentration and band edge profile using coupled Schrödinger-Poisson calculations. During plasma oxidation, hydrocarbon surface impurities are effectively removed and surface defect states, attributed to oxygen vacancies, vanish. The recurring surface electron accumulation after subsequent vacuum annealing can be consequently explained by surface oxygen vacancies.

Comparative surface energetic study of Matrigel® and collagen I interactions with endothelial cells.

PubMed

Hill, Michael J; Sarkar, Debanjan

2017-07-01

Understanding of the surface energetic aspects of the spontaneously deposited proteins on biomaterial surfaces and how this influences cell adhesion and differentiation is an area of regenerative medicine that has not received adequate attention. Current controversies surround the role of the biomaterial substratum surface chemistry, the range of influence of said substratum, and the effects of different surface energy components of the protein interface. Endothelial cells (ECs) are a highly important cell type for regenerative medicine applications, such as tissue engineering, and In-vivo they interact with collagen I based stromal tissue and basement membranes producing different behavioral outcomes. The surface energetic properties of these tissue types and how they control EC behavior is not well known. In this work we studied the surface energetic properties of collagen I and Matrigel ® on various previously characterized substratum polyurethanes (PU) via contact angle analysis and examined the subsequent EC network forming characteristics. A combinatorial surface energy approach was utilized that compared Zisman's critical surface tension, Kaelble's numerical method, and van Oss-Good-Chaudhury theory (vOGCT). We found that the unique, rapid network forming characteristics of ECs on Matrigel ® could be attributed to the apolar or monopolar basic interfacial characteristics according to Zisman/Kaelble or vOGCT, respectively. We also found a lack of significant substratum influence on EC network forming characteristics for Matrigel ® but collagen I showed a distinct influence where more apolar PU substrata tended to produce higher Lewis acid character collagen I interfaces which led to a greater interaction with ECs. Collagen I interfaces on more polar PU substrata lacked Lewis acid character and led to similar EC network characteristics as Matrigel ® . We hypothesized that bipolar character of the protein film favored cell-substratum over cell-cell adhesive interactions which resulted in less rapidly forming but more stable networks. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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 Australian methane budget: Interpreting surface and train-borne measurements using a chemistry transport model

NASA Astrophysics Data System (ADS)

Fraser, Annemarie; Chan Miller, Christopher; Palmer, Paul I.; Deutscher, Nicholas M.; Jones, Nicholas B.; Griffith, David W. T.

2011-10-01

We investigate the Australian methane budget from 2005-2008 using the GEOS-Chem 3D chemistry transport model, focusing on the relative contribution of emissions from different sectors and the influence of long-range transport. To evaluate the model, we use in situ surface measurements of methane, methane dry air column average (XCH4) from ground-based Fourier transform spectrometers (FTSs), and train-borne surface concentration measurements from an in situ FTS along the north-south continental transect. We use gravity anomaly data from Gravity Recovery and Climate Experiment to describe the spatial and temporal distribution of wetland emissions and scale it to a prior emission estimate, which better describes observed atmospheric methane variability at tropical latitudes. The clean air sites of Cape Ferguson and Cape Grim are the least affected by local emissions, while Wollongong, located in the populated southeast with regional coal mining, samples the most locally polluted air masses (2.5% of the total air mass versus <1% at other sites). Averaged annually, the largest single source above background of methane at Darwin is long-range transport, mainly from Southeast Asia, accounting for ˜25% of the change in surface concentration above background. At Cape Ferguson and Cape Grim, emissions from ruminant animals are the largest source of methane above background, at approximately 20% and 30%, respectively, of the surface concentration. At Wollongong, emissions from coal mining are the largest source above background representing 60% of the surface concentration. The train data provide an effective way of observing transitions between urban, desert, and tropical landscapes.

Femtosecond movies of water near interfaces at sub-Angstrom resolution

NASA Astrophysics Data System (ADS)

Coridan, Robert; Hwee Lai, Ghee; Schmidt, Nathan; Abbamonte, Peter; Wong, Gerard C. L.

2010-03-01

The behavior of liquid water near interfaces with nanoscopic variations in chemistry influences a broad range of phenomena in biology. Using inelastic x-ray scattering (IXS) data from 3rd-generation synchrotron x-ray sources, we reconstruct the Greens function of liquid water, which describes the å-scale spatial and femtosecond-scale temporal evolution of density fluctuations. We extend this response function formalism to reconstruct the evolution of hydration structures near dynamic surfaces with different charge distributions, in order to define more precisely the molecular signature of hydrophilicity and hydrophobicity. Moreover, we investigate modifications to surface hydration structures and dynamics as the size of hydrophilic and hydrophobic patches are varied.

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.

Ab Initio-Based Predictions of Hydrocarbon Combustion Chemistry

DTIC Science & Technology

2015-07-15

There are two prime objectives of the research. One is to develop and apply efficient methods for using ab initio potential energy surfaces (PESs...31-Mar-2015 Approved for Public Release; Distribution Unlimited Final Report: Ab Initio -Based Predictions of Hydrocarbon Combustion Chemistry The...Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 hydrocarbon combustion, ab initio quantum chemistry, potential energy surfaces, chemical

Soil and periphyton indicators of anthropogenic water-quality changes in a rainfall-driven wetland

USGS Publications Warehouse

McCormick, P.V.

2011-01-01

Surface soils and periphyton communities were sampled across an oligotrophic, soft-water wetland to document changes associated with pulsed inputs of nutrient- and mineral-rich canal drainage waters. A gradient of canal-water influence was indicated by the surface-water specific conductance, which ranged between 743 and 963 ??S cm-1 in the canals to as low as 60 ??S cm-1 in the rainfall-driven wetland interior. Changes in soil chemistry and periphyton taxonomic composition across this gradient were described using piecewise regressions models. The greatest increase in soil phosphorus (P) concentration occurred at sites closest to the canal while soil mineral (sulfur, calcium) concentrations increased most rapidly at the lower end of the gradient. Multiple periphyton shifts occurred at the lower end of the gradient and included; (1) a decline in desmids and non-desmid filamentous chlorophytes, and their replacement by a diatom-dominated community; (2) the loss of soft-water diatom indicator species and their replacement by hard-water species. Increased dominance by cyanobacteria and eutrophic diatom indicators occurred closer to the canals. Soil and periphyton changes indicated four zones of increasing canal influence across the wetland: (1) a zone of increasing mineral concentrations where soft-water taxa remained dominant; (2) a transition towards hard-water, oligotrophic diatoms as mineral concentrations increased further; (3) a zone of dominance by these hard-water species; (4) a zone of rapidly increasing P concentrations and dominance by eutrophic taxa. In contrast to conclusions drawn from routine water-chemistry monitoring, measures of chemical and biological change presented here indicate that most of this rainfall-driven peatland receives some influence from canal discharges. These changes are multifaceted and induced by shifts in multiple chemical constituents. ?? 2010 US Government.

Light reflected from colored mulches affects aroma and phenol content of sweet basil (Ocimum basilicum L.) leaves.

PubMed

Loughrin, J H; Kasperbauer, M J

2001-03-01

Basil (Ocimum basilicum L.) is an herb the leaves of which are used to add a distinct aroma and flavor to food. It was hypothesized that the size and chemical composition of sun-grown basil leaves could be influenced by the color of light reflected from the soil surface and by the action of the reflected light through the natural growth regulatory system within the growing plants. Leaf morphology, aroma compounds, and soluble phenolics were compared in basil that had been grown over six colors of polyethylene row covers. Altering the ratios of blue, red, and far-red light reflected to growing plants influenced both leaf morphology and chemistry. Leaves developing over red surfaces had greater area, moisture percentage (succulence), and fresh weight than those developing over black surfaces. Basil grown over yellow and green surfaces produced significantly higher concentrations of aroma compounds than did basil grown over white and blue covers. Leaves grown over yellow and green mulches also contained significantly higher concentrations of phenolics than those grown over the other colors. Clearly, the wavelengths (color) of light reflected to growing basil plants affected leaf size, aroma, and concentrations of soluble phenolics, some of which are antioxidants.

Copper-free click chemistry in living animals

PubMed Central

Chang, Pamela V.; Prescher, Jennifer A.; Sletten, Ellen M.; Baskin, Jeremy M.; Miller, Isaac A.; Agard, Nicholas J.; Lo, Anderson; Bertozzi, Carolyn R.

2010-01-01

Chemical reactions that enable selective biomolecule labeling in living organisms offer a means to probe biological processes in vivo. Very few reactions possess the requisite bioorthogonality, and, among these, only the Staudinger ligation between azides and triarylphosphines has been employed for direct covalent modification of biomolecules with probes in the mouse, an important model organism for studies of human disease. Here we explore an alternative bioorthogonal reaction, the 1,3-dipolar cycloaddition of azides and cyclooctynes, also known as “Cu-free click chemistry,” for labeling biomolecules in live mice. Mice were administered peracetylated N-azidoacetylmannosamine (Ac4ManNAz) to metabolically label cell-surface sialic acids with azides. After subsequent injection with cyclooctyne reagents, glycoconjugate labeling was observed on isolated splenocytes and in a variety of tissues including the intestines, heart, and liver, with no apparent toxicity. The cyclooctynes tested displayed various labeling efficiencies that likely reflect the combined influence of intrinsic reactivity and bioavailability. These studies establish Cu-free click chemistry as a bioorthogonal reaction that can be executed in the physiologically relevant context of a mouse. PMID:20080615

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...

Influence of climate on alpine stream chemistry and water sources

USGS Publications Warehouse

Foks, Sydney; Stets, Edward; Singha, Kamini; Clow, David W.

2018-01-01

The resilience of alpine/subalpine watersheds may be viewed as the resistance of streamflow or stream chemistry to change under varying climatic conditions, which is governed by the relative size (volume) and transit time of surface and subsurface water sources. Here, we use end‐member mixing analysis in Andrews Creek, an alpine stream in Rocky Mountain National Park, Colorado, from water year 1994 to 2015, to explore how the partitioning of water sources and associated hydrologic resilience change in response to climate. Our results indicate that four water sources are significant contributors to Andrews Creek, including snow, rain, soil water, and talus groundwater. Seasonal patterns in source‐water contributions reflected the seasonal hydrologic cycle, which is driven by the accumulation and melting of seasonal snowpack. Flushing of soil water had a large effect on stream chemistry during spring snowmelt, despite making only a small contribution to streamflow volume. Snow had a large influence on stream chemistry as well, contributing large amounts of water with low concentrations of weathering products. Interannual patterns in end‐member contributions reflected responses to drought and wet periods. Moderate and significant correlations exist between annual end‐member contributions and regional‐scale climate indices (the Palmer Drought Severity Index, the Palmer Hydrologic Drought Index, and the Modified Palmer Drought Severity Index). From water year 1994 to 2015, the percent contribution from the talus‐groundwater end member to Andrews Creek increased an average of 0.5% per year (p < 0.0001), whereas the percent contributions from snow plus rain decreased by a similar amount (p = 0.001). Our results show how water and solute sources in alpine environments shift in response to climate variability and highlight the role of talus groundwater and soil water in providing hydrologic resilience to the system.

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

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

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

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.

Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

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

Not Available

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

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.

Surface ozone seasonality under global change: Influence from dry deposition and isoprene emissions at northern mid-latitudes

NASA Astrophysics Data System (ADS)

Clifton, O.; Paulot, F.; Fiore, A. M.; Horowitz, L. W.; Malyshev, S.; Shevliakova, E.; Correa, G. J. P.; Lin, M.

2017-12-01

Identifying the contributions of nonlinear chemistry and transport to observed surface ozone seasonal cycles over land using global models relies on an accurate representation of ozone uptake by vegetation (dry deposition). It is well established that in the absence of ozone precursor emission changes, a warming climate will increase surface ozone in polluted regions, and that a rise in temperature-dependent isoprene emissions would exacerbate this "climate penalty". However, the influence of changes in ozone dry deposition, expected to evolve with climate and land use, is often overlooked in air quality projections. With a new scheme that represents dry deposition within the NOAA GFDL dynamic vegetation land model (LM3) coupled to the NOAA GFDL atmospheric chemistry-climate model (AM3), we simulate the impact of 21st century climate and land use on ozone dry deposition and isoprene emissions. This dry deposition parameterization is a version of the Wesely scheme, but uses parameters explicitly calculated by LM3 that respond to climate and land use (e.g., stomatal conductance, canopy interception of water, leaf area index). The parameterization includes a nonstomatal deposition dependence on humidity. We evaluate climatological present-day seasonal cycles of ozone deposition velocities and abundances with those observed at northern mid-latitude sites. With a set of 2010s and 2090s decadal simulations under a high climate warming scenario (RCP8.5) and a sensitivity simulation with well-mixed greenhouse gases following RCP8.5 but air pollutants held at 2010 levels (RCP8.5_WMGG), we examine changes in surface ozone seasonal cycles. We build on our previous findings, which indicate that strong reductions in anthropogenic NOx emissions under RCP8.5 cause the surface ozone seasonal cycle over the NE USA to reverse, shifting from a summer peak at present to a winter peak by 2100. Under RCP8.5_WMGG, we parse the separate effects of climate and land use on ozone dry deposition vs. isoprene emissions to quantify the impact of each process on surface ozone seasonal cycles and compare to the changes induced by declining anthropogenic NOx emissions (RCP8.5).

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.

The spatial variability of water chemistry and DOC in bog pools: the importance of slope position, diurnal turnover and pool type

NASA Astrophysics Data System (ADS)

Holden, Joseph; Turner, Ed; Baird, Andy; Beadle, Jeannie; Billett, Mike; Brown, Lee; Chapman, Pippa; Dinsmore, Kerry; Dooling, Gemma; Grayson, Richard; Moody, Catherine; Gee, Clare

2017-04-01

We have previously shown that marine influence is an important factor controlling regional variability of pool water chemistry in blanket peatlands. Here we examine within-site controls on pool water chemistry. We surveyed natural and artificial (restoration sites) bog pools at blanket peatland sites in northern Scotland and Sweden. DOC, pH, conductivity, dissolved oxygen, temperature, cations, anions and absorbance spectra from 220-750nm were sampled. We sampled changes over time but also conducted intensive spatial surveys within individual pools and between pools on the same sampling days at individual study sites. Artificial pools had significantly greater DOC concentrations and different spectral absorbance characteristics when compared to natural pools at all sites studied. Within-pool variability in water chemistry tended to be small, even for very large pools ( 400 m2), except where pools had a layer of loose, mobile detritus on their beds. In these instances rapid changes took place between the overlying water column and the mobile sediment layer wherein dissolved oxygen concentrations dropped from values of around 12-10 mg/L to values less than 0.5 mg/L over just 2-3 cm of the depth profile. Such strong contrasts were not observed for pools which had a hard peat floor and which lacked a significant detritus layer. Strong diurnal turnover occurred within the pools on summer days, including within small, shallow pools (e.g. < 30 cm deep, 1 m2 area). For many pools on these summer days there was an evening spike in dissolved oxygen concentrations which originated at the surface and was then cycled downwards as the pool surface waters cooled. Slope location was a significant control on several pool water chemistry variables including pH and DOC concentration with accumulation (higher concentrations) in pools that were located further downslope in both natural and artificial pool systems. These processes have important implications for our interpretation of water chemistry and gas flux data from pool systems, how we design our sampling strategies and how we upscale results.

Effect of surface pre-treatments on biocompatibility of magnesium.

PubMed

Lorenz, Carla; Brunner, Johannes G; Kollmannsberger, Philip; Jaafar, Leila; Fabry, Ben; Virtanen, Sannakaisa

2009-09-01

This study reports the influence of Mg surface passivation on the survival rate of human HeLa cells and mouse fibroblasts in cell culture experiments. Polished samples of commercially pure Mg show high reactivity in the cell culture medium, leading to a pH shift in the alkaline direction, and therefore cell adhesion and survival is strongly impaired. Passivation of the Mg surface in 1M NaOH can strongly enhance cell survival. The best initial cell adhesion is observed for Mg samples incubated in simulated body fluid (M-SBF), which leads to the formation of a biomimetic, amorphous Ca/Mg-phosphate layer with high surface roughness. This surface layer, however, passivates and seals the Mg surface only partially. Subsequent Mg dissolution leads to a significantly stronger pH increase compared to NaOH-passivated samples, which prevents long-term cell survival. These results demonstrate that surface passivation with NaOH and M-SBF together with the associated changes of surface reactivity, chemistry and roughness provide a viable strategy to facilitate cell survival on otherwise non-biocompatible Mg surfaces.

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.

Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

NASA Astrophysics Data System (ADS)

Benetti, F.; Fedel, M.; Minati, L.; Speranza, G.; Migliaresi, C.

2013-06-01

Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

Updating sea spray aerosol emissions in the Community Multiscale Air Quality (CMAQ) model version 5.0.2

NASA Astrophysics Data System (ADS)

Gantt, B.; Kelly, J. T.; Bash, J. O.

2015-11-01

Sea spray aerosols (SSAs) impact the particle mass concentration and gas-particle partitioning in coastal environments, with implications for human and ecosystem health. Model evaluations of SSA emissions have mainly focused on the global scale, but regional-scale evaluations are also important due to the localized impact of SSAs on atmospheric chemistry near the coast. In this study, SSA emissions in the Community Multiscale Air Quality (CMAQ) model were updated to enhance the fine-mode size distribution, include sea surface temperature (SST) dependency, and reduce surf-enhanced emissions. Predictions from the updated CMAQ model and those of the previous release version, CMAQv5.0.2, were evaluated using several coastal and national observational data sets in the continental US. The updated emissions generally reduced model underestimates of sodium, chloride, and nitrate surface concentrations for coastal sites in the Bay Regional Atmospheric Chemistry Experiment (BRACE) near Tampa, Florida. Including SST dependency to the SSA emission parameterization led to increased sodium concentrations in the southeastern US and decreased concentrations along parts of the Pacific coast and northeastern US. The influence of sodium on the gas-particle partitioning of nitrate resulted in higher nitrate particle concentrations in many coastal urban areas due to increased condensation of nitric acid in the updated simulations, potentially affecting the predicted nitrogen deposition in sensitive ecosystems. Application of the updated SSA emissions to the California Research at the Nexus of Air Quality and Climate Change (CalNex) study period resulted in a modest improvement in the predicted surface concentration of sodium and nitrate at several central and southern California coastal sites. This update of SSA emissions enabled a more realistic simulation of the atmospheric chemistry in coastal environments where marine air mixes with urban pollution.

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.

Uncertainties in United States agricultural N2O emissions: comparing forward model simulations to atmospheric N2O data.

NASA Astrophysics Data System (ADS)

Nevison, C. D.; Saikawa, E.; Dlugokencky, E. J.; Andrews, A. E.; Sweeney, C.

2014-12-01

Atmospheric N2O concentrations have increased from 275 ppb in the preindustrial to about 325 ppb in recent years, a ~20% increase with important implications for both anthropogenic greenhouse forcing and stratospheric ozone recovery. This increase has been driven largely by synthetic fertilizer production and other perturbations to the global nitrogen cycle associated with human agriculture. Several recent regional atmospheric inversion studies have quantified North American agricultural N2O emissions using top-down constraints based on atmospheric N2O data from the National Oceanic and Atmospheric Administration (NOAA) Global Greenhouse Gas Reference Network, including surface, aircraft and tall tower platforms. These studies have concluded that global N2O inventories such as EDGAR may be underestimating the true U.S. anthropogenic N2O source by a factor of 3 or more. However, simple back-of-the-envelope calculations show that emissions of this magnitude are difficult to reconcile with the basic constraints of the global N2O budget. Here, we explore some possible reasons why regional atmospheric inversions might overestimate the U.S. agricultural N2O source. First, the seasonality of N2O agricultural sources is not well known, but can have an important influence on inversion results, particularly when the inversions are based on data that are concentrated in the spring/summer growing season. Second, boundary conditions can strongly influence regional inversions but the boundary conditions used may not adequately account for remote influences on surface data such as the seasonal stratospheric influx of N2O-depleted air. We will present a set of forward model simulations, using the Community Land Model (CLM) and two atmospheric chemistry tracer transport models, MOZART and the Whole Atmosphere Community Climate Model (WACCM), that examine the influence of terrestrial emissions and atmospheric chemistry and dynamics on atmospheric variability in N2O at U.S. and global monitoring sites.

Weathering of a carbon nanotube/epoxy nanocomposite under UV light and in water bath: impact on abraded particles.

PubMed

Schlagenhauf, Lukas; Kianfar, Bahareh; Buerki-Thurnherr, Tina; Kuo, Yu-Ying; Wichser, Adrian; Nüesch, Frank; Wick, Peter; Wang, Jing

2015-11-28

Weathering processes can influence the surface properties of composites with incorporated nanoparticles. These changes may affect the release behavior of nanoparticles when an abrasion process is applied. Therefore, the influence of two different weathering processes, immersion in water and exposure to UV light, on the properties of abraded particles from a carbon nanotube (CNT)/epoxy nanocomposite was investigated. The investigation included the measurement of the weathering impact on the surface chemistry of the exposed samples, the particle size of abraded particles, the quantity of exposed CNTs in the respirable part of the abraded particles, and the toxicity of abraded particles, measured by in vitro toxicity tests using the THP-1 monocyte-derived macrophages. The results showed that weathering by immersion in water had no influence on the properties of abraded particles. The exposure to UV light caused a degradation of the epoxy on the surface, followed by delamination of an approx. 2.5 μm thick layer. An increased quantity of exposed CNTs in abraded particles was not found; on the contrary, longer UV exposure times decreased the released fraction of CNTs from 0.6% to 0.4%. The toxicity tests revealed that abraded particles from the nanocomposites did not induce additional acute cytotoxic effects compared to particles from the neat epoxy.

Observational assessment of the role of nocturnal residual-layer chemistry in determining daytime surface particulate nitrate concentrations

NASA Astrophysics Data System (ADS)

Prabhakar, Gouri; Parworth, Caroline L.; Zhang, Xiaolu; Kim, Hwajin; Young, Dominique E.; Beyersdorf, Andreas J.; Ziemba, Luke D.; Nowak, John B.; Bertram, Timothy H.; Faloona, Ian C.; Zhang, Qi; Cappa, Christopher D.

2017-12-01

This study discusses an analysis of combined airborne and ground observations of particulate nitrate (NO3-(p)) concentrations made during the wintertime DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically resolved observations relevant to Air Quality) study at one of the most polluted cities in the United States - Fresno, CA - in the San Joaquin Valley (SJV) and focuses on developing an understanding of the various processes that impact surface nitrate concentrations during pollution events. The results provide an explicit case-study illustration of how nighttime chemistry can influence daytime surface-level NO3-(p) concentrations, complementing previous studies in the SJV. The observations exemplify the critical role that nocturnal chemical production of NO3-(p) aloft in the residual layer (RL) can play in determining daytime surface-level NO3-(p) concentrations. Further, they indicate that nocturnal production of NO3-(p) in the RL, along with daytime photochemical production, can contribute substantially to the buildup and sustaining of severe pollution episodes. The exceptionally shallow nocturnal boundary layer (NBL) heights characteristic of wintertime pollution events in the SJV intensify the importance of nocturnal production aloft in the residual layer to daytime surface concentrations. The observations also demonstrate that dynamics within the RL can influence the early-morning vertical distribution of NO3-(p), despite low wintertime wind speeds. This overnight reshaping of the vertical distribution above the city plays an important role in determining the net impact of nocturnal chemical production on local and regional surface-level NO3-(p) concentrations. Entrainment of clean free-tropospheric (FT) air into the boundary layer in the afternoon is identified as an important process that reduces surface-level NO3-(p) and limits buildup during pollution episodes. The influence of dry deposition of HNO3 gas to the surface on daytime particulate nitrate concentrations is important but limited by an excess of ammonia in the region, which leads to only a small fraction of nitrate existing in the gas phase even during the warmer daytime. However, in the late afternoon, when diminishing solar heating leads to a rapid fall in the mixed boundary layer height (BLH), the impact of surface deposition is temporarily enhanced and can lead to a substantial decline in surface-level particulate nitrate concentrations; this enhanced deposition is quickly arrested by a decrease in surface temperature, which drops the gas-phase fraction to near zero. The overall importance of enhanced late-afternoon gas-phase loss to the multiday buildup of pollution events is limited by the very shallow nocturnal boundary layer. The case study here demonstrates that mixing down of NO3-(p) from the RL can contribute a majority of the surface-level NO3-(p) in the morning (here, ˜ 80 %), and a strong influence can persist into the afternoon even when photochemical production is maximum. The particular day-to-day contribution of aloft nocturnal NO3-(p) production to surface concentrations will depend on prevailing chemical and meteorological conditions. Although specific to the SJV, the observations and conceptual framework further developed here provide general insights into the evolution of pollution episodes in wintertime environments.

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…

Estimating the Analytical and Surface Enhancement Factors in Surface-Enhanced Raman Scattering (SERS): A Novel Physical Chemistry and Nanotechnology Laboratory Experiment

ERIC Educational Resources Information Center

Pavel, Ioana E.; Alnajjar, Khadijeh S.; Monahan, Jennifer L.; Stahler, Adam; Hunter, Nora E.; Weaver, Kent M.; Baker, Joshua D.; Meyerhoefer, Allie J.; Dolson, David A.

2012-01-01

A novel laboratory experiment was successfully implemented for undergraduate and graduate students in physical chemistry and nanotechnology. The main goal of the experiment was to rigorously determine the surface-enhanced Raman scattering (SERS)-based sensing capabilities of colloidal silver nanoparticles (AgNPs). These were quantified by…

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.

Global Radiative Forcing of Coupled Tropospheric Ozone and Aerosols in a Unified General Circulation Model

NASA Technical Reports Server (NTRS)

Liao, Hong; Seinfeld, John H.; Adams, Peter J.; Mickley, Loretta J.

2008-01-01

Global simulations of sea salt and mineral dust aerosols are integrated into a previously developed unified general circulation model (GCM), the Goddard Institute for Space Studies (GISS) GCM II', that simulates coupled tropospheric ozone-NOx-hydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m(sup -2) at TOA and +0.07 W m(sup -2) at the Earth's surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as -0.72 and -4.04 W m(sup -2), respectively. While the predicted highest aerosol cooling and heating at TOA are -10 and +12 W m(sup -2) respectively, surface forcing can reach values as high as -30 W m(sup -2), mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%.

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.

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.

Exploring Diverse Students' Trends in Chemistry Self-Efficacy throughout a Semester of College-Level Preparatory Chemistry

ERIC Educational Resources Information Center

Villafañe, Sachel M.; Garcia, C. Alicia; Lewis, Jennifer E.

2014-01-01

Chemistry self-efficacy has been defined as a student's beliefs about his or her own capability to perform a given chemistry task. These chemistry self-efficacy beliefs can be influenced by students' experiences in a course, and eventually, these beliefs could affect students' decisions to continue into STEM related-careers. In this study, we…

Is Chemistry Attractive for Pupils? Czech Pupils' Perception of Chemistry

ERIC Educational Resources Information Center

Kubiatko, Milan

2015-01-01

Chemistry is an important subject due to understanding the composition and structure of the things around us. The main aim of the study was to find out the perception of chemistry by lower secondary school pupils. The partial aims were to find out the influence of gender, year of study and favorite subject on the perception of chemistry. The…

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

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

2017-02-16

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

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)

DOC and DON Dynamics along the Bagmati Drainage Network in Kathmandu Valley

NASA Astrophysics Data System (ADS)

Bhatt, M. P.; McDowell, W. H.

2005-05-01

We studied organic matter dynamics and inorganic chemistry of the Bagmati River in Kathmandu valley, Nepal, to understand the influence of human and geochemical processes on chemical loads along the drainage system. Population density appears to be the most fundamental control on the chemistry of surface waters within the Bagmati drainage system. DOC concentration increases 10-fold with distance downstream (from 2.38 to 23.95 mg/L) and shows a strong relationship with human population density. The composition of river water (nutrients, Cl) suggests that sewage effluent to the river has a major effect on water quality. Concentrations were highest during summer, and lowest during the winter monsoon season. In contrast to DOC, DON concentration shows surprisingly little variation, and tends to decrease in concentration with distance downstream. Ammonium contributes almost all nitrogen in the total dissolved nitrogen fraction and the concentration of nitrate is negligible, probably due to rapid denitrification within the stream channel under relatively low-oxygen conditions. Decreases in sulfate along the stream channel may also be due to the reduction of sulfate to sulfide due to the heavy organic matter loading. Water quality is unacceptable for any use and the whole ecosystem is severely affected within the urban areas. Based on a comparison of downstream and upstream water quality, it appears that human activities along the Bagmati, principally inputs of human sewage, are largely responsible for the changes in surface water chemistry within Kathmandu valley.

Halogen Chemistry in the CMAQ Model

EPA Science Inventory

Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

Copolymer Synthesis and Characterization by Post-Polymerization Modification

NASA Astrophysics Data System (ADS)

Galvin, Casey James

This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in developing technologies that use SGPAs in aqueous environments, and point to a need for potential alternative grafting chemistries. The behavior of SGPAs in vapor environments remains an underexplored phenomenon. By changing systematically the chemistry of SGPAs derived from a parent sample, the influence of side chain functional groups on the swelling of weak and strong polyelectrolyte brushes in the presence of water, methanol and ethanol vapors is explored. The extent of swelling and solvent uptake depends strongly on the chemistry in the polymer side chain and of the solvent. Despite bearing a permanent electrostatic charge in the side chain, the strong polyelectrolyte brushes exhibit no behavior typical of polyelectrolytes in water due to no dissociation of the counterion. Of particular interest is the behavior in humid environments of an SGPA bearing a zwitterionic group in its side chain, which results in exposure of electrostatic charges without counterions. Using substrates bearing the aforementioned sigma gradient of polymeric grafts, evidence of inter- and intramolecular complex formation is presented. Finally, a method of developing SGPAs by polymerizing bulk polymer chains through surface-grafted monomers (SGMs) is described. The SGMs are incorporated onto a solid substrate using the same PPM reaction employed in the degrafting and vapor swelling experiments, highlighting the versatility of PPM. The thickness of these SGPAs is correlated to the bulk polymer chains MW, suggesting this technique can be used in existing industrial bulk polymerization processes.

Effects of numerical tolerance levels on an atmospheric chemistry model for mercury

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

Ferris, D.C.; Burns, D.S.; Shuford, J.

1996-12-31

A Box Model was developed to investigate the atmospheric oxidation processes of mercury in the environment. Previous results indicated the most important influences on the atmospheric concentration of HgO(g) are (i) the flux of HgO(g) volatilization, which is related to the surface medium, extent of contamination, and temperature, and (ii) the presence of Cl{sub 2} in the atmosphere. The numerical solver which has been incorporated into the ORganic CHemistry Integrated Dispersion (ORCHID) model uses the Livermore Solver of Ordinary Differential Equations (LSODE). In the solution of the ODE`s, LSODE uses numerical tolerances. The tolerances effect computer run time, the relativemore » accuracy of ODE calculated species concentrations and whether or not LSODE converges to a solution using this system of equations. The effects of varying these tolerances on the solution of the box model and the ORCHID model will be discussed.« less

Favorable Influence of Hydrophobic Surfaces on Protein Structure in Porous Organically-modified Silica Glasses

PubMed Central

Menaa, Bouzid; Herrero, Mar; Rives, Vicente; Lavrenko, Mayya; Eggers, Daryl K.

2008-01-01

Organically-modified siloxanes were used as host materials to examine the influence of surface chemistry on protein conformation in a crowded environment. The sol-gel materials were prepared from tetramethoxysilane and a series of monosubstituted alkoxysilanes, RSi(OR′)3, featuring alkyl groups of increasing chain length in the R-position. Using circular dichroism spectroscopy in the far-UV region, apomyoglobin was found to transit from an unfolded state to a native-like helical state as the content of the hydrophobic precursor increased from 0–15%. At a fixed molar content of 5% RSi(OR’)3, the helical structure of apomyoglobin increased with the chain length of the R-group, i.e. methyl < ethyl < n-propyl < n-butyl < n-hexyl. This trend also was observed for the tertiary structure of ribonuclease A, suggesting that protein folding and biological activity are sensitive to the hydrophilic/hydrophobic balance of neighboring surfaces. The observed changes in protein structure did not correlate with total surface area or the average pore size of the modified glasses, but scanning electron microscopy images revealed an interesting relationship between surface morphology and alkyl chain length. The unexpected benefit of incorporating a low content of hydrophobic groups into a hydrophilic surface may lead to materials with improved biocompatibility for use in biosensors and implanted devices. PMID:18359512

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.

Global distribution and surface activity of macromolecules in offline simulations of marine organic chemistry

DOE PAGES

Ogunro, Oluwaseun O.; Burrows, Susannah M.; Elliott, Scott; ...

2015-10-13

Here, organic macromolecules constitute high percentage components of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer organic macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean biogeochemistry model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed formore » labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of protein, polysaccharide and refractory heteropolycondensate. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally quite reasonable. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant distributions. Results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.« less

Elucidating the role of surface chemistry on cationic phosphorus dendrimer-siRNA complexation.

PubMed

Deriu, Marco A; Tsapis, Nicolas; Noiray, Magali; Grasso, Gianvito; El Brahmi, Nabil; Mignani, Serge; Majoral, Jean-Pierre; Fattal, Elias; Danani, Andrea

2018-06-14

In the field of dendrimers targeting small interfering RNA (siRNA) delivery, dendrimer structural properties, such as the flexibility/rigidity ratio, play a crucial role in the efficiency of complexation. However, advances in organic chemistry have enabled the development of dendrimers that differ only by a single atom on their surface terminals. This is the case for cationic phosphorus dendrimers functionalized with either pyrrolidinium (DP) or morpholinium (DM) terminal groups. This small change was shown to strongly affect the dendrimer-siRNA complexation, leading to more efficient anti-inflammatory effects in the case of DP. Reasons for this different behavior can hardly be inferred only by biological in vitro and in vivo experiments due to the high number of variables and complexity of the investigated biological system. However, an understanding of how small chemical surface changes may completely modify the overall dendrimer-siRNA complexation is a significant breakthrough towards the design of efficient dendrimers for nucleic acid delivery. Herein, we present experimental and computational approaches based on isothermal titration calorimetry and molecular dynamics simulations to elucidate the molecular reasons behind different efficiencies and activities of DP and DM. Results of the present research highlight how chemical surface modifications may drive the overall dendrimer-siRNA affinity by influencing enthalpic and entropic contributions of binding free energy. Moreover, this study elucidates molecular reasons related to complexation stoichiometry that may be crucial in determining the dendrimer complexation efficiency.

Fracture mechanics and surface chemistry studies of fatigue crack growth in an aluminum alloy

NASA Astrophysics Data System (ADS)

Wei, R. P.; Pao, P. S.; Hart, R. G.; Weir, T. W.; Simmons, G. W.

1980-12-01

Fracture mechanics and surface chemistry studies were carried out to develop further understanding of the influence of water vapor on fatigue crack growth in aluminum alloys. The room temperature fatigue crack growth response was determined for 2219-T851 aluminum alloy exposed to water vapor at pressures from 1 to 30 Pa over a range of stress intensity factors ( K). Data were also obtained in vacuum (at < 0.50 μPa), and dehumidified argon. The test results showed that, at a frequency of 5 Hz, the rate of crack growth is essentially unaffected by water vapor until a threshold pressure is reached. Above this threshold, the rates increased, reaching a maximum within one order of magnitude increase in vapor pressure. This maximum crack growth rate is equal to that obtained in air (40 to 60 pct relative humidity), distilled water and 3.5 pct NaCl solution on the same material. Parallel studies of the reactions of water vapor with fresh alloy surfaces (produced either by in situ impact fracture or by ion etching) were made by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The extent of surface reaction was monitored by changes in the oxygen AES and XPS signals. Correlation between the fatigue crack growth response and the surface reaction kinetics has been made, and is consistent with a transport-limited model for crack growth. The results also suggest that enhancement of fatigue crack growth by water vapor in the aluminum alloys occurs through a “hydrogen embrittle ment” mechanism.

Surface pre-treatment for barrier coatings on polyethylene terephthalate

NASA Astrophysics Data System (ADS)

Bahre, H.; Bahroun, K.; Behm, H.; Steves, S.; Awakowicz, P.; Böke, M.; Hopmann, Ch; Winter, J.

2013-02-01

Polymers have favourable properties such as light weight, flexibility and transparency. Consequently, this makes them suitable for food packaging, organic light-emitting diodes and flexible solar cells. Nonetheless, raw plastics do not possess sufficient barrier functionality against oxygen and water vapour, which is of paramount importance for most applications. A widespread solution is to deposit thin silicon oxide layers using plasma processes. However, silicon oxide layers do not always fulfil the requirements concerning adhesion and barrier performance when deposited on films. Thus, plasma pre-treatment is often necessary. To analyse the influence of a plasma-based pre-treatment on barrier performance, different plasma pre-treatments on three reactor setups were applied to a very smooth polyethylene terephthalate film before depositing a silicon oxide barrier layer. In this paper, the influence of oxygen and argon plasma pre-treatments towards the barrier performance is discussed examining the chemical and topological change of the film. It was observed that a short one-to-ten-second plasma treatment can reduce the oxygen transmission rate by a factor of five. The surface chemistry and the surface topography change significantly for these short treatment times, leading to an increased surface energy. The surface roughness rises slowly due to the development of small spots in the nanometre range. For very long treatment times, surface roughness of the order of the barrier layer's thickness results in a complete loss of barrier properties. During plasma pre-treatment, the trade-off between surface activation and roughening of the surface has to be carefully considered.

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

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.

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.

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

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

Laser micropolishing of AISI 304 stainless steel surfaces for cleanability and bacteria removal capability

NASA Astrophysics Data System (ADS)

De Giorgi, Chiara; Furlan, Valentina; Demir, Ali Gökhan; Tallarita, Elena; Candiani, Gabriele; Previtali, Barbara

2017-06-01

In this work, laser micropolishing (LμP) was employed to reduce the surface roughness and waviness of cold-rolled AISI 304 stainless steel sheets. A pulsed fibre laser operating in the ns regime was used and the influence of laser parameters in a N2-controlled atmospheres was evaluated. In the optimal conditions, the surface remelting induced by the process allowed to reduce the surface roughness by closing cracks and defects formed during the rolling process. Other conditions that did not improve the surface quality were analysed for defect typology. Moreover, laser treatments allowed the production of more hydrophobic surfaces, and no surface chemistry modification was identified. Surface cleanability was investigated with Escherichia coli (E. coli), evaluating the number of residual bacteria adhering to the substrate after a washing procedure. These results showed that LμP is a suitable way to lower the average surface roughness by about 58% and average surface waviness by approximately 38%. The LμP process proved to be effective on the bacteria cleanability as approximately five times fewer bacteria remained on the surfaces treated with the optimized LμP parameters compared to the untreated surfaces.

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.

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.

Grain shape influence on semiconducting metal oxide based gas sensor performance: modeling versus experiment.

PubMed

Rebholz, Julia; Bonanati, Peter; Weimar, Udo; Barsan, Nicolae

2014-06-01

A model for sensing with semiconducting metal oxide (SMOX)-based gas sensors was developed which takes the effect of the shape of the grains in the sensing layers into account. Its validity is limited to materials in which the grains of the SMOX sensing layer are large enough to have an undepleted bulk region (large grains). This means that in all experimental conditions, the SMOX properties ensure that the influence of surface phenomena is not extended to the whole grain. The model takes the surface chemistry and its impact on the electrical properties of the sensing material into consideration. In this way, it relates the sensor signal--defined as the relative change of the sensor's conductance--directly to the concentration of the target gas and also exhibits meaningful chemical parameters, such as the type of reactive oxygen species, the reaction constants, and the concentration of adsorption sites. The validity of the model is confirmed experimentally by applying it to data gathered by measuring homemade sensors in relevant conditions.

Development of chemistry attitudes and experiences questionnaire (CAEQ)

NASA Astrophysics Data System (ADS)

Dalgety, Jacinta; Coll, Richard K.; Jones, Alister

2003-09-01

In this article we describe the development of the Chemistry Attitudes and Experiences Questionnaire (CAEQ) that measures first-year university chemistry students' attitude toward chemistry, chemistry self-efficacy, and learning experiences. The instrument was developed as part of a larger study and sought to fulfill a need for an instrument to investigate factors that influence student enrollment choice. We set out to design the instrument in a manner that would maximize construct validity. The CAEQ was piloted with a cohort of science and technology students (n = 129) at the end of their first year. Based on statistical analysis the instrument was modified and subsequently administered on two occasions at two tertiary institutions (n = 669). Statistical data along with additional data gathered from interviews suggest that the CAEQ possesses good construct validity and will prove a useful tool for tertiary level educators who wish to gain an understanding of factors that influence student choice of chemistry enrolment.

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...

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.

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.

Reduced transport potential of a palladium-doped zero valent iron nanoparticle in a water saturated loamy sand.

PubMed

Basnet, Mohan; Di Tommaso, Caroline; Ghoshal, Subhasis; Tufenkji, Nathalie

2015-01-01

Direct in situ injection of palladium-doped nanosized zero valent iron (Pd-NZVI) particles can contribute to remediation of various environmental contaminants. A major challenge encountered is rapid aggregation of Pd-NZVI and hence very limited mobility. To reduce aggregation and concurrently improve particle mobility, the surface of bare Pd-NZVI can be modified with stabilizing surface modifiers. Selected surface-modified Pd-NZVI has shown dramatically improved stability and transport. However, little is known regarding the effects of aquifer grain geochemical heterogeneity on the transport and deposition behavior of surface-modified Pd-NZVI. Herein, the mobility of surface stabilized Pd-NZVI in two granular matrices representative of model ground water environments (quartz sand and loamy sand) was assessed over a wide range of environmentally relevant ionic strengths (IS). Carboxymethyl cellulose (CMC), soybean flour and rhamnolipid biosurfactant were used as Pd-NZVI surface modifiers. Our results show that, both in quartz sand and loamy sand, an increase in solution IS results in reduced Pd-NZVI transport. Moreover, at a given water chemistry, Pd-NZVI transport is notably attenuated in loamy sand implying that geochemical heterogeneity associated with loamy sand is a key factor influencing Pd-NZVI transport potential. Experiments conducted at a higher Pd-NZVI particle concentration, to be more representative of field conditions, show that rhamnolipid and CMC are effective stabilizing agents even when 1 g/L Pd-NZVI is injected into quartz sand. Overall, this study emphasizes the extent to which variation in groundwater chemistry, coupled with changes in aquifer geochemistry, could dramatically alter the transport potential of Pd-NZVI in the subsurface environment.

Chemical and Topographical Modification of Polycarbonate Surfaces through Diffusion/Photocuring Processes of Hydrogel Precursors Based on Vinylpyrrolidone.

PubMed

Gallardo, Alberto; Lujan, Noelia; Reinecke, Helmut; García, Carolina; Campo, Adolfo Del; Rodriguez-Hernandez, Juan

2017-02-21

Facile procedures capable of simultaneously conferring hydrophilicity and tailored topography to surfaces of hydrophobic supports, such as polycarbonate (PC), are very attractive but rare. In this work, we describe a simple methodology to wrinkle PC surfaces after a process of (a) contacting with a photopolymerizable vinylic solution, (b) UV curing of such solutions, and (c) detachment of the formed polymer network, upon swelling in ethanol. The influence of different parameters such as contact lag time between the PC surface and the polymerizable solution, the monomer concentration and type of solvents, as well as the cross-linking degree on the formation of wrinkles, has been studied. The dimensions of the wrinkles can be tailored to some extent by altering the different parameters. Surface chemistry has been analyzed by contact angle measurements and by confocal Raman microscopy. The results are consistent with a chemical alteration of the surface and the formation of an outer hydrogel layer, which is interpenetrated into the PC structure. A mechanism of monomer diffusion and PC swelling that produces surface instabilities and wrinkling is proposed.

Exploiting the flexibility and the polarization of ferroelectric perovskite surfaces to achieve efficient photochemistry and enantiospecificity

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

Rappe, Andrew

This research project explored the catalytic properties of complex surfaces of functional materials. The PI used first-principles density functional theory (DFT) calculations to explore a tightly integrated set of properties. The physical properties of complex functional materials that influence surface chemistry were explored, including bulk and surface electric dipoles, and surface conductivity. The energetic, compositional, electronic, and chemical properties of the surfaces of these materials were explored in detail, and connections between material properties and chemical reactivity were established. This project led to 28 publications, including Nat. Comm., JACS, 3 PRL, 7 PRB, 2 ACS Nano, 2 Nano Lett., 4more » JPCL, 2 JCP, Chem. Mater., ACS Appl. Mater. Interfaces, Phys. Rev. Appl., and a U.S. Patent on surface catalysts. The key accomplishments in this project involved work in six coordinated areas: pioneering ways to control bulk dipoles in order to dynamically affect catalysis, exploring novel ways of bringing charge to the surface for redox catalysis, nonstoichiometric surfaces offering new sites for heterogeneous catalysis, illustrating how surface catalysis responds to applied pressure, catalytic growth of carbon-based materials, and new computational methods allowing more accurate exploration of molecule-surface interactions« 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.

Analysis of dissolved gas and fluid chemistry in mountainous region of Goaping river watershed in southern Taiwan

NASA Astrophysics Data System (ADS)

Tang, Kai-Wen; Chen, Cheng-Hong; Liu, Tsung-Kwei

2016-04-01

Annual rainfall in Taiwan is up to 2500 mm, about 2.5 times the average value of the world. However due to high topographic relief of the Central Mountain Range in Taiwan, groundwater storage is critical for water supply. Mountain region of the Goaping river watershed in southern Taiwan is one of the potential areas to develop groundwater recharge model. Therefore the target of this study is to understand sources of groundwater and surface water using dissolved gas and fluid chemistry. Four groundwater and 6 surface water samples were collected from watershed, 5 groundwater and 13 surface water samples were collected from downstream. All samples were analyzed for stable isotopes (hydrogen and oxygen), dissolved gases (including nitrogen, oxygen, argon, methane and carbon dioxide), noble gases (helium and radon) and major ions. Hydrogen and oxygen isotopic ratios of surface water and groundwater samples aligned along meteoric water line. For surface water, dissolved gases are abundant in N2 (>80%) and O2 (>10%); helium isotopic ratio is approximately equal to 1 RA (RA is 3He/4He ratio of air); radon-222 concentration is below the detection limit (<200 Bq/m3); and concentrations of major anions and cations are low (Na+ <20 ppm, Ca2+ < 60 ppm, Cl- <2 ppm). All these features indicate that surface waters are predominately recharged by precipitation. For groundwater, helium isotopic ratios (0.9˜0.23 RA) are lower and radon-222 concentrations (300˜6000 Bq/m3) are much higher than the surface water. Some samples have high amounts of dissolved gases, such as CH4 (>20%) or CO2 (>10%), most likely contributed by biogenic or geogenic sources. On the other hand, few samples that have temperature 5° higher than the average of other samples, show significantly high Na+ (>1000 ppm), Ca2+ (>150 ppm) and Cl- (>80 ppm) concentrations. An interaction between such groundwater and local hot springs is inferred. Watershed and downstream samples differ in dissolved gas species and fluid chemistry for groundwater and surface water. The higher hydrogen and oxygen isotopic ratios for surface water from downstream are most probably caused by evaporation. Low radon-222 concentrations of some groundwater from downstream may represent sources from different aquifers. Therefore, we conclude that surface water from downstream are recharged directly from its watershed, but groundwater are influenced by the local geological environment. Keywords: groundwater, dissolved gas, noble gas, radon in water, 3He/4He

Ionic strength effects on silicic acid (H4SiO4) sorption and oligomerization on an iron oxide surface: an interesting interplay between electrostatic and chemical forces.

PubMed

Hamid, Rossuriati Dol; Swedlund, Peter J; Song, Yantao; Miskelly, Gordon M

2011-11-01

The effect of ionic strength on reactions at aqueous interfaces can provide insights into the nature of the chemistry involved. The adsorption of H(4)SiO(4) on iron oxides at low surface silicate concentration (Γ(Si)) forms monomeric silicate complexes with Fe-O-Si linkages, but as Γ(Si) increases silicate oligomers with Si-O-Si linkages become increasingly prevalent. In this paper, the effect of ionic strength (I) on both Γ(Si) and the extent of silicate oligomerization on the ferrihydrite surface is determined at pH 4, 7, and 10, where the surface is, respectively, positive, nearly neutral, and negatively charged. At pH 4, an increase in ionic strength causes Γ(Si) to decrease at a given H(4)SiO(4) solution concentration, while the proportion of oligomers on the surface at a given Γ(Si) increases. At pH 10, the opposite is observed; Γ(Si) increases as I increases, while the proportion of surface oligomers at a given Γ(Si) decreases. Ionic strength has only a small effect on the surface chemistry of H(4)SiO(4) at pH 7, but at low Γ(Si) this effect is in the direction observed at pH 4 while at high Γ(Si) the effect is in the direction observed at pH 10. The pH where the surface has zero charge decreases from ≈8 to 6 as Γ(Si) increases so that the surface potential (Ψ) is positive at pH 4 for all Γ(Si) and at pH 7 with low Γ(Si). Likewise, Ψ < 0 at pH 10 for all Γ(Si) and at pH 7 with high Γ(Si). The diffuse layer model is used to unravel the complex and subtle interactions between surface potential (Ψ) and chemical parameters that influence interfacial silicate chemistry. This analysis reveals that the decrease in the absolute value of Ψ as I increases causes Γ(Si) to decrease or increase where Ψ is, respectively, positive or negative. Therefore, at a given Γ(Si), the solution H(4)SiO(4) concentration changes with I, and because oligomerization has a higher H(4)SiO(4) stoichiometry coefficient than monomer adsorption, this results in the observed dependence of the extent of silicate oligomerization on I.

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.

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.

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.

Understanding Particulate Matter Dynamics in the San Joaquin Valley during DISCOVER-AQ, 2013

NASA Astrophysics Data System (ADS)

Prabhakar, G.; Zhang, X.; Kim, H.; Parworth, C.; Pusede, S. E.; Wooldridge, P. J.; Cohen, R. C.; Zhang, Q.; Cappa, C. D.

2015-12-01

Air quality in the California San Joaquin Valley (SJV) during winter continues to be the worst in the state, failing EPA's 24-hour standard for particulate matter. Despite our improved understanding of the sources of particulate matter (PM) in the valley, air-quality models are unable to predict PM concentrations accurately. We aim to characterize periods of high particulate matter concentrations in the San Joaquin Valley based on ground and airborne measurements of aerosols and gaseous pollutants, during the DISCOVER-AQ campaign, 2013. A highly instrumented aircraft flew across the SJV making three transects in a repeatable pattern, with vertical spirals over select locations. The aircraft measurements were complemented by ground measurements at these locations, with extensive chemically-speciated measurements at a ground "supersite" at Fresno. Hence, the campaign provided a comprehensive three-dimensional view of the particulate and gaseous pollutants around the valley. The vertical profiles over the different sites indicate significant variability in the concentrations and vertical distribution of PM around the valley, which are most likely driven by differences in the combined effects of emissions, chemistry and boundary layer dynamics at each site. The observations suggest that nighttime PM is dominated by surface emissions of PM from residential fuel combustion, while early morning PM is strongly influenced by mixing of low-level, above-surface, nitrate-rich layers formed from dark chemistry overnight to the surface.

REGIONAL RELATIONSHIPS BETWEEN GEOMORPHIC/HYDROLOGIC PARAMETERS AND SURFACE WATER CHEMISTRY RELATIVE TO ACIDIC DEPOSITION

EPA Science Inventory

We determined geomorphic and hydrologic parameters for 144 forested, lake watersheds in the Northeast (NE) of the United States based primarily on measurements from topographic maps. hese parameters were used to test for relationships with selected surface water chemistry relevan...

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.

Comparative study of fluvial lakes in floodplains of the Elbe, Lužnice and Svratka Rivers based on hydrochemical and biological approach.

PubMed

Havlíková, Petra; Chuman, Tomáš; Janský, Bohumír

2017-11-17

The aim of the thesis was to specify key differences in chemistry and biota (zooplankton communities) among fluvial lakes in three regions of the Czech Republic: the central part of the Elbe River, the upper part of the Lužnice River and the upper part of the Svratka River. The ten studied lakes of the three regions differ in size, geology, shading, connection with the river and the level of anthropogenic impact. The following hypotheses were tested: (1) The water chemistry of fluvial lakes significantly differs in different floodplains. In the central Elbe River floodplain, there are the highest values of conductivity and concentrations of organic matter and nutrients. Fluvial lakes of the Svratka River floodplain show the lowest level of these parameters, and fluvial lakes of the upper Lužnice River have levels intermediate between the two previous regions. (2) The chemistry of fluvial lakes that have contact with the river through surface connection is significantly influenced by the river. (3) The structure of zooplankton differs in different lakes due to the geographical distance between locations, their different altitude and water chemistry. The PCA analysis of selected parameters of the water chemistry revealed a close relationship of locations in the central Elbe River floodplain on the one side and close relationship of the locations in the upper Lužnice River and Svratka River on the other. However, the amount of organic matter, nitrogen (with the exception of nitrates) and phosphorus was independent of the region. The relationship between the extent of the lake-river connection and the water chemistry was not significant. The hypothesis that the zooplankton differ in different lakes was not proved-the species composition was similar in all the lakes.

Evaluation of the Influence of Wording Changes and Course Type on Motivation Instrument Functioning in Chemistry

ERIC Educational Resources Information Center

Komperda, Regis; Hosbein, Kathryn N.; Barbera, Jack

2018-01-01

Increased understanding of the importance of the affective domain in chemistry education research has led to the development and adaptation of instruments to measure chemistry-specific affective traits, including motivation. Many of these instruments are adapted from other fields by using the word "chemistry" in place of other…

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

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.

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.

A New Retrieval Algorithm for OMI NO2: Tropospheric Results and Comparisons with Measurements and Models

NASA Technical Reports Server (NTRS)

Swartz, W. H.; Bucesla, E. J.; Lamsal, L. N.; Celarier, E. A.; Krotkov, N. A.; Bhartia, P, K,; Strahan, S. E.; Gleason, J. F.; Herman, J.; Pickering, K.

2012-01-01

Nitrogen oxides (NOx =NO+NO2) are important atmospheric trace constituents that impact tropospheric air pollution chemistry and air quality. We have developed a new NASA algorithm for the retrieval of stratospheric and tropospheric NO2 vertical column densities using measurements from the nadir-viewing Ozone Monitoring Instrument (OMI) on NASA's Aura satellite. The new products rely on an improved approach to stratospheric NO2 column estimation and stratosphere-troposphere separation and a new monthly NO2 climatology based on the NASA Global Modeling Initiative chemistry-transport model. The retrieval does not rely on daily model profiles, minimizing the influence of a priori information. We evaluate the retrieved tropospheric NO2 columns using surface in situ (e.g., AQS/EPA), ground-based (e.g., DOAS), and airborne measurements (e.g., DISCOVER-AQ). The new, improved OMI tropospheric NO2 product is available at high spatial resolution for the years 200S-present. We believe that this product is valuable for the evaluation of chemistry-transport models, examining the spatial and temporal patterns of NOx emissions, constraining top-down NOx inventories, and for the estimation of NOx lifetimes.

Climate-driven flushing of pore water in peatlands

NASA Astrophysics Data System (ADS)

Siegel, D. I.; Reeve, A. S.; Glaser, P. H.; Romanowicz, E. A.

1995-04-01

NORTHERN peatlands can act as either important sources or sinks for atmospheric carbon1,2. It is therefore important to understand how carbon cycling in these regions will respond to a changing climate. Existing carbon balance models for peatlands assume that fluid flow and advective mass transport are negligible at depth3,4, and that the effects of climate change should be essentially limited to the near-surface. Here we report the response of groundwater flow and porewater chemistry in the Glacial Lake Agassiz peat-lands of northern Minnesota to the regional drought cycle. Comparison of field observations and numerical simulations indicates that climate fluctuations of short duration may temporarily reverse the vertical direction of fluid flow through the peat, although this has little effect on water chemistry5. On the other hand, periods of drought persisting for at least 3-5 years produce striking changes in the chemistry of the pore water. These longer-term changes in hydrology influence the flux of nutrients and dissolved organic matter through the deeper peat, and therefore affect directly the rates of fermentation and methanogenesis, and the export of dissolved carbon compounds from the peatland.

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.

Reproducibility of geochemical and climatic signals in the Atlantic coral Montastraea faveolata

USGS Publications Warehouse

Smith, Joseph M.; Quinn, T.M.; Helmle, K.P.; Halley, R.B.

2006-01-01

Monthly resolved, 41-year-long stable isotopic and elemental ratio time series were generated from two separate heads of Montastraea faveolata from Looe Key, Florida, to assess the fidelity of using geochemical variations in Montastraea, the dominant reef-building coral of the Atlantic, to reconstruct sea surface environmental conditions at this site. The stable isotope time series of the two corals replicate well; mean values of ??18O and ??13C are indistinguishable between cores (compare 0.70??? versus 0.68??? for ??13C and -3.90??? versus - 3.94??? for ??18O). Mean values from the Sr/Ca time series differ by 0.037 mmol/mol, which is outside of analytical error and indicates that nonenvironmental factors are influencing the coral Sr/ Ca records at Looe Key. We have generated significant ?? 18O-sea surface temperature (SST) (R = -0.84) and Sr/ Ca-SST (R = -0.86) calibration equations at Looe Key; however, these equations are different from previously published equations for Montastraea. Variations in growth parameters or kinetic effects are not sufficient to explain either the observed differences in the mean offset between Sr/Ca time series or the disagreement between previous calibrations and our calculated ??18O-SST and Sr/Ca-SST relationships. Calibration differences are most likely due to variations in seawater chemistry in the continentally influenced waters at Looe Key. Additional geochemical replication studies of Montastraea are needed and should include multiple coral heads from open ocean localities complemented whenever possible by seawater chemistry determinations. Copyright 2006 by the American Geophysical Union.

Causes of Interannual Variability over the Southern Hemispheric Tropospheric Ozone Maximum

NASA Technical Reports Server (NTRS)

Liu, Junhua; Rodriguez, Jose M.; Steenrod, Stephen D.; Douglass, Anne R.; Logan, Jennifer A.; Olsen, Mark A.; Wargan, Krzysztog; Ziemke, Jerald R.

2017-01-01

We examine the relative contribution of processes controlling the interannual variability (IAV) of tropospheric ozone over four sub-regions of the southern hemispheric tropospheric ozone maximum (SHTOM) over a 20-year period. Our study is based on hindcast simulations from the National Aeronautics and Space Administration Global Modeling Initiative chemistry transport model (NASA GMI-CTM) of tropospheric and stratospheric chemistry, driven by assimilated Modern Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields. Our analysis shows that over SHTOM region, the IAV of the stratospheric contribution is the most important factor driving the IAV of upper tropospheric ozone (270 hectopascals), where ozone has a strong radiative effect. Over the South Atlantic region, the contribution from surface emissions to the IAV of ozone exceeds that from stratospheric input at and below 430 hectopascals. Over the South Indian Ocean, the IAV of stratospheric ozone makes the largest contribution to the IAV of ozone with little or no influence from surface emissions at 270 and 430 hectopascals in austral winter. Over the tropical South Atlantic region, the contribution from IAV of stratospheric input dominates in austral winter at 270 hectopascals and drops to less than half but is still significant at 430 hectopascals. Emission contributions are not significant at these two levels. The IAV of lightning over this region also contributes to the IAV of ozone in September and December. Over the tropical southeastern Pacific, the contribution of the IAV of stratospheric input is significant at 270 and 430 hectopascals in austral winter, and emissions have little influence.

Causes of interannual variability over the southern hemispheric tropospheric ozone maximum

NASA Astrophysics Data System (ADS)

Liu, Junhua; Rodriguez, Jose M.; Steenrod, Stephen D.; Douglass, Anne R.; Logan, Jennifer A.; Olsen, Mark A.; Wargan, Krzysztof; Ziemke, Jerald R.

2017-03-01

We examine the relative contribution of processes controlling the interannual variability (IAV) of tropospheric ozone over four sub-regions of the southern hemispheric tropospheric ozone maximum (SHTOM) over a 20-year period. Our study is based on hindcast simulations from the National Aeronautics and Space Administration Global Modeling Initiative chemistry transport model (NASA GMI-CTM) of tropospheric and stratospheric chemistry, driven by assimilated Modern Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields. Our analysis shows that over SHTOM region, the IAV of the stratospheric contribution is the most important factor driving the IAV of upper tropospheric ozone (270 hPa), where ozone has a strong radiative effect. Over the South Atlantic region, the contribution from surface emissions to the IAV of ozone exceeds that from stratospheric input at and below 430 hPa. Over the South Indian Ocean, the IAV of stratospheric ozone makes the largest contribution to the IAV of ozone with little or no influence from surface emissions at 270 and 430 hPa in austral winter. Over the tropical South Atlantic region, the contribution from IAV of stratospheric input dominates in austral winter at 270 hPa and drops to less than half but is still significant at 430 hPa. Emission contributions are not significant at these two levels. The IAV of lightning over this region also contributes to the IAV of ozone in September and December. Over the tropical southeastern Pacific, the contribution of the IAV of stratospheric input is significant at 270 and 430 hPa in austral winter, and emissions have little influence.

A comprehensive review of milk fouling on heated surfaces.

PubMed

Sadeghinezhad, E; Kazi, S N; Dahari, M; Safaei, Mohammad Reza; Sadri, Rad; Badarudin, A

2015-01-01

Heat exchanger performance degrades rapidly during operation due to formation of deposits on heat transfer surfaces which ultimately reduces service life of the equipment. Due to scaling, product deteriorates which causes lack of proper heating. Chemistry of milk scaling is qualitatively understood and the mathematical models for fouling at low temperatures have been produced but the behavior of systems at ultra high temperature processing has to be studied further to understand in depth. In diversified field, the effect of whey protein fouling along with pressure drop in heat exchangers were conducted by many researchers. Adding additives, treatment of heat exchanger surfaces and changing of heat exchanger configurations are notable areas of investigation in milk fouling. The present review highlighted information about previous work on fouling, influencing parameters of fouling and its mitigation approach and ends up with recommendations for retardation of milk fouling and necessary measures to perform the task.

Investigation of passive films on nickel Alloy 690 in lead-containing environments

NASA Astrophysics Data System (ADS)

Peng, B.; Lu, B. T.; Luo, J. L.; Lu, Y. C.; Ma, H. Y.

2008-09-01

Passive films formed on Alloy UNS N06690 were investigated in simulated crevice chemistries. It was found the role of lead in corrosion processes is strongly dependent on the pH value of the testing solutions. At pH 1.5 the effect of lead is narrowly noticeable; while at pH 12.7, lead has a significant influence on the electrochemical performance of alloy UNS N06690. The lead alters the surface morphologies at both pH and account for higher hydroxide content in the surface film at pH 12.7. The lead incorporation hinders the formation of spinel oxides during the passivation in alkaline solution. Nanoindentation tests indicate a significant lead-induced degradation in the mechanical properties of passive films. The passivation degradation is attributed to detrimental effects of lead via interrupting the dehydration process and hindering the formation of protective layers on the alloy surface.

Antibacterial Performance of Alginic Acid Coating on Polyethylene Film

PubMed Central

Karbassi, Elika; Asadinezhad, Ahmad; Lehocký, Marian; Humpolíček, Petr; Vesel, Alenka; Novák, Igor; Sáha, Petr

2014-01-01

Alginic acid coated polyethylene films were examined in terms of surface properties and bacteriostatic performance against two most representative bacterial strains, that is, Escherichia coli and Staphylococcus aureus. Microwave plasma treatment followed by brush formation in vapor state from three distinguished precursors (allylalcohol, allylamine, hydroxyethyl methacrylate) was carried out to deposit alginic acid on the substrate. Surface analyses via various techniques established that alginic acid was immobilized onto the surface where grafting (brush) chemistry influenced the amount of alginic acid coated. Moreover, alginic acid was found to be capable of bacterial growth inhibition which itself was significantly affected by the brush type. The polyanionic character of alginic acid as a carbohydrate polymer was assumed to play the pivotal role in antibacterial activity. The cell wall composition of two bacterial strains along with the substrates physicochemical properties accounted for different levels of bacteriostatic performance. PMID:25196604

Adsorption of aromatic compounds from the biodegradation of azo dyes on activated carbon

NASA Astrophysics Data System (ADS)

Faria, P. C. C.; Órfão, J. J. M.; Figueiredo, J. L.; Pereira, M. F. R.

2008-03-01

The adsorption of three selected aromatic compounds (aniline, sulfanilic acid and benzenesulfonic acid) on activated carbons with different surface chemical properties was investigated at different solution pH. A fairly basic commercial activated carbon was modified by means of chemical treatment with HNO 3, yielding an acid activated carbon. The textural properties of this sample were not significantly changed after the oxidation treatment. Equilibrium isotherms of the selected compounds on the mentioned samples were obtained and the results were discussed in relation to their surface chemistry. The influence of electrostatic and dispersive interactions involved in the uptake of the compounds studied was evaluated. The Freundlich model was used to fit the experimental data. Higher uptakes are attained when the compounds are present in their molecular form. In general, adsorption was disfavoured by the introduction of oxygen-containing groups on the surface of the activated carbon.

Aquifer susceptibility to perchlorate contamination in a highly urbanized environment

USGS Publications Warehouse

Woolfenden, Linda R.; Trefly, Michael G.

2007-01-01

Perchlorate contamination from anthropogenic sources has been released into the Rialto-Colton, California, USA, groundwater flow system since the 1940s during its production, distribution, storage, and use. Preliminary analysis of lithological, geophysical, and water-chemistry data provided new understanding of the pathways of perchlorate migration that aid in assessing the susceptibility of drinking-water supplies to contamination within the Rialto-Colton basin. Vertical migration of perchlorate into the main water-producing aquifers is restricted by an areally extensive old soil surface; however, perchlorate data indicate contamination below this soil surface. Possible pathways for the downward migration of the contaminated water include wellbore flow and discontinuities in the old soil surface. Horizontal migration of perchlorate is influenced by lithology and faults within the basin. The basin fill is a heterogeneous mixture of boulders, gravel, sand, silt, and clay, and internal faults may restrict perchlorate migration in some areas.

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.

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)

Anthropogenic disturbance of element cycles at the Earth's surface.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard

2012-08-21

The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes.

Doped and codoped silicon nanocrystals: The role of surfaces and interfaces

NASA Astrophysics Data System (ADS)

Marri, Ivan; Degoli, Elena; Ossicini, Stefano

2017-12-01

Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals differs from the one of the bulk. Theory and experiments have underlined that doping and codoping are influenced by a large number of parameters such as size, shape, passivation and chemical environment of the silicon nanocrystals. However, the connection between these parameters and dopant localization as well as the occurrence of self-purification effects are still not clear. In this review we summarize the latest progress in this fascinating research field considering free-standing and matrix-embedded Si nanocrystals both from the theoretical and experimental point of view, with special attention given to the results obtained by ab-initio calculations and to size-, surface- and interface-induced effects.

Influence of solvent polarity and supersaturation on template-induced nucleation of carbamazepine crystal polymorphs

NASA Astrophysics Data System (ADS)

Parambil, Jose V.; Poornachary, Sendhil K.; Tan, Reginald B. H.; Heng, Jerry Y. Y.

2017-07-01

Studies on the use of template surfaces to induce heterogeneous crystal nucleation have gained momentum in recent years-with potential applications in selective crystallisation of polymorphs and in the generation of seed crystals in a continuous crystallisation process. In developing a template-assisted solution crystallisation process, the kinetics of homogeneous versus heterogeneous crystal nucleation could be influenced by solute-solvent, solute-template, and solvent-template interactions. In this study, we report the effect of solvents of varying polarity on the nucleation of carbamazepine (CBZ) crystal polymorphs, a model active pharmaceutical ingredient. The experimental results demonstrate that functionalised template surfaces are effective in promoting crystallisation of either the metastable (form II) or stable (form III) polymorphs of CBZ only in moderately (methanol, ethanol, isopropanol) and low polar (toluene) solvents. A solvent with high polarity (acetonitrile) is thought to mask the template effect on heterogeneous nucleation due to strong solute-solvent and solvent-template interactions. The current study highlights that a quality-by-design (QbD) approach-considering the synergistic effects of solute concentration, solvent type, solution temperature, and template surface chemistry on crystal nucleation-is critical to the development of a template-induced crystallisation process.

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.

Surface modification of Ni–Ti alloys for stent application after magnetoelectropolishing

PubMed Central

Musaramthota, Vishal; Munroe, Norman; Datye, Amit; Dua, Rupak; Haider, Waseem; McGoron, Anthony; Rokicki, Ryszard

2015-01-01

The constant demand for new implant materials and the multidisciplinary design approaches for stent applications have expanded vastly over the past decade. The biocompatibility of these implant materials is a function of their surface characteristics such as morphology, surface chemistry, roughness, surface charge and wettability. These surface characteristics can directly influence the material's corrosion resistance and biological processes such as endothelialization. Surface morphology affects the thermodynamic stability of passivating oxides, which renders corrosion resistance to passivating alloys. Magnetoelectropolishing (MEP) is known to alter the morphology and composition of surface films, which assist in improving corrosion resistance of Nitinol alloys. This work aims at analyzing the surface characteristics of MEP Nitinol alloys by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The wettability of the alloys was determined by contact angle measurements and the mechanical properties were assessed by Nanoindentation. Improved mechanical properties were observed with the addition of alloying elements. Cyclic potentiodynamic polarization tests were performed to determine the corrosion susceptibility. Further, the alloys were tested for their cytotoxicity and cellular growth with endothelial cells. Improved corrosion resistance and cellular viability were observed with MEP surface treated alloys. PMID:25746243

Increasing the hydrophobicity degree of stonework by means of laser surface texturing: An application on Zimbabwe black granites

NASA Astrophysics Data System (ADS)

Chantada, A.; Penide, J.; Riveiro, A.; del Val, J.; Quintero, F.; Meixus, M.; Soto, R.; Lusquiños, F.; Pou, J.

2017-10-01

Tailoring the wetting characteristics of materials has gained much interest in applications related to surface cleaning in both industry and home. Zimbabwe black granite is a middle-to-fine-grained natural stone commonly used as countertops in kitchens and bathrooms. In this study, the laser texturing of Zimbabwe black granite surfaces is investigated with the aim to enhance its hydrophobic character, thus reducing the attachment of contaminants on the surface. Two laser sources (λ = 1064 and 532 nm) were used for this purpose. The treatment is based on the irradiation of the stone by a laser focused on the surface of the targeting sample. The influence of different laser processing parameters on the surface characteristics of granite (wettability, roughness, and chemistry) was statistically assessed. Most suitable laser processing parameters required to obtain the highest hydrophobicity degree were identified. It has been possible to identify the 532 nm laser wavelength as the most effective one to increase the hydrophobic degree of Zimbabwe black granite surface. The phenomenon governing wettability changes was found to be the surface roughness patterns, given the unaltered chemical surface composition after laser processing.

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.

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

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.

Representing Chemistry: How Instructional Use of Symbolic, Microscopic, and Macroscopic Mode Influences Student Conceptual Understanding in Chemistry

ERIC Educational Resources Information Center

Wood, Lorelei

2013-01-01

Chemistry as a subject is difficult to learn and understand, due in part to the specific language used by practitioners in their professional and scientific communications. The language and ways of representing chemical interactions have been grouped into three modes of representation used by chemistry instructors, and ultimately by students in…

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.

The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited

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

Henderson, Michael A.

2002-05-01

Water is perhaps the most important and most pervasive chemical on our planet. The influence of water permeates virtually all areas of biochemical, chemical and physical importance, and is especially evident in phenomena occurring at the interfaces of solid surfaces. Since 1987, when Thiel and Madey (TM) published their review titled "The Interaction of Water with Solid Surfaces: Fundamental Aspects" in Surface Science Reports, there has been considerable progress made in further understanding the fundamental interactions of water with solid surfaces. In the decade and a half, the increased capability of surface scientists to probe at the molecular-level has resultedmore » in more detailed information of the properties of water on progressively more complicated materials and under more stringent conditions. This progress in understanding the properties of water on solid surfaces is evident both in areas for which surface science methodology has traditionally been strong (catalysis and electronic materials) and also in new areas not traditionally studied by surface scientists, such as electrochemistry, photoconversion, mineralogy, adhesion, sensors, atmospheric chemistry, and tribology. Researchers in all these fields grapple with very basic questions regarding the interactions of water with solid surfaces, such as how is water adsorbed, what are the chemical and electrostatic forces that constitute the adsorbed layer, how is water thermally or non-thermally activated, and how do coadsorbates influence these properties of water. The attention paid to these and other fundamental questions in the past decade and a half has been immense. In this review, experimental studies published since the TM review are assimilated with those covered by TM to provide a current picture of the fundamental interactions of water with solid surfaces.« less

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 (...

Effects of surface charges of gold nanoclusters on long-term in vivo biodistribution, toxicity, and cancer radiation therapy.

PubMed

Wang, Jun-Ying; Chen, Jie; Yang, Jiang; Wang, Hao; Shen, Xiu; Sun, Yuan-Ming; Guo, Meili; Zhang, Xiao-Dong

2016-01-01

Gold nanoclusters (Au NCs) have exhibited great advantages in medical diagnostics and therapies due to their efficient renal clearance and high tumor uptake. The in vivo effects of the surface chemistry of Au NCs are important for the development of both nanobiological interfaces and potential clinical contrast reagents, but these properties are yet to be fully investigated. In this study, we prepared glutathione-protected Au NCs of a similar hydrodynamic size but with three different surface charges: positive, negative, and neutral. Their in vivo biodistribution, excretion, and toxicity were investigated over a 90-day period, and tumor uptake and potential application to radiation therapy were also evaluated. The results showed that the surface charge greatly influenced pharmacokinetics, particularly renal excretion and accumulation in kidney, liver, spleen, and testis. Negatively charged Au NCs displayed lower excretion and increased tumor uptake, indicating a potential for NC-based therapeutics, whereas positively charged clusters caused transient side effects on the peripheral blood system.

Seasonal and spatial variabilities in the water chemistry of prairie pothole wetlands influence the photoproduction of reactive intermediates.

PubMed

McCabe, Andrew J; Arnold, William A

2016-07-01

The hydrology and water chemistry of prairie pothole wetlands vary spatially and temporally, on annual and decadal timescales. Pesticide contamination of wetlands arising from agricultural activities is a foremost concern. Photochemical reactions are important in the natural attenuation of pesticides and may be important in limiting ecological and human exposure. Little is known, however, about the variable influence of wetland water chemistry on indirect photochemistry. In this study, seasonal water samples were collected from seven sites throughout the prairie pothole region over three years to understand the spatiotemporal dynamics of reactive intermediate photoproduction. Samples were classified by the season in which they were collected (spring, summer, or fall) and the typical hydroperiod of the wetland surface water (temporary or semi-permanent). Under photostable conditions, steady-state concentrations and apparent quantum yields or quantum yield coefficients were measured for triplet excited states of dissolved organic matter, singlet oxygen, hydroxyl radical, and carbonate radical under simulated sunlight. Steady-state concentrations and quantum yields increased on average by 15% and 40% from spring to fall, respectively. Temporary wetlands had 40% higher steady-state concentrations of reactive intermediates than semi-permanent wetlands, but 50% lower quantum yields. Computed quantum yields for reactive intermediate formation were used to predict the indirect photochemical half-lives of seven pesticides in average temporary and semi-permanent prairie pothole wetlands. As a first approximation, the predictions agree to within two orders of magnitude of previously reported half-lives. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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

One decade of research into the fate and transport of carbon-based nanomaterials - Lessons learnt and future perspectives

NASA Astrophysics Data System (ADS)

Hüffer, Thorsten; Hofmann, Thilo

2016-04-01

Carbon-based nanomaterials (CNM) exhibit unique physico-chemical properties (e.g., large surface area to volume ratios, electron delocalization), which make them promising for a great number of applications. The production, use, and disposal of CNM and CNM-containing products will inevitably result in the release of these materials into the environment. The fate and transport of CNM greatly depends on their physico-chemical properties and surrounding environmental conditions. This field of research has constantly increased over recent years. Yet little is known on how transformation processes such as changes in surface properties or aggregation influence their interaction with other environmental species (i.e., solid surfaces or contaminants). For example, changes in redox chemistry in combination with irradiation have shown to significantly alter the surface chemistry of C60 fullerenes and consequently decreased their sorption affinity towards non-polar organic contaminants [1]. The presence of natural organic matter (NOM) seems to play a major role on the aggregation of CNM; however, the results are not consistent whether this leads to an increase or decrease in interactions with solid surfaces or contaminants. Either increased interactions resulting from a higher dispersion of CNM or decreased interactions of CNM, which was assigned to an offset of "creating" new sorption sites due to increased dispersion by a reduced accessibility of polar moieties. For the latter effect, NOM was proposed to either directly compete for sorption sites on CNM surface or a blocking of CNM pores by large NOM molecules [2]. The potential consequences of these changes in surface properties of CNM on their toxic effects on microorganisms have only been partially examined. For an environmental risk assessment, data on the occurrence of CNM is obligatory but to date the environmental concentrations of CNM are still difficult to assess due to still unsolved analytical issues in matrix separation and the discrimination of CNM from naturally present particles with similar dimensions and properties (e.g., soot or colloids). Recently, progress has been made to characterize the aggregation and to determine the occurrence of (functionalized) fullerenes using asymmetrical flow field-flow fractionation coupled to a LC-HR-MS [3]. In this contribution, the major results during the last decade of environmental research into CNM will be reviewed with the focus on their analyses and characterization, and interactions with solid surfaces. References: [1] Hüffer, T., Kah, M., Hofmann, T., Schmidt, T.C. (2013) How Redox Conditions and Irradiation Affect Sorption of PAHs by Dispersed Fullerenes (nC60). Environmental Science & Technology, 47(13), 6935-6942. [2] Hüffer, T., Schroth, S., Schmidt, T.C. (2015) Influence of humic acids on sorption of alkanes by carbon nanotubes - Implications for the dominant sorption mode. Chemosphere, 119, 1169-1175. [3] Kolkman, A., Emke, E., Bauerlein, P.S., Carboni, A., Tran, D.T., terLaak, T.L., vanWezel, A.P., deVoogt, P. (2013) Analysis of (Functionalized) Fullerenes in Water Samples by Liquid Chromatography Coupled to High-Resolution Mass Spectrometry. Analytical Chemistry, 85(12), 5867-5874.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

NASA Astrophysics Data System (ADS)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Groundwater Discharges to Rivers in the Western Canadian Oil Sands Region

NASA Astrophysics Data System (ADS)

Ellis, J.; Jasechko, S.

2016-12-01

Groundwater discharges into rivers impacts the movement and fate of nutrients and contaminants in the environment. Understanding groundwater-surface water interactions is especially important in the western Canadian oil sands, where groundwater contamination risks are elevated and baseline water chemistry data is lacking, leading to substantial uncertainties about anthropogenic influences on local river quality. High salinity groundwater springs sourced from deep aquifers, comprised of Pleistocene-aged glacial meltwater, are known to discharge into many rivers in the oil sands. Understanding connections between deep aquifers and surficial waterways is important in order to determine natural inputs into these rivers and to assess the potential for injected wastewater or oil extraction fluids to enter surface waters. While these springs have been identified, their spatial distribution along rivers has not been fully characterized. Here we present river chemistry data collected along a number of major river corridors in the Canadian oil sands region. We show that saline groundwater springs vary spatially along the course of these rivers and tend to be concentrated where the rivers incise Devonian- or Cretaceous-aged aquifers along an evaporite dissolution front. Our results suggest that water sourced from Devonian aquifers may travel through bitumen-bearing Cretaceous units and discharge into local rivers, implying a strong groundwater-surface water connection in specialized locations. These findings indicate that oil sands process-affected waters that are injected at depth have the potential to move through these aquifers and reach the rivers at the surface at some time in the future. Groundwater-surface water interactions remain key to understanding the risks oil sands activities pose to aquatic ecosystems and downstream communities.

Atmospheric chemistry of hydrogen fluoride

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

Cheng, Meng -Dawn

In this study, the atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) is summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, we suggest that the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousandsmore » of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.« less

Atmospheric chemistry of hydrogen fluoride

DOE PAGES

Cheng, Meng -Dawn

2017-04-11

In this study, the atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) is summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, we suggest that the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousandsmore » of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.« less

Improving UK Air Quality Modelling Through Exploitation of Satellite Observations

NASA Astrophysics Data System (ADS)

Pope, Richard; Chipperfield, Martyn; Savage, Nick

2014-05-01

In this work the applicability of satellite observations to evaluate the operational UK Met Office Air Quality in the Unified Model (AQUM) have been investigated. The main focus involved the AQUM validation against satellite observations, investigation of satellite retrieval error types and of synoptic meteorological-atmospheric chemistry relationships simulated/seen by the AQUM/satellite. The AQUM is a short range forecast model of atmospheric chemistry and aerosols up to 5 days. It has been designed to predict potentially hazardous air pollution events, e.g. high concentrations of surface ozone. The AQUM has only been validated against UK atmospheric chemistry recording surface stations. Therefore, satellite observations of atmospheric chemistry have been used to further validate the model, taking advantage of better satellite spatial coverage. Observations of summer and winter 2006 tropospheric column NO2 from both OMI and SCIAMACHY show that the AQUM generally compares well with the observations. However, in northern England positive biases (AQUM - satellite) suggest that the AQUM overestimates column NO2; we present results of sensitivity experiments on UK emissions datasets suspected to be the cause. In winter, the AQUM over predicts background column NO2 when compared to both satellite instruments. We hypothesise that the cause is the AQUM winter night-time chemistry, where the NO2 sinks are not substantially defined. Satellite data are prone to errors/uncertainty such as random, systematic and smoothing errors. We have investigated these error types and developed an algorithm to calculate and reduce the random error component of DOAS NO2 retrievals, giving more robust seasonal satellite composites. The Lamb Weather Types (LWT), an objective method of classifying the daily synoptic weather over the UK, were used to create composite satellite maps of column NO2 under different synoptic conditions. Under cyclonic conditions, satellite observed UK column NO2 is reduced as the indicative south-westerly flow transports it away from the UK over the North Sea. However, under anticyclonic conditions, the satellite shows that the stable conditions enhance the build-up of column NO2 over source regions. The influence of wind direction on column NO2 can also be seen from space with transport leeward of the source regions.

The dopant type and amount governs the electrochemical performance of graphene platforms for the antioxidant activity quantification

NASA Astrophysics Data System (ADS)

Hui, Kai Hwee; Ambrosi, Adriano; Sofer, Zdeněk; Pumera, Martin; Bonanni, Alessandra

2015-05-01

Graphene doped with heteroatoms can show new or improved properties as compared to the original undoped material. It has been reported that the type of heteroatoms and the doping conditions can have a strong influence on the electronic and electrochemical properties of the resulting material. Here, we wish to compare the electrochemical behavior of two n-type and two p-type doped graphenes, namely boron-doped graphenes and nitrogen-doped graphenes containing different amounts of heteroatoms. We show that the boron-doped graphene containing a higher amount of dopants provides the best electroanalytical performance in terms of calibration sensitivity, selectivity and linearity of response for the detection of gallic acid normally used as the standard probe for the quantification of antioxidant activity of food and beverages. Our findings demonstrate that the type and amount of heteroatoms used for the doping have a profound influence on the electrochemical detection of gallic acid rather than the structural properties of the materials such as amounts of defects, oxygen functionalities and surface area. This finding has a profound influence on the application of doped graphenes in the field of analytical chemistry.Graphene doped with heteroatoms can show new or improved properties as compared to the original undoped material. It has been reported that the type of heteroatoms and the doping conditions can have a strong influence on the electronic and electrochemical properties of the resulting material. Here, we wish to compare the electrochemical behavior of two n-type and two p-type doped graphenes, namely boron-doped graphenes and nitrogen-doped graphenes containing different amounts of heteroatoms. We show that the boron-doped graphene containing a higher amount of dopants provides the best electroanalytical performance in terms of calibration sensitivity, selectivity and linearity of response for the detection of gallic acid normally used as the standard probe for the quantification of antioxidant activity of food and beverages. Our findings demonstrate that the type and amount of heteroatoms used for the doping have a profound influence on the electrochemical detection of gallic acid rather than the structural properties of the materials such as amounts of defects, oxygen functionalities and surface area. This finding has a profound influence on the application of doped graphenes in the field of analytical chemistry. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01045d

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

The effect of bean origin and temperature on grinding roasted coffee

NASA Astrophysics Data System (ADS)

Uman, Erol; Colonna-Dashwood, Maxwell; Colonna-Dashwood, Lesley; Perger, Matthew; Klatt, Christian; Leighton, Stephen; Miller, Brian; Butler, Keith T.; Melot, Brent C.; Speirs, Rory W.; Hendon, Christopher H.

2016-04-01

Coffee is prepared by the extraction of a complex array of organic molecules from the roasted bean, which has been ground into fine particulates. The extraction depends on temperature, water chemistry and also the accessible surface area of the coffee. Here we investigate whether variations in the production processes of single origin coffee beans affects the particle size distribution upon grinding. We find that the particle size distribution is independent of the bean origin and processing method. Furthermore, we elucidate the influence of bean temperature on particle size distribution, concluding that grinding cold results in a narrower particle size distribution, and reduced mean particle size. We anticipate these results will influence the production of coffee industrially, as well as contribute to how we store and use coffee daily.

The effect of bean origin and temperature on grinding roasted coffee.

PubMed

Uman, Erol; Colonna-Dashwood, Maxwell; Colonna-Dashwood, Lesley; Perger, Matthew; Klatt, Christian; Leighton, Stephen; Miller, Brian; Butler, Keith T; Melot, Brent C; Speirs, Rory W; Hendon, Christopher H

2016-04-18

Coffee is prepared by the extraction of a complex array of organic molecules from the roasted bean, which has been ground into fine particulates. The extraction depends on temperature, water chemistry and also the accessible surface area of the coffee. Here we investigate whether variations in the production processes of single origin coffee beans affects the particle size distribution upon grinding. We find that the particle size distribution is independent of the bean origin and processing method. Furthermore, we elucidate the influence of bean temperature on particle size distribution, concluding that grinding cold results in a narrower particle size distribution, and reduced mean particle size. We anticipate these results will influence the production of coffee industrially, as well as contribute to how we store and use coffee daily.

The effect of bean origin and temperature on grinding roasted coffee

PubMed Central

Uman, Erol; Colonna-Dashwood, Maxwell; Colonna-Dashwood, Lesley; Perger, Matthew; Klatt, Christian; Leighton, Stephen; Miller, Brian; Butler, Keith T.; Melot, Brent C.; Speirs, Rory W.; Hendon, Christopher H.

2016-01-01

Coffee is prepared by the extraction of a complex array of organic molecules from the roasted bean, which has been ground into fine particulates. The extraction depends on temperature, water chemistry and also the accessible surface area of the coffee. Here we investigate whether variations in the production processes of single origin coffee beans affects the particle size distribution upon grinding. We find that the particle size distribution is independent of the bean origin and processing method. Furthermore, we elucidate the influence of bean temperature on particle size distribution, concluding that grinding cold results in a narrower particle size distribution, and reduced mean particle size. We anticipate these results will influence the production of coffee industrially, as well as contribute to how we store and use coffee daily. PMID:27086837

Mortality tradeoff between air quality and skin cancer from changes in stratospheric ozone

NASA Astrophysics Data System (ADS)

Eastham, Sebastian D.; Keith, David W.; Barrett, Steven R. H.

2018-03-01

Skin cancer mortality resulting from stratospheric ozone depletion has been widely studied. Similarly, there is a deep body of literature on surface ozone and its health impacts, with modeling and observational studies demonstrating that surface ozone concentrations can be increased when stratospheric air mixes to the Earth’s surface. We offer the first quantitative estimate of the trade-off between these two effects, comparing surface air quality benefits and UV-related harms from stratospheric ozone depletion. Applying an idealized ozone loss term in the stratosphere of a chemistry-transport model for modern-day conditions, we find that each Dobson unit of stratospheric ozone depletion results in a net decrease in the global annual mortality rate of ~40 premature deaths per billion population (d/bn/DU). The impacts are spatially heterogeneous in sign and magnitude, composed of a reduction in premature mortality rate due to ozone exposure of ~80 d/bn/DU concentrated in Southeast Asia, and an increase in skin cancer mortality rate of ~40 d/bn/DU, mostly in Western Europe. This is the first study to quantify air quality benefits of stratospheric ozone depletion, and the first to find that marginal decreases in stratospheric ozone around modern-day values could result in a net reduction in global mortality due to competing health impact pathways. This result, which is subject to significant methodological uncertainty, highlights the need to understand the health and environmental trade-offs involved in policy decisions regarding anthropogenic influences on ozone chemistry over the 21st century.

Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

PubMed

Arenillas, Ana; Rubiera, Fernando; Pis, José J

2002-12-15

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (<800 degrees C), NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range (>800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

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.

Engineering a Biocompatible Scaffold with Either Micrometre or Nanometre Scale Surface Topography for Promoting Protein Adsorption and Cellular Response

PubMed Central

Le, Xuan; Poinern, Gérrard Eddy Jai; Ali, Nurshahidah; Berry, Cassandra M.; Fawcett, Derek

2013-01-01

Surface topographical features on biomaterials, both at the submicrometre and nanometre scales, are known to influence the physicochemical interactions between biological processes involving proteins and cells. The nanometre-structured surface features tend to resemble the extracellular matrix, the natural environment in which cells live, communicate, and work together. It is believed that by engineering a well-defined nanometre scale surface topography, it should be possible to induce appropriate surface signals that can be used to manipulate cell function in a similar manner to the extracellular matrix. Therefore, there is a need to investigate, understand, and ultimately have the ability to produce tailor-made nanometre scale surface topographies with suitable surface chemistry to promote favourable biological interactions similar to those of the extracellular matrix. Recent advances in nanoscience and nanotechnology have produced many new nanomaterials and numerous manufacturing techniques that have the potential to significantly improve several fields such as biological sensing, cell culture technology, surgical implants, and medical devices. For these fields to progress, there is a definite need to develop a detailed understanding of the interaction between biological systems and fabricated surface structures at both the micrometre and nanometre scales. PMID:23533416

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.

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

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

Robust Non-Wetting PTFE Surfaces by Femtosecond Laser Machining

PubMed Central

Liang, Fang; Lehr, Jorge; Danielczak, Lisa; Leask, Richard; Kietzig, Anne-Marie

2014-01-01

Nature shows many examples of surfaces with extraordinary wettability, which can often be associated with particular air-trapping surface patterns. Here, robust non-wetting surfaces have been created by femtosecond laser ablation of polytetrafluoroethylene (PTFE). The laser-created surface structure resembles a forest of entangled fibers, which support structural superhydrophobicity even when the surface chemistry is changed by gold coating. SEM analysis showed that the degree of entanglement of hairs and the depth of the forest pattern correlates positively with accumulated laser fluence and can thus be influenced by altering various laser process parameters. The resulting fibrous surfaces exhibit a tremendous decrease in wettability compared to smooth PTFE surfaces; droplets impacting the virgin or gold coated PTFE forest do not wet the surface but bounce off. Exploratory bioadhesion experiments showed that the surfaces are truly air-trapping and do not support cell adhesion. Therewith, the created surfaces successfully mimic biological surfaces such as insect wings with robust anti-wetting behavior and potential for antiadhesive applications. In addition, the fabrication can be carried out in one process step, and our results clearly show the insensitivity of the resulting non-wetting behavior to variations in the process parameters, both of which make it a strong candidate for industrial applications. PMID:25110862

In situ measurement and simulation of nano-magnetite mobility in porous media subject to transient salinity

NASA Astrophysics Data System (ADS)

Becker, Matthew D.; Wang, Yonggang; L. Paulsen, Jeffrey; Song, Yi-Qiao; Abriola, Linda M.; Pennell, Kurt D.

2014-12-01

Nanotechnologies have been proposed for a variety of environmental applications, including subsurface characterization, enhanced oil recovery, and in situ contaminant remediation. For such applications, quantitative predictive models will be of great utility for system design and implementation. Electrolyte chemistry, which can vary substantially within subsurface pore waters, has been shown to strongly influence nanoparticle aggregation and deposition in porous media. Thus, it is essential that mathematical models be capable of tracking changes in electrolyte chemistry and predicting its influence on nanoparticle mobility. In this work, a modified version of a multi-dimensional multispecies transport simulator (SEAWAT) was employed to model nanoparticle transport under transient electrolyte conditions. The modeling effort was supported by experimental measurements of paramagnetic magnetite (Fe3O4) nanoparticle, coated with polyacrylamide-methylpropane sulfonic acid - lauryl acrylate (nMag-PAMPS), mobility in columns packed with 40-50 mesh Ottawa sand. Column effluent analyses and magnetic resonance imaging (MRI) were used to quantify nanoparticle breakthrough and in situ aqueous phase concentrations, respectively. Experimental observations revealed that introduction of de-ionized water into the brine saturated column (80 g L-1 NaCl + 20 g L-1 CaCl2) promoted release and remobilization of deposited nanoparticles along a diagonal front, coincident with the variable density flow field. This behavior was accurately captured by the simulation results, which indicated that a two-site deposition-release model provided the best fit to experimental observations, suggesting that heterogeneous nanoparticle-surface interactions governed nanoparticle attachment. These findings illustrate the importance of accounting for both physical and chemical processes associated with changes in electrolyte chemistry when predicting nanoparticle transport behavior in subsurface formations.Nanotechnologies have been proposed for a variety of environmental applications, including subsurface characterization, enhanced oil recovery, and in situ contaminant remediation. For such applications, quantitative predictive models will be of great utility for system design and implementation. Electrolyte chemistry, which can vary substantially within subsurface pore waters, has been shown to strongly influence nanoparticle aggregation and deposition in porous media. Thus, it is essential that mathematical models be capable of tracking changes in electrolyte chemistry and predicting its influence on nanoparticle mobility. In this work, a modified version of a multi-dimensional multispecies transport simulator (SEAWAT) was employed to model nanoparticle transport under transient electrolyte conditions. The modeling effort was supported by experimental measurements of paramagnetic magnetite (Fe3O4) nanoparticle, coated with polyacrylamide-methylpropane sulfonic acid - lauryl acrylate (nMag-PAMPS), mobility in columns packed with 40-50 mesh Ottawa sand. Column effluent analyses and magnetic resonance imaging (MRI) were used to quantify nanoparticle breakthrough and in situ aqueous phase concentrations, respectively. Experimental observations revealed that introduction of de-ionized water into the brine saturated column (80 g L-1 NaCl + 20 g L-1 CaCl2) promoted release and remobilization of deposited nanoparticles along a diagonal front, coincident with the variable density flow field. This behavior was accurately captured by the simulation results, which indicated that a two-site deposition-release model provided the best fit to experimental observations, suggesting that heterogeneous nanoparticle-surface interactions governed nanoparticle attachment. These findings illustrate the importance of accounting for both physical and chemical processes associated with changes in electrolyte chemistry when predicting nanoparticle transport behavior in subsurface formations. Electronic supplementary information (ESI) available: A schematic diagram of the nMag-MRI experimental systems, description of the mathematical modeling domain, further information regarding calibration of R2 to nMag concentration in sand, comparison of one- and two-site simulations of phases 1 and 2, DLVO interaction energy profiles for the system, and a time lapse movie of the best fit two-site model simulation of the nMag experimental data. See DOI: 10.1039/c4nr05088f

Resistless lithography - selective etching of silicon with gallium doping regions

NASA Astrophysics Data System (ADS)

Abdullaev, D.; Milovanov, R.; Zubov, D.

2016-12-01

This paper presents the results for used of resistless lithography with a further reactive-ion etching (RIE) in various chemistry after local (Ga+) implantation of silicon with different doping dose and different size doped regions. We describe the different etching regimes for pattern transfer of FIB implanted Ga masks in silicon. The paper studied the influence of the implantation dose on the silicon surface, the masking effect and the mask resistance to erosion at dry etching. Based on these results we conclude about the possibility of using this method to create micro-and nanoscale silicon structures.

Changes in atmospheric CO2 - Influence of the marine biota at high latitude

NASA Technical Reports Server (NTRS)

Knox, F.; Mcelroy, M. B.

1984-01-01

Approximately half of the nitrogen and phosphorus entering deep waters of the contemporary ocean are transported from the surface in inorganic form as preformed nutrients. A simple model for ocean chemistry is presented and shown to account for the present level of atmospheric CO2. Fluctuations in preformed nutrients, modulated by changes in insolation and circulation at high latitudes, can result in significant variations in CO2. It is suggested that these changes may account for the apparent control on climate exercised by secular variations in the orbital parameters of the earth.

Cations and microbial indicators: strong relationships in waters of urban/mixed land use watersheds of Southwest, VA

NASA Astrophysics Data System (ADS)

Steele, M.; Badgley, B.

2016-12-01

Background The salinity and composition of salts in freshwater streams, rivers, and waterbodies varies substantially, often impacted by human urban, agricultural, and mining land uses. While extreme fluctuations in salinity have been shown to influence both microbial communities and biogeochemical cycles, the differential effects of specific ion species at low salinity levels is poorly understood. The objective of this study was to examine the relationship between water chemistry and microbial water quality indicators. We collected weekly grab samples from nine sub-watersheds in Southwest Virginia. Samples were measured for standard physical and chemical properties: dissolved oxygen, temperature, specific conductance, pH, calcium, magnesium, potassium, chloride, fluoride, sulfate, nitrogen species, phosphorus, and dissolved organic carbon. In addition, three types of microbial fecal indicators were measured: total coliforms, E. coli, and HF183 (a human specific genomic marker). Results The relationships within and between water chemistry and water quality indicators are complex and frequently co-correlated. Concentrations of traditional biogeochemical elements (N, P, C) were less strongly related to water quality indicators than were Ca, Mg, Na in watersheds. Ca and Mg were strongly correlated with total coliforms, r2 = 0.88 and r2 = 0.86 respectively. While potassium is very strongly related to E. coli (r2 = 0.96). Currently, we cannot reasonably explain these relationships by the land use composition or common sources within the landscape. The human specific fecal indicator was not well correlated with other microbial water quality indicators, and yet found ubiquitously across the developed watersheds and most strongly correlated with sodium concentrations (r2 = 0.84). The results suggest that 1) wastewater via subsurface flowpaths may more broadly impact surface water chemistry and quality than expected, and 2) that cation chemistry may influence the microbial community and serve as a mediator of watershed biogeochemical cycling.

Mechanised nanoparticles for drug delivery

NASA Astrophysics Data System (ADS)

Cotí, Karla K.; Belowich, Matthew E.; Liong, Monty; Ambrogio, Michael W.; Lau, Yuen A.; Khatib, Hussam A.; Zink, Jeffrey I.; Khashab, Niveen M.; Stoddart, J. Fraser

2009-09-01

Time and time again humanity is faced with a unifying global crisis that crosses the many great divides in different societies and serves to bring once segregated communities back together as a collective whole. This global community instinctively turns to science to develop the means of addressing its most pressing problems. More often than not, these forces dictate the direction that scientific research takes. This influence is no more apparent than in the field of supramolecular chemistry where, for decades now, its responsibility to tackle such issues has been put on the back burner as a consequence of a lack of platforms with which to deliver this contemporary brand of chemistry to meaningful applications. However, the tide is slowly turning as new materials emerge from the field of nanotechnology that are poised to host the many attractive attributes that are inherent in the chemistry of these supermolecules and also in the mechanostereochemistry of mechanically interlocked molecules (MIMs), which can be reused as a sequel to supramolecular chemistry. Mesoporous silica nanoparticles (SNPs) have proven to be supremely effective solid supports as their surfaces are easily functionalised with either supermolecules or MIMs. In turn, the blending of supramolecular chemistry and mechanostereochemistry with mesoporous SNPs has led to a new class of materials - namely, mechanised SNPs that are effectively biological nanoscale `bombs' that have the potential to infiltrate cells and then, upon the pulling of a chemical trigger, explode! The development of these materials has been driven by the need to devise new therapies for the treatment of cancer. Recent progress in research promises not only to control the acuteness of this widespread and insidious disease, but also to make the harsh treatment less debilitating to patients. This global scourge is the unifying force that has brought together supramolecular chemistry, mechanostereochemistry and nanotechnology, uniting these three communities for the common good. At the nanoscale level, the mechanism for the release of cargos from the confines of the nanopores in the SNPs is accomplished by way of mechanical modifications made on the surface of these functionalised supports. These mechanical motions rely on both supramolecular, i.e., host-guest complexes, and mechanostereochemical phenomena (e.g., bistable rotaxanes), which are often stimulated by changes in pH, light and redox potentials, in addition to enzymatic catalysis. The future of this field lies in the development of `smart bombs' wherein the loaded mechanised SNPs are endocytosed selectively by cancer cells, whereupon an intracellular trigger causes release of a cytotoxin, effectively leading to apoptosis. This review serves to highlight (1) the evolution of surface-functionalisation of SNPs with supermolecules and also with MIMs, (2) the mechanisms through which controlled-release of cargo from mechanised SNPs occurs, and (3) results from the in vitro application of these mechanised SNPs.

Breaking down the Boundary between High School and University Chemistry

ERIC Educational Resources Information Center

Cunningham, Natashia; Knorr, Kris; Lock, Pippa E.; Vajoczki, Susan L.

2013-01-01

This study examined some of the factors that influence students' transition from Ontario high school chemistry to university introductory chemistry. The study was a mixed-methods, multi-phase research study carried out by an undergraduate honours thesis student who had experienced some of these transition issues. Students' transition into…

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

Physical and Chemical Behaviors of HCl on Ice Surface: Insights from an XPS and NEXAFS Study

NASA Astrophysics Data System (ADS)

Kong, X.; Waldner, A.; Orlando, F.; Birrer, M.; Artiglia, L.; Ammann, M.; Bartels-Rausch, T.

2016-12-01

Ice and snow play active roles for the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. Trace gases can be taken up by ice, and physical and chemical fates of the impurities could modify surface properties significantly and consequently influence atmospheric chemistry and the climate system. However, the understanding of chemical behaviour of impurities on ice surface are very poor, which is largely limited by the difficulties to apply high sensitivity experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray photoelectron spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art near-ambient pressure photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS, on volatile surfaces, i.e. ice at temperatures approaching 0°C. XPS and NEXAFS together provide unique information of hydrogen bonding network, dopants surface concentration, dopant depth profile, and acidic dissociation on the surfaces1. Taking the advantages of the highly sensitive techniques, the adsorption, dissociation and depth profile of Hydrogen Chloride (HCl) on ice were studied. In brief, two states of Chloride on ice surface are identified from the adsorbed HCl, and they are featured with different depth profiles along the ice layers. Combining our results and previously reported constants from literatures (e.g. HCl diffusion coefficients in ice)2, a layered kinetic model has been constructed to fit the depth profiles of two states of Chloride. On the other side, pure ice and doped ice are compared for their surface structure change caused by temperature and the presence of HCl, which shows how the strong acid affect the ice surface in turn. 1. Orlando, F., et al., Top Catal 2016, 59, 591-604. 2. Huthwelker, T.; Malmstrom, M. E.; Helleis, F.; Moortgat, G. K.; Peter, T., J Phys Chem A 2004, 108, 6302-6318.

Rock-fluid chemical interactions at reservoir conditions: The influence of brine chemistry and extent of reaction

NASA Astrophysics Data System (ADS)

Anabaraonye, B. U.; Crawshaw, J.; Trusler, J. P. M.

2016-12-01

Following carbon dioxide injection in deep saline aquifers, CO2 dissolves in the formation brines forming acidic solutions that can subsequently react with host reservoir minerals, altering both porosity and permeability. The direction and rates of these reactions are influenced by several factors including properties that are associated with the brine system. Consequently, understanding and quantifying the impacts of the chemical and physical properties of the reacting fluids on overall reaction kinetics is fundamental to predicting the fate of the injected CO2. In this work, we present a comprehensive experimental study of the kinetics of carbonate-mineral dissolution in different brine systems including sodium chloride, sodium sulphate and sodium bicarbonate of varying ionic strengths. The impacts of the brine chemistry on rock-fluid chemical reactions at different extent of reactions are also investigated. Using a rotating disk technique, we have investigated the chemical interactions between the CO2-saturated brines and carbonate minerals at conditions of pressure (up to 10 MPa) and temperature (up to 373 K) pertinent to carbon storage. The changes in surface textures due to dissolution reaction were studied by means of optical microscopy and vertical scanning interferometry. Experimental results are compared to previously derived models.

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.

Electronically non-adiabatic interactions of molecules at metal surfaces

NASA Astrophysics Data System (ADS)

Wodtke, Alec M.; Tully, John C.; Auerbach, Daniel J.

When neutral molecules with low levels of vibrational excitation collide at metal surfaces, vibrational coupling to electron-hole pairs (EHPs) is not thought to be strong unless incidence energies are high. However, there is accumulating evidence that coupling of large-amplitude molecular vibration to metallic electron degrees of freedom can be much stronger even at the lowest accessible incidence energies. As reaching a chemical transition-state also involves large-amplitude vibrational motion, we pose the basic question: are electronically non-adiabatic couplings important at transition states of reactions at metal surfaces? We have indirect evidence in at least one example that the dynamics and rates of chemical reactions at metal surfaces may be strongly influenced by electronically non-adiabatic coupling. This implies that theoretical approaches relying on the Born-Oppenheimer approximation (BOA) may not accurately reflect the nature of transition-state traversal in reactions of catalytic importance. Developing a predictive understanding of surface reactivity beyond the BOA represents one of the most important challenges to current research in physical chemistry. This article reviews the experimental evidence and underlying theoretical framework concerning these and related topics.

Filaments in curved streamlines: rapid formation of Staphylococcus aureus biofilm streamers

NASA Astrophysics Data System (ADS)

Kim, Minyoung Kevin; Drescher, Knut; Pak, On Shun; Bassler, Bonnie L.; Stone, Howard A.

2014-06-01

Biofilms are surface-associated conglomerates of bacteria that are highly resistant to antibiotics. These bacterial communities can cause chronic infections in humans by colonizing, for example, medical implants, heart valves, or lungs. Staphylococcus aureus, a notorious human pathogen, causes some of the most common biofilm-related infections. Despite the clinical importance of S. aureus biofilms, it remains mostly unknown how physical effects, in particular flow, and surface structure influence biofilm dynamics. Here we use model microfluidic systems to investigate how environmental factors, such as surface geometry, surface chemistry, and fluid flow affect biofilm development of S. aureus. We discovered that S. aureus rapidly forms flow-induced, filamentous biofilm streamers, and furthermore if surfaces are coated with human blood plasma, streamers appear within minutes and clog the channels more rapidly than if the channels are uncoated. To understand how biofilm streamer filaments reorient in flows with curved streamlines to bridge the distances between corners, we developed a mathematical model based on resistive force theory of slender filaments. Understanding physical aspects of biofilm formation of S. aureus may lead to new approaches for interrupting biofilm formation of this pathogen.

Filaments in curved flow: Rapid formation of Staphylococcus aureus biofilm streamers

NASA Astrophysics Data System (ADS)

Kim, Min Young; Drescher, Knut; Pak, On Shun; Bassler, Bonnie L.; Stone, Howard A.

2014-03-01

Biofilms are surface-associated conglomerates of bacteria that are highly resistant to antibiotics. These bacterial communities can cause chronic infections in humans by colonizing, for example, medical implants, heart valves, or lungs. Staphylococcus aureus, a notorious human pathogen, causes some of the most common biofilm-related infections. Despite the clinical importance of S. aureus biofilms, it remains mostly unknown how physical effects, in particular flow, and surface structure influence biofilm dynamics. Here we use model microfluidic systems to investigate how environmental factors, such as surface geometry, surface chemistry, and fluid flow affect biofilm development in S. aureus.We discovered that S. aureus rapidly forms flow-induced, filamentous biofilm streamers, and furthermore if surfaces are coated with human blood plasma, streamers appear within minutes and clog the channels more rapidly than if the channels are uncoated. To understand how biofilm streamer filaments reorient in curved flow to bridge the distances between corners, we developed a mathematical model based on resistive force theory and slender filaments. Understanding physical aspects of biofilm formation in S. aureus may lead to new approaches for interrupting biofilm formation of this pathogen.

The lanthanide contraction beyond coordination chemistry

DOE PAGES

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.; ...

2016-04-06

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

The lanthanide contraction beyond coordination chemistry

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

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

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.

Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

NASA Astrophysics Data System (ADS)

Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

2018-01-01

Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.

PubMed

Taylor, Martin J; Jiang, Li; Reichert, Joachim; Papageorgiou, Anthoula C; Beaumont, Simon K; Wilson, Karen; Lee, Adam F; Barth, Johannes V; Kyriakou, Georgios

2017-04-20

Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.

Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts

PubMed Central

2017-01-01

Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation. PMID:29225721

Solute sources in stream water during consecutive fall storms in a northern hardwood forest watershed: A combined hydrological, chemical and isotopic approach

USGS Publications Warehouse

Mitchell, M.J.; Piatek, K.B.; Christopher, S.; Mayer, B.; Kendall, C.; McHale, P.

2006-01-01

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO 3- (??15N and ??18O) and SO 42- (??34S and ??18O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14-18, 18.5 mm; Storm 2: Sept. 21-24, 33 mm; Storm 3: Sept. 27-29, 42.9 mm; Storm 4: Oct. 16-21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in Cb (sum of base cations), Si, NO 3- , and SO 42- , DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO 42- and NO 3- . There was a strong inverse relationship between SO 42- concentrations and ??34S values suggesting the importance of S biogeochemical redox processes in contributing to SO 42- export. The isotopic composition of NO 3- in stream water indicated that this N had been microbially processed. Linkages between SO 42- and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO 3- suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change. ?? Springer 2006.

For the Love of Learning Science: Connecting Learning Orientation and Career Productivity in Physics and Chemistry

ERIC Educational Resources Information Center

Hazari, Zahra; Potvin, Geoff; Tai, Robert H.; Almarode, John

2010-01-01

An individual's motivational orientation serves as a drive to action and can influence their career success. This study examines how goal orientation toward the pursuit of a graduate degree in physics and chemistry influences later success outcomes of practicing physicists and chemists. Two main categories of goal orientation are examined in this…

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...

A two-dimensional atmospheric chemistry modeling investigation of Earth's Phanerozoic O3 and near-surface ultraviolet radiation history

NASA Astrophysics Data System (ADS)

Harfoot, Michael B. J.; Beerling, David J.; Lomax, Barry H.; Pyle, John A.

2007-04-01

We use the Cambridge two-dimensional (2-D) chemistry-radiation transport model to investigate the implications for column O3 and near-surface ultraviolet radiation (UV), of variations in atmospheric O2 content over the Phanerozoic (last 540 Myr). Model results confirm some earlier 1-D model investigations showing that global annual mean O3 column increases monotonically with atmospheric O2. Sensitivity studies indicate that changes in temperature and N2O exert a minor influence on O3 relative to O2. We reconstructed Earth's O3 history by interpolating the modeled relationship between O3 and O2 onto two Phanerozoic O2 histories. Our results indicate that the largest variation in Phanerozoic column O3 occurred between 400 and 200 Myr ago, corresponding to a rise in atmospheric O2 to ˜1.5 times the present atmospheric level (PAL) and subsequent fall to ˜0.5 PAL. The O3 response to this O2 decline shows latitudinal differences, thinning most at high latitudes (30-40 Dobson units (1 DU = 0.001 atm cm) at 66°N) and least at low latitudes (5-10 DU at 9°N) where a "self-healing" effect is evident. This O3 depletion coincides with significant increases in the near-surface biologically active UV radiation at high latitudes, +28% as weighted by the Thimijan spectral weighting function. O3 and UV changes were exacerbated when we incorporated a direct feedback of the terrestrial biosphere on atmospheric chemistry, through enhanced N2O production as the climate switched from an icehouse to a greenhouse mode. On the basis of a summary of field and laboratory experimental evidence, we suggest that these UV radiation increases may have exerted subtle rather than catastrophic effects on ecosystem processes.

Surface chemistry of photoluminescent F8BT conjugated polymer nanoparticles determines protein corona formation and internalization by phagocytic cells.

PubMed

Ahmad Khanbeigi, Raha; Abelha, Thais Fedatto; Woods, Arcadia; Rastoin, Olivia; Harvey, Richard D; Jones, Marie-Christine; Forbes, Ben; Green, Mark A; Collins, Helen; Dailey, Lea Ann

2015-03-09

Conjugated polymer nanoparticles are being developed for a variety of diagnostic and theranostic applications. The conjugated polymer, F8BT, a polyfluorene derivative, was used as a model system to examine the biological behavior of conjugated polymer nanoparticle formulations stabilized with ionic (sodium dodecyl sulfate; F8BT-SDS; ∼207 nm; -31 mV) and nonionic (pegylated 12-hydroxystearate; F8BT-PEG; ∼175 nm; -5 mV) surfactants, and compared with polystyrene nanoparticles of a similar size (PS200; ∼217 nm; -40 mV). F8BT nanoparticles were as hydrophobic as PS200 (hydrophobic interaction chromatography index value: 0.96) and showed evidence of protein corona formation after incubation with serum-containing medium; however, unlike polystyrene, F8BT nanoparticles did not enrich specific proteins onto the nanoparticle surface. J774A.1 macrophage cells internalized approximately ∼20% and ∼60% of the F8BT-SDS and PS200 delivered dose (calculated by the ISDD model) in serum-supplemented and serum-free conditions, respectively, while cell association of F8BT-PEG was minimal (<5% of the delivered dose). F8BT-PEG, however, was more cytotoxic (IC50 4.5 μg cm(-2)) than F8BT-SDS or PS200. The study results highlight that F8BT surface chemistry influences the composition of the protein corona, while the properties of the conjugated polymer nanoparticle surfactant stabilizer used determine particle internalization and biocompatibility profile.

Influence of School Characteristics on the Achievement of Secondary School Chemistry Students in the Cognitive Science Process Skill of Evaluation in Kenya

ERIC Educational Resources Information Center

Anditi, Zephania O.; Okere, Mark, I. O.; Muchiri, Daniel R.

2013-01-01

Chemistry is one of the subjects that students sit for in the Kenya Certificate of Secondary Education (KCSE). The attainment of students in chemistry in KCSE has been quite low. An analysis of the past Chemistry examination papers taken in KCSE reveals that the papers test students' competencies in various aspects of Cognitive Science Process…

Tectonic evolution of the terrestrial planets.

PubMed

Head, J W; Solomon, S C

1981-07-03

The style and evolution of tectonics on the terrestrial planets differ substantially. The style is related to the thickness of the lithosphere and to whether the lithosphere is divided into distinct, mobile plates that can be recycled into the mantle, as on Earth, or is a single spherical shell, as on the moon, Mars, and Mercury. The evolution of a planetary lithosphere and the development of plate tectonics appear to be influenced by several factors, including planetary size, chemistry, and external and internal heat sources. Vertical tectonic movement due to lithospheric loading or uplift is similar on all of the terrestrial planets and is controlled by the local thickness and rheology of the lithosphere. The surface of Venus, although known only at low resolution, displays features both similar to those on Earth (mountain belts, high plateaus) and similar to those on the smaller planets (possible impact basins). Improved understanding of the tectonic evolution of Venus will permit an evaluation of the relative roles of planetary size and chemistry in determining evolutionary style.

Ozone reaction with interior building materials: Influence of diurnal ozone variation, temperature and humidity

NASA Astrophysics Data System (ADS)

Rim, Donghyun; Gall, Elliott T.; Maddalena, Randy L.; Nazaroff, William W.

2016-01-01

Elevated tropospheric ozone concentrations are associated with increased morbidity and mortality. Indoor ozone chemistry affects human exposure to ozone and reaction products that also may adversely affect health and comfort. Reactive uptake of ozone has been characterized for many building materials; however, scant information is available on how diurnal variation of ambient ozone influences ozone reaction with indoor surfaces. The primary objective of this study is to investigate ozone-surface reactions in response to a diurnally varying ozone exposure for three common building materials: ceiling tile, painted drywall, and carpet tile. A secondary objective is to examine the effects of air temperature and humidity. A third goal is to explore how conditioning of materials in an occupied office building might influence subsequent ozone-surface reactions. Experiments were performed at bench-scale with inlet ozone concentrations varied to simulate daytime (ozone elevated) and nighttime (ozone-free in these experiments) periods. To simulate office conditions, experiments were conducted at two temperatures (22 °C and 28 °C) and three relative humidity values (25%, 50%, 75%). Effects of indoor surface exposures were examined by placing material samples in an occupied office and repeating bench-scale characterization after exposure periods of 1 and 2 months. Deposition velocities were observed to be highest during the initial hour of ozone exposure with slow decrease in the subsequent hours of simulated daytime conditions. Daily-average ozone reaction probabilities for fresh materials are in the respective ranges of (1.7-2.7) × 10-5, (2.8-4.7) × 10-5, and (3.0-4.5) × 10-5 for ceiling tile, painted drywall, and carpet tile. The reaction probability decreases by 7%-47% across the three test materials after two 8-h periods of ozone exposure. Measurements with the samples from an occupied office reveal that deposition velocity can decrease or increase with time. Influence of temperature and humidity on ozone-surface reactivity was not strong.

Characterization of boronized graphite in NSTX-U and its effect on plasma performance

NASA Astrophysics Data System (ADS)

Bedoya, Felipe; Allain, Jean Paul; Kaita, Robert; Skinner, Charles; University of Illinois Team; Princeton Plasma Physics Laboratory Collaboration

2017-10-01

Plasma Facing Components (PFC) conditioning can have a crucial influence in plasma performance in tokamak machines. The National Spherical Torus Experiment (NSTX-U) used boronization as the main wall conditioning technique during the FY16 experimental campaign. The Materials Analysis Particle Probe (MAPP), a characterization facility, was used to investigate the surface of ATJ graphite exposed to boronization and plasma in the tokamak using X-ray Photoelectron Spectroscopy (XPS). The measurements showed that plasma induced oxidation plays a critical role in the chemical evolution of the surfaces and as a consequence in plasma performance. Additionally, ex-vessel in-situ laboratory experiments and post-mortem studies of extracted NSTX-U tiles were performed to complement the observations made with MAPP, including controlled D irradiations and XPS depth profiles. These three methodologies show congruent results where D exposures increase the oxygen concentration between 20-30%, highlighting the influence of these two species on the chemistry of the samples. USDOE Contract DE-AC02-09CH11466, USDOE Contract DE-SC0010717 and Award Number DE-SC0012890.

Ocean acidification adversely influences metabolism, extracellular pH and calcification of an economically important marine bivalve, Tegillarca granosa.

PubMed

Zhao, Xinguo; Shi, Wei; Han, Yu; Liu, Saixi; Guo, Cheng; Fu, Wandong; Chai, Xueliang; Liu, Guangxu

2017-04-01

Oceanic uptake of CO 2 from the atmosphere has significantly reduced surface seawater pH and altered the carbonate chemistry within, leading to global Ocean Acidification (OA). The blood clam, Tegillarca granosa, is an economically and ecologically significant marine bivalve that is widely distributed along the coastal and estuarine areas of Asia. To investigate the physiological responses to OA, blood clams were exposed to ambient and three reduced seawater pH levels (8.1, 7.8, 7.6 and 7.4) for 40 days, respectively. Results obtained suggest that OA suppresses the feeding activity and aerobic metabolism, but elevates proteins catabolism of blood clams. OA also causes extracellular acidosis and decreases haemolymph Ca 2+ concentration. In addition, our data also suggest that OA impairs the calcification process and inner shell surface integrity. Overall, OA adversely influences metabolism, acid-base status and calcification of blood clams, subsequently leading to a decrease in the fitness of this marine bivalve species. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabrication of biomimetic nanomaterials and their effect on cell behavior

NASA Astrophysics Data System (ADS)

Porri, Teresa Jane

Cells in vivo respond to an intricate combination of chemical and mechanical signals. The corneal epithelium, a structure which prevents the admission of bacteria and undesirable molecules into the eye, grows on a basement membrane which presents both nanoscale topographic and adhesive chemical signals. An effective approach to biomaterials design takes advantage of the synergistic effects of the multiple cellular inputs which are available to engineer cell-substrate interactions. We have previously demonstrated the effects of nanoscale topography on a variety of corneal epithelial cell behaviors. To gain a better understanding of cell-level control in vivo, we employ a systems-level approach which looks at the effect of nanoscale topography in conjunction with a biomimetic surface chemistry. First, we discuss a novel method of fabricating nanoscale topography through templated electroless deposition of gold into PVP-coated polycarbonate membranes. This technique creates nanowires of gold with an uniform outer diameter that is dependent upon the size of the pores in the membrane used, and a nanowire length that is dependent upon the extent of etching into the polymer membrane. The gold nanowires can be modified with self-assembled monolayers (SAMs) of alkanethiols. Using these substrates, we study the effect of topographic length scale and surface chemistry on cells attached to a discontinuous nanoscale topography, and find a transition in cellular behavior at a length scale (between 600 and 2000 nm inter-wire spacing) that is commensurate with the transition length scale seen on surfaces presenting continuous grooves and ridges. Secondly, we study the effect of non-fouling peptide-modified SAMs on cellular behavior. We examine the effect of co-presented RGD and AG73 peptides and show that cell spreading is a function of the relative ratios of RGD and AG73 present on the surface. Finally, we explore the combinatorial effects of biologically relevant chemistry with anisotropic nanoscale topography with dimensions that vary from the micron to the nanoscale. We show that integrin binding, syndecan binding, and topographic length scale each independently influence epithelial cell response to nanoscale features, lending a high degree of control over cell morphologic responses.

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

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Pfrang, Christian; Pöschl, Ulrich

2010-05-01

Aerosols are ubiquitous in the atmosphere and have strong effects on climate and public health. Gas-particle interactions can significantly change the physical and chemical properties of aerosols such as toxicity, reactivity, hygroscopicity and radiative properties. Chemical reactions and mass transport lead to continuous transformation and changes in the composition of atmospheric aerosols ("chemical aging"). Resistor model formulations are widely used to describe and investigate heterogeneous reactions and multiphase processes in laboratory, field and model studies of atmospheric chemistry. The traditional resistor models, however, are usually based on simplifying assumptions such as steady state conditions, homogeneous mixing, and limited numbers of non-interacting species and processes. In order to overcome these limitations, Pöschl, Rudich and Ammann have developed a kinetic model framework (PRA framework) with a double-layer surface concept and universally applicable rate equations and parameters for mass transport and chemical reactions at the gas-particle interface of aerosols and clouds [1]. Based on the PRA framework, we present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB) [2]. The model includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical life-times of multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (~10-10 cm2 s-1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models. References [1] Pöschl et al., Atmos. Chem. and Phys., 7, 5989-6023 (2007). [2] Shiraiwa et al., Atmos. Chem. Phys. Discuss., 10, 281-326 (2010).

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.

Tuning filler shape, surface chemistry and ion content in nanofilled polymer electrolytes

NASA Astrophysics Data System (ADS)

Ganapatibhotla, Lalitha V. N. R.

We investigate how nanofiller surface chemistry and aspect ratio affect the performance of nanofilled solid polymer electrolytes. Polymer-based electrolytes are an attractive alternative to the organic electrolytes currently used in lithium ion batteries. We characterize acidic nanoparticle filled electrolytes and compare them to neutral particle-filled electrolytes previously measured in our lab. Dielectric spectroscopy measurements indicate that the highest increase in conductivity occurs at the eutectic composition (EO/Li=10) and is independent of filler surface chemistry. We measure PEO dynamics using quasi-elastic neutron scattering and do not observe any change in polymer dynamics with particle surface chemistry. When we examine the elastic incoherent structure factor associated with the rotational process, fillers are found to restrict the rotation of the highly conducting PEO6:LiClO4 tunnels. At the eutectic composition, these tunnels are stabilized at the filler surface even above PEO melting temperature. Marginal stability theory predicts formation of alternating layers of coexisting phases at the eutectic composition. We propose a new mechanism, via stabilization of alternating layers of PEO and highly conducting PEO 6:LiClO4 tunnels at the filler surface. When compared to spherical particles, more such structures would be stabilized at a filler surface with high aspect ratio. Consistent with this hypothesis, neutral gamma-Al2O3 nanowhiskers (2-4 nm in diameter and 200-400 nm in length) intensify the effect of neutral gamma-Al 2O3 nanoparticles. The diameters of the two fillers are similar, but the change in aspect ratio (1 to 100) improves conductivity by a factor of 5. This enhancement occurs at battery operation temperatures! Although the change in aspect ratio does not affect thermal transitions and segmental dynamics at optimal whisker loading, the rotation of PEO6 remnants is distinct at the eutectic composition. Because the mechanism by which nanofillers enhance conductivity is related to stabilization of conducting structures at the filler-electrolyte interface, we determine the interface morphology using neutron reflectometry. For this, we spin-coat the unfilled electrolytes EO/Li = 8, 10 on sapphire substrate, which has the same surface chemistry as alpha-Al2O3. When freshly-spin coated on sapphire substrate, the non-eutectic sample does not exhibit any segregation of layers. The freshly spin-coated eutectic sample forms layers with alternating high and low salt concentrations, very similar to the eutectic lamellae predicted by the marginal stability theory for eutectic solidification. Such lamellae do not develop further when the sample is annealed at eutectic temperature and the salt concentration in the polymer decreases gradually away from the surface of sapphire. To take fullest advantage of the surface mechanism and obtain larger increases in conductivity we tailor the aspect ratio of high aspect ratio fillers. Commercial availability of alumina nanowhiskers is limited to neutral surface chemistry and aspect ratio of 100, cellulose nanowhiskers provide a model system where a wide range of surface chemistries may be accessed with variable aspect ratio. We synthesized cellulose whiskers of two different aspect ratios [cotton whiskers: aspect ratio ˜ 10, acetobacter whiskers: aspect ratio ˜ 200] and tested their influence on conductivity and morphology of polymer electrolytes. Similar to all fillers studied in this work, both types of cellulose whiskers provide highest increase in conductivity at the eutectic composition, with the longer acetobacter whiskers providing a marginally higher increase than the cotton whiskers. Although both cellulose whiskers do not alter the crystallinity or glass transition temperature at the optimal 1 wt% loading, they amplify the faint cold crystallization behavior observed in the unfilled eutectic electrolyte without changing the overall crystallinity. At the non-eutectic compositions, cellulose whiskers behave similar to the acidic nanoparticles. To determine the function of nanofillers in entire composition range of the phase diagram, we extend the range of measurements on the nanofilled PEO+LiClO4 electrolyte to EO/Li = 4 to 100. Because PEO+LiAsF 6 electrolytes have similar phase diagram as the PEO+LiClO4 electrolytes, we augment the study of nanofilled PEO+LiAsF6 complexes to the PEO+LiClO4 electrolytes. At compositions near the high and low ends of the phase diagram, the effect of nanofillers on conductivity is governed by reduction in crystallinity of PEO and PEO-salt complexes. In the absence of PEO6, fillers interact directly with PEO and suppress crystallization. This is consistent with the reflectometry experiment where sapphire surface prefers to interact with the salt-rich layers. Around the eutectic composition fillers restrict the highly conducting PEO6 complex at their surface and any increase in conductivity is due to stabilization of these conducting tunnels. For room temperature applications, lithium hexafluoroarsenate seems to be the better salt than lithium perchlorate. At temperatures higher than the eutectic temperature (50°C), conductivity levels off at the value set by the eutectic composition. (Abstract shortened by ProQuest.).

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 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

Predicting fire frequency with chemistry and climate

Treesearch

Richard P. Guyette; Michael C. Stambaugh; Daniel C. Dey; Rose-Marie Muzika

2012-01-01

A predictive equation for estimating fire frequency was developed from theories and data in physical chemistry, ecosystem ecology, and climatology. We refer to this equation as the Physical Chemistry Fire Frequency Model (PC2FM). The equation was calibrated and validated with North American fire data (170 sites) prior to widespread industrial influences (before ...

The Role of Teacher Questions in the Chemistry Classroom

ERIC Educational Resources Information Center

Dohrn, Sofie Weiss; Dohn, Niels Bonderup

2018-01-01

The purpose of this study was to investigate how a chemistry teacher's questions influence the classroom discourse. It presents a fine-grained analysis of the rich variety of one teacher's questions and the roles they play in an upper secondary chemistry classroom. The study identifies six different functions for the teacher's questions:…

Intuitive Judgments Govern Students' Answering Patterns in Multiple-Choice Exercises in Organic Chemistry

ERIC Educational Resources Information Center

Graulich, Nicole

2015-01-01

Research in chemistry education has revealed that students going through their undergraduate and graduate studies in organic chemistry have a fragmented conceptual knowledge of the subject. Rote memorization, rule-based reasoning, and heuristic strategies seem to strongly influence students' performances. There appears to be a gap between what we…

The Influence of PBL on Students' Self-Efficacy Beliefs in Chemistry

ERIC Educational Resources Information Center

Mataka, Lloyd M.; Grunert Kowalske, Megan

2015-01-01

A convergent mixed methods research study was used to investigate whether or not undergraduate students who participated in a problem-based learning (PBL) laboratory environment improved their self-efficacy beliefs in chemistry. The Chemistry Attitude and Experience Questionnaire (CAEQ) was used as a pre- and post-test to determine changes in…

Laser-Excited Opto-Acoustic Pulses in a Flame

DTIC Science & Technology

1981-06-01

I. INTRODUCTION ........... ....................... . A. Laser Probes and Combustion Chemistry ............. ... B. Cpto...unweighted least-squares fit ...... ................ 32 |Z I: **. t•I U 5-u•. ,. I. .-IRODUCTION A. Laser Probes and Combustion Chemistry The...influencing the chemistry . Although th; presence of particulate matter can be a serious problem, extremes of temperature and pressure offer no hostility

Active molecular iodine photochemistry in the Arctic

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

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in Februarymore » 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.« less

Active molecular iodine photochemistry in the Arctic

DOE PAGES

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.; ...

2017-09-05

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I -) measurements, which were conducted near Utqiagvik, AK,more » in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na +, consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. Furthermore, these results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.« less

Active molecular iodine photochemistry in the Arctic

NASA Astrophysics Data System (ADS)

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.; Tanner, David; Newburn, Matt K.; Walker, Lawrence; Moore, Ronald J.; Huey, L. G.; Alexander, Liz; Shepson, Paul B.; Pratt, Kerri A.

2017-09-01

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I- measurements showed enrichments of up to ˜1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

Active molecular iodine photochemistry in the Arctic.

PubMed

Raso, Angela R W; Custard, Kyle D; May, Nathaniel W; Tanner, David; Newburn, Matt K; Walker, Lawrence; Moore, Ronald J; Huey, L G; Alexander, Liz; Shepson, Paul B; Pratt, Kerri A

2017-09-19

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2 ) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I - ) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I - measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I - /Na + , consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.

Effect of perfluorodecyltrichlorosilane on the surface properties and anti-corrosion behavior of poly(dimethylsiloxane)-ZnO coatings

NASA Astrophysics Data System (ADS)

Arukalam, Innocent O.; Meng, Meijiang; Xiao, Haigang; Ma, Yuantai; Oguzie, Emeka E.; Li, Ying

2018-03-01

Poly(dimethylsiloxane)-ZnO coatings modified with different amounts of perfluorodecyltrichlorosilane (FDTS) were prepared using sol-gel technique. The results of field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) examinations showed that the surface structures and roughness of the coatings were respectively influenced by the increasing addition of FDTS. The water contact angle measurements showed maximum value of 130.52° with the 0.10 g FDTS-modified coating sample. The X-ray photoelectron spectroscopy (XPS) results indicated the coatings' hydrophobicity was also influenced by surface chemistry. The FTIR-ATR characterization results showed there was remarkable increase in the crystallinity of 0.10 g FDTS-modified coating after modification, and was confirmed by differential scanning calorimetry (DSC) analysis of crystallization temperature and the X-ray diffraction (XRD) results with an estimation of 71.29% percent crystallinity. The mechanical properties of the coatings were also conducted. The EIS measurements for anti-corrosion behavior showed that 0.10 g FDTS-modified coating had the highest barrier performance and lowest rate of degradation. Indeed, the obtained data have demonstrated that 0.10 g (≈ 0.18%) FDTS produced the most significantly effect on the surface and barrier properties of the coatings and thus, can effectively be used for anti-corrosion application in the marine environments.

Mineral Ecology: Surface Specific Colonization and Geochemical Drivers of Biofilm Accumulation, Composition, and Phylogeny

PubMed Central

Jones, Aaron A.; Bennett, Philip C.

2017-01-01

This study tests the hypothesis that surface composition influences microbial community structure and growth of biofilms. We used laboratory biofilm reactors (inoculated with a diverse subsurface community) to explore the phylogenetic and taxonomic variability in microbial communities as a function of surface type (carbonate, silicate, aluminosilicate), media pH, and carbon and phosphate availability. Using high-throughput pyrosequencing, we found that surface type significantly controlled ~70–90% of the variance in phylogenetic diversity regardless of environmental pressures. Consistent patterns also emerged in the taxonomy of specific guilds (sulfur-oxidizers/reducers, Gram-positives, acidophiles) due to variations in media chemistry. Media phosphate availability was a key property associated with variation in phylogeny and taxonomy of whole reactors and was negatively correlated with biofilm accumulation and α-diversity (species richness and evenness). However, mineral-bound phosphate limitations were correlated with less biofilm. Carbon added to the media was correlated with a significant increase in biofilm accumulation and overall α-diversity. Additionally, planktonic communities were phylogenetically distant from those in biofilms. All treatments harbored structurally (taxonomically and phylogenetically) distinct microbial communities. Selective advantages within each treatment encouraged growth and revealed the presence of hundreds of additional operational taxonomix units (OTU), representing distinct consortiums of microorganisms. Ultimately, these results provide evidence that mineral/rock composition significantly influences microbial community structure, diversity, membership, phylogenetic variability, and biofilm growth in subsurface communities. PMID:28400754

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.

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.

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.

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

Effect of bioactive extruded PLA/HA composite films on focal adhesion formation of preosteoblastic cells.

PubMed

Persson, Maria; Lorite, Gabriela S; Kokkonen, Hanna E; Cho, Sung-Woo; Lehenkari, Petri P; Skrifvars, Mikael; Tuukkanen, Juha

2014-09-01

The quality of the initial cell attachment to a biomaterial will influence any further cell function, including spreading, proliferation, differentiation and viability. Cell attachment is influenced by the material's ability to adsorb proteins, which is related to the surface chemistry and topography of the material. In this study, we incorporated hydroxyapatite (HA) particles into a poly(lactic acid) (PLA) composite and evaluated the surface structure and the effects of HA density on the initial cell attachment in vitro of murine calvarial preosteoblasts (MC3T3-EI). Scanning electron microscopy (SEM), atomic force microscopy (AFM) and infrared spectroscopy (FTIR) showed that the HA particles were successfully incorporated into the PLA matrix and located at the surface which is of importance in order to maintain the bioactive effect of the HA particles. SEM and AFM investigation revealed that the HA density (particles/area) as well as surface roughness increased with HA loading concentration (i.e. 5, 10, 15 and 20wt%), which promoted protein adsorption. Furthermore, the presence of HA on the surface enhanced cell spreading, increased the formation of actin stress fibers and significantly improved the expression of vinculin in MC3T3-E1 cells which is a key player in the regulation of cell adhesion. These results suggest the potential utility of PLA/HA composites as biomaterials for use as a bone substitute material and in tissue engineering applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamic contact angle cycling homogenizes heterogeneous surfaces.

PubMed

Belibel, R; Barbaud, C; Mora, L

2016-12-01

In order to reduce restenosis, the necessity to develop the appropriate coating material of metallic stent is a challenge for biomedicine and scientific research over the past decade. Therefore, biodegradable copolymers of poly((R,S)-3,3 dimethylmalic acid) (PDMMLA) were prepared in order to develop a new coating exhibiting different custom groups in its side chain and being able to carry a drug. This material will be in direct contact with cells and blood. It consists of carboxylic acid and hexylic groups used for hydrophilic and hydrophobic character, respectively. The study of this material wettability and dynamic surface properties is of importance due to the influence of the chemistry and the potential motility of these chemical groups on cell adhesion and polymer kinetic hydrolysis. Cassie theory was used for the theoretical correction of contact angles of these chemical heterogeneous surfaces coatings. Dynamic Surface Analysis was used as practical homogenizer of chemical heterogeneous surfaces by cycling during many cycles in water. In this work, we confirmed that, unlike receding contact angle, advancing contact angle is influenced by the difference of only 10% of acidic groups (%A) in side-chain of polymers. It linearly decreases with increasing acidity percentage. Hysteresis (H) is also a sensitive parameter which is discussed in this paper. Finally, we conclude that cycling provides real information, thus avoiding theoretical Cassie correction. H(10)is the most sensible parameter to %A. Copyright © 2016 Elsevier B.V. All rights reserved.

Management intensity alters decomposition via biological pathways

USGS Publications Warehouse

Wickings, Kyle; Grandy, A. Stuart; Reed, Sasha; Cleveland, Cory

2011-01-01

Current conceptual models predict that changes in plant litter chemistry during decomposition are primarily regulated by both initial litter chemistry and the stage-or extent-of mass loss. Far less is known about how variations in decomposer community structure (e.g., resulting from different ecosystem management types) could influence litter chemistry during decomposition. Given the recent agricultural intensification occurring globally and the importance of litter chemistry in regulating soil organic matter storage, our objectives were to determine the potential effects of agricultural management on plant litter chemistry and decomposition rates, and to investigate possible links between ecosystem management, litter chemistry and decomposition, and decomposer community composition and activity. We measured decomposition rates, changes in litter chemistry, extracellular enzyme activity, microarthropod communities, and bacterial versus fungal relative abundance in replicated conventional-till, no-till, and old field agricultural sites for both corn and grass litter. After one growing season, litter decomposition under conventional-till was 20% greater than in old field communities. However, decomposition rates in no-till were not significantly different from those in old field or conventional-till sites. After decomposition, grass residue in both conventional- and no-till systems was enriched in total polysaccharides relative to initial litter, while grass litter decomposed in old fields was enriched in nitrogen-bearing compounds and lipids. These differences corresponded with differences in decomposer communities, which also exhibited strong responses to both litter and management type. Overall, our results indicate that agricultural intensification can increase litter decomposition rates, alter decomposer communities, and influence litter chemistry in ways that could have important and long-term effects on soil organic matter dynamics. We suggest that future efforts to more accurately predict soil carbon dynamics under different management regimes may need to explicitly consider how changes in litter chemistry during decomposition are influenced by the specific metabolic capabilities of the extant decomposer communities.

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

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.

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.

Plants and Medicinal Chemistry--2

ERIC Educational Resources Information Center

Bailey, D.

1977-01-01

Second of a two part article on the influence of plants on medicinal chemistry. This part considers how drugs work, the attempts to develop anaesthetics safer than cocaine, and useful poisons. (Author/SL)

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.

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