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

Chemistry of acetylene on platinum (111) and (100) surfaces

PubMed Central

Muetterties, E. L.; Tasi, M.-C.; Kelemen, S. R.

1981-01-01

An ultra-high vacuum experimental study of acetylene chemisorption on Pt(111) and Pt(100) and of the reaction of hydrogen with the acetylene adsorbate has established distinguishing features of carbon-hydrogen bond breaking and making processes as a function of pressure, temperature, and surface crystallography. The rates for both processes are substantially higher on the Pt(100) surface. Net acetylene-hydrogen processes, in the temperature range of 20°C to ≈130°C, are distinctly different on the two surfaces: on Pt(100) the net reaction is hydrogen exchange (1H-2H exchange) and on Pt(111) the only detectable reaction is hydrogenation. Stereochemical differences in the acetylene adsorbate structure are considered to be a contributing factor to the differences in acetylene chemistry on these two surfaces. Images PMID:16593110

Incorporation of coupled nonequilibrium chemistry into a two-dimensional nozzle code (SEAGULL)

NASA Technical Reports Server (NTRS)

Ratliff, A. W.

1979-01-01

A two-dimensional multiple shock nozzle code (SEAGULL) was extended to include the effects of finite rate chemistry. The basic code that treats multiple shocks and contact surfaces was fully coupled with a generalized finite rate chemistry and vibrational energy exchange package. The modified code retains all of the original SEAGULL features plus the capability to treat chemical and vibrational nonequilibrium reactions. Any chemical and/or vibrational energy exchange mechanism can be handled as long as thermodynamic data and rate constants are available for all participating species.

OSCAR4: a flexible architecture for chemical text-mining.

PubMed

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

2011-10-14

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

Conclusions and recommendations: Exploration of the Saturn system

NASA Technical Reports Server (NTRS)

Hunten, D. M.

1978-01-01

Saturn missions have the following principal goals, in order of importance: (1) Intensive investigation of the atmosphere of Saturn; (2) determination of regional surface chemistry and properties of the surface features of satellites and properties of ring particles; (3) intensive investigation of Titan; and (4) atmospheric dynamics and structure of Saturn satellites and Saturn rings.

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.

On the Formation of Interstellar Water Ice: Constraints from a Search for Hydrogen Peroxide Ice in Molecular Clouds

NASA Technical Reports Server (NTRS)

Smith, R. G.; Charnely, S. B.; Pendleton, Y. J.; Wright, C. M.; Maldoni, M. M.; Robinson, G.

2011-01-01

Recent surface chemistry experiments have shown that the hydrogenation of molecular oxygen on interstellar dust grains is a plausible formation mechanism, via hydrogen peroxide (H2O2), for the production of water (H2O) ice mantles in the dense interstellar medium. Theoretical chemistry models also predict the formation of a significant abundance of H2O2 ice in grain mantles by this route. At their upper limits, the predicted and experimental abundances are sufficiently high that H2O2 should be detectable in molecular cloud ice spectra. To investigate this further, laboratory spectra have been obtained for H2O2/H2O ice films between 2.5 and 200 micron, from 10 to 180 K, containing 3%, 30%, and 97% H2O2 ice. Integrated absorbances for all the absorption features in low-temperature H2O2 ice have been derived from these spectra. For identifying H2O2 ice, the key results are the presence of unique features near 3.5, 7.0, and 11.3 micron. Comparing the laboratory spectra with the spectra of a group of 24 protostars and field stars, all of which have strong H2O ice absorption bands, no absorption features are found that can definitely be identified with H2O2 ice. In the absence of definite H2O2 features, the H2O2 abundance is constrained by its possible contribution to the weak absorption feature near 3.47 micron found on the long-wavelength wing of the 3 micron H2O ice band. This gives an average upper limit for H2O2, as a percentage of H2O, of 9% +/- 4%. This is a strong constraint on parameters for surface chemistry experiments and dense cloud chemistry models.

OSCAR4: a flexible architecture for chemical text-mining

PubMed Central

2011-01-01

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

Hydrogen peroxide on the surface of Europa

USGS Publications Warehouse

Carlson, R.W.; Anderson, M.S.; Johnson, R.E.; Smythe, W.D.; Hendrix, A.R.; Barth, C.A.; Soderblom, L.A.; Hansen, G.B.; McCord, T.B.; Dalton, J.B.; Clark, R.N.; Shirley, J.H.; Ocampo, A.C.; Matson, D.L.

1999-01-01

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Hydrogen peroxide on the surface of Europa.

PubMed

Carlson, R W; Anderson, M S; Johnson, R E; Smythe, W D; Hendrix, A R; Barth, C A; Soderblom, L A; Hansen, G B; McCord, T B; Dalton, J B; Clark, R N; Shirley, J H; Ocampo, A C; Matson, D L

1999-03-26

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Controlling Film Morphology in Conjugated Polymer

PubMed Central

Park, Lee Y.; Munro, Andrea M.; Ginger, David S.

2009-01-01

We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells. PMID:18983150

Materials Chemistry and Performance of Silicone-Based Replicating Compounds.

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

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

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

Ablation, Thermal Response, and Chemistry Program for Analysis of Thermal Protection Systems

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Chen, Yih-Kanq

2010-01-01

In previous work, the authors documented the Multicomponent Ablation Thermochemistry (MAT) and Fully Implicit Ablation and Thermal response (FIAT) programs. In this work, key features from MAT and FIAT were combined to create the new Fully Implicit Ablation, Thermal response, and Chemistry (FIATC) program. FIATC is fully compatible with FIAT (version 2.5) but has expanded capabilities to compute the multispecies surface chemistry and ablation rate as part of the surface energy balance. This new methodology eliminates B' tables, provides blown species fractions as a function of time, and enables calculations that would otherwise be impractical (e.g. 4+ dimensional tables) such as pyrolysis and ablation with kinetic rates or unequal diffusion coefficients. Equations and solution procedures are presented, then representative calculations of equilibrium and finite-rate ablation in flight and ground-test environments are discussed.

Nonequilibrium chemistry boundary layer integral matrix procedure

NASA Technical Reports Server (NTRS)

Tong, H.; Buckingham, A. C.; Morse, H. L.

1973-01-01

The development of an analytic procedure for the calculation of nonequilibrium boundary layer flows over surfaces of arbitrary catalycities is described. An existing equilibrium boundary layer integral matrix code was extended to include nonequilibrium chemistry while retaining all of the general boundary condition features built into the original code. For particular application to the pitch-plane of shuttle type vehicles, an approximate procedure was developed to estimate the nonequilibrium and nonisentropic state at the edge of the boundary layer.

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

PubMed

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

2017-03-15

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

Nanometer polymer surface features: the influence on surface energy, protein adsorption and endothelial cell adhesion

NASA Astrophysics Data System (ADS)

Carpenter, Joseph; Khang, Dongwoo; Webster, Thomas J.

2008-12-01

Current small diameter (<5 mm) synthetic vascular graft materials exhibit poor long-term patency due to thrombosis and intimal hyperplasia. Tissue engineered solutions have yielded functional vascular tissue, but some require an eight-week in vitro culture period prior to implantation—too long for immediate clinical bedside applications. Previous in vitro studies have shown that nanostructured poly(lactic-co-glycolic acid) (PLGA) surfaces elevated endothelial cell adhesion, proliferation, and extracellular matrix synthesis when compared to nanosmooth surfaces. Nonetheless, these studies failed to address the importance of lateral and vertical surface feature dimensionality coupled with surface free energy; nor did such studies elicit an optimum specific surface feature size for promoting endothelial cell adhesion. In this study, a series of highly ordered nanometer to submicron structured PLGA surfaces of identical chemistry were created using a technique employing polystyrene nanobeads and poly(dimethylsiloxane) (PDMS) molds. Results demonstrated increased endothelial cell adhesion on PLGA surfaces with vertical surface features of size less than 18.87 nm but greater than 0 nm due to increased surface energy and subsequently protein (fibronectin and collagen type IV) adsorption. Furthermore, this study provided evidence that the vertical dimension of nanometer surface features, rather than the lateral dimension, is largely responsible for these increases. In this manner, this study provides key design parameters that may promote vascular graft efficacy.

Terminal velocity and drag reduction measurements on superhydrophobic spheres

NASA Astrophysics Data System (ADS)

McHale, G.; Shirtcliffe, N. J.; Evans, C. R.; Newton, M. I.

2009-02-01

Super water-repellent surfaces occur naturally on plants and aquatic insects and are created in the laboratory by combining micro- or nanoscale surface topographic features with hydrophobic surface chemistry. When such types of water-repellent surfaces are submerged they can retain a film of air (a plastron). In this work, we report measurements of the terminal velocity of solid acrylic spheres with various surface treatments settling under the action of gravity in water. We observed increases in terminal velocity corresponding to drag reduction of between 5% and 15% for superhydrophobic surfaces that carry plastrons.

Feature Profile Evolution of SiO2 Trenches In Fluorocarbon Plasmas

NASA Technical Reports Server (NTRS)

Hwang, Helen; Govindan, T. R.; Meyyappan, M.; Arunachalam, Valli; Rauf, Shahid; Coronell, Dan; Carroll, Carol W. (Technical Monitor)

1999-01-01

Etching of silicon microstructures for semiconductor manufacturing in chlorine plasmas has been well characterized. The etching proceeds in a two-part process, where the chlorine neutrals passivate the Si surface and then the ions etch away SiClx. However, etching in more complicated gas mixtures and materials, such as etching of SiO2 in Ar/C4F8, requires knowledge of the ion and neutral distribution functions as a function of angle and velocity, in addition to modeling the gas surface reactions. In order to address these needs, we have developed and integrated a suite of models to simulate the etching process from the plasma reactor level to the feature profile evolution level. This arrangement allows for a better understanding, control, and prediction of the influence of equipment level process parameters on feature profile evolution. We are currently using the HPEM (Hybrid Plasma Equipment Model) and PCMCM (Plasma Chemistry Monte Carlo Model) to generate plasma properties and ion and neutral distribution functions for argon/fluorocarbon discharges in a GEC Reference Cell. These quantities are then input to the feature scale model, Simulation of Profile Evolution by Level Sets (SPELS). A surface chemistry model is used to determine the interaction of the incoming species with the substrate material and simulate the evolution of the trench profile. The impact of change of gas pressure and inductive power on the relative flux of CFx and F to the wafer, the etch and polymerization rates, and feature profiles will be examined. Comparisons to experimental profiles will also be presented.

DNA-Mediated Electrochemistry

PubMed Central

Gorodetsky, Alon A.; Buzzeo, Marisa C.

2009-01-01

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

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.

A simple definitive test for chloride salts on Europa

NASA Astrophysics Data System (ADS)

Brown, Michael

2016-10-01

Europa is a prime location for exploring our concepts of habitability throughout the solar system. As importantly, Europa is a case study for how liquid water drives the geochemistry and geophysics in a world very different from our own. One of the keys to understanding the liquid water's effect on habitability, geochemistry, and even on geophysics is understanding the chemistry of the internal ocean. Evaporites on the surface of Europa provide a window into this ocean chemistry. Recent observations have overturned 15 years worth of assumptions about the chemistry of Europa's ocean and have suggested that chloride salts - rather than sulfate salts - could be the most abundant constituent in the ocean and in the surface evaporites. The possibility of chloride salts has major implications for geophysics and habitability, but, because chloride salts are basically featureless, definitive spectral evidence was thought impossible.New laboratory data now shows, however, that electron irradiation with Europa-like fluxes imparts distinct spectral absorption features on chloride salts. These spectral features, in specific bands between 430 and 830 nm, are uniquely accessible to high spatial resolution HST spectroscopy. We propose a very simple program to obtain four separate high spatial resolution STIS slit scans across the disk of Europa to construct a global spectral map which will detect and map these surface salts. These observations can definitively identify chloride salts on Europa and fundamentally change our understanding of this world. Rarely can such a simple and short program with HST have the possibility of obtaining such conclusive and transformative results.

Development and Optical Testing of the Camera, Hand Lens, and Microscope Probe with Scannable Laser Spectroscopy (CHAMP-SLS)

NASA Technical Reports Server (NTRS)

Mungas, Greg S.; Gursel, Yekta; Sepulveda, Cesar A.; Anderson, Mark; La Baw, Clayton; Johnson, Kenneth R.; Deans, Matthew; Beegle, Luther; Boynton, John

2008-01-01

Conducting high resolution field microscopy with coupled laser spectroscopy that can be used to selectively analyze the surface chemistry of individual pixels in a scene is an enabling capability for next generation robotic and manned spaceflight missions, civil, and military applications. In the laboratory, we use a range of imaging and surface preparation tools that provide us with in-focus images, context imaging for identifying features that we want to investigate at high magnification, and surface-optical coupling that allows us to apply optical spectroscopic analysis techniques for analyzing surface chemistry particularly at high magnifications. The camera, hand lens, and microscope probe with scannable laser spectroscopy (CHAMP-SLS) is an imaging/spectroscopy instrument capable of imaging continuously from infinity down to high resolution microscopy (resolution of approx. 1 micron/pixel in a final camera format), the closer CHAMP-SLS is placed to a feature, the higher the resultant magnification. At hand lens to microscopic magnifications, the imaged scene can be selectively interrogated with point spectroscopic techniques such as Raman spectroscopy, microscopic Laser Induced Breakdown Spectroscopy (micro-LIBS), laser ablation mass-spectrometry, Fluorescence spectroscopy, and/or Reflectance spectroscopy. This paper summarizes the optical design, development, and testing of the CHAMP-SLS optics.

Investigation of Diffusion Characteristics through Microfluidic Channels for Passive Drug Delivery Applications

PubMed Central

Ghuman, Alyssa P.; Collins, Stephanie B.; Handa, Hitesh

2016-01-01

Microfluidics has many drug delivery applications due to the ability to easily create complex device designs with feature sizes reaching down to the 10s of microns. In this work, three different microchannel designs for an implantable device are investigated for treatment of ocular diseases such as glaucoma, age-related macular degeneration (AMD), and diabetic retinopathy. Devices were fabricated using polydimethylsiloxane (PDMS) and soft lithography techniques, where surface chemistry of the channels was altered using 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane (PEG-silane). An estimated delivery rate for a number of common drugs was approximated for each device through the ratio of the diffusion coefficients for the dye and the respective drug. The delivery rate of the model drugs was maintained at a physiological condition and the effects of channel design and surface chemistry on the delivery rate of the model drugs were recorded over a two-week period. Results showed that the surface chemistry of the device had no significant effect on the delivery rate of the model drugs. All designs were successful in delivering a constant daily dose for each model drug. PMID:27313895

Pollenkitt wetting mechanism enables species-specific tunable pollen adhesion.

PubMed

Lin, Haisheng; Gomez, Ismael; Meredith, J Carson

2013-03-05

Plant pollens are microscopic particles exhibiting a remarkable breadth of complex solid surface features. In addition, many pollen grains are coated with a viscous liquid, "pollenkitt", thought to play important roles in pollen dispersion and adhesion. However, there exist no quantitative studies of the effects of solid surface features or pollenkitt on adhesion of pollen grains, and it remains unclear what role these features play in pollen adhesion and transport. We report AFM adhesion measurements of five pollen species with a series of test surfaces in which each pollen has a unique solid surface morphology and pollenkitt volume. The results indicate that the combination of surface morphology (size and shape of echinate or reticulate features) with the pollenkitt volume provides pollens with a remarkably tunable adhesion to surfaces. With pollenkitt removed, pollen grains had relatively low adhesion strengths that were independent of surface chemistry and scalable with the tip radius of the pollen's ornamentation features, according to the Hamaker model. With the pollenkitt intact, adhesion was up to 3-6 times higher than the dry grains and exhibited strong substrate dependence. The adhesion enhancing effect of pollenkitt was driven by the formation of pollenkitt capillary bridges and was surprisingly species-dependent, with echinate insect-pollinated species (dandelion and sunflower) showing significantly stronger adhesion and higher substrate dependence than wind-pollinated species (ragweed, poplar, and olive). The combination of high pollenkitt volume and large convex, spiny surface features in echinate entomophilous varieties appears to enhance the spreading area of the liquid pollenkitt relative to varieties of pollen with less pollenkitt volume and less pronounced surface features. Measurements of pollenkitt surface energy indicate that the adhesive strength of capillary bridges is primarily dependent on nonpolar van der Waals interactions, with some contribution from the Lewis basic component of surface energy.

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.

Chemistry of Stream Sediments and Surface Waters in New England

USGS Publications Warehouse

Robinson, Gilpin R.; Kapo, Katherine E.; Grossman, Jeffrey N.

2004-01-01

Summary -- This online publication portrays regional data for pH, alkalinity, and specific conductance for stream waters and a multi-element geochemical dataset for stream sediments collected in the New England states of Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont. A series of interpolation grid maps portray the chemistry of the stream waters and sediments in relation to bedrock geology, lithology, drainage basins, and urban areas. A series of box plots portray the statistical variation of the chemical data grouped by lithology and other features.

What should we look for when we return to Mars?. [possibility of extraterrestrial life

NASA Technical Reports Server (NTRS)

Soffen, G. A.

1988-01-01

The current state of knowledge about Mars is examined, and the details of current planned missions (Phobos and the Mars Orbiter) are considered. Speculations on some of the major future avenues of Mars research are presented; particular attention is given to questions relating to the early geological processes that resulted in Martian surface features, the effect liquid water has had on the planet, the volatile dynamics and chemistry, the chemistry of the iron-rich clays, the organic-compound mystery, and the biological issue.

Surface structure and chemistry of Pt/Cu/Pt(1 1 1) near surface alloy model catalyst in CO

NASA Astrophysics Data System (ADS)

Zeng, Shibi; Nguyen, Luan; Cheng, Fang; Liu, Lacheng; Yu, Ying; Tao, Franklin (Feng)

2014-11-01

Near surface alloy (NSA) model catalyst Pt/Cu/Pt(1 1 1) was prepared on Pt(1 1 1) through a controlled vapor deposition of Cu atoms. Different coordination environments of Pt atoms of the topmost Pt layer with the underneath Cu atoms in the subsurface result in different local electronic structures of surface Pt atoms. Surface structure and chemistry of the NAS model catalyst in Torr pressure of CO were studied with high pressure scanning tunneling microscopy (HP-STM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In Torr pressure of CO, the topmost Pt layer of Pt/Cu/Pt(1 1 1) is restructured to thin nanoclusters with size of about 1 nm. Photoemission feature of O 1s of CO on Pt/Cu/Pt(1 1 1) suggests CO adsorbed on both edge and surface of these formed nanoclusters. This surface is active for CO oxidation. Atomic layers of carbon are formed on Pt/Cu/Pt(1 1 1) at 573 K in 2 Torr of CO.

Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

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

Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney

The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further themore » similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.« less

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.

Lunar surface chemistry: A new imaging technique

USGS Publications Warehouse

Andre, C.G.; Bielefeld, M.J.; Eliason, E.; Soderblom, L.A.; Adler, I.; Philpotts, J.A.

1977-01-01

Detailed chemical maps of the lunar surface have been constructed by applying a new weighted-filter imaging technique to Apollo 15 and Apollo 16 x-ray fluorescence data. The data quality improvement is amply demonstrated by (i) modes in the frequency distribution, representing highland and mare soil suites, which are not evident before data filtering and (ii) numerous examples of chemical variations which are correlated with small-scale (about 15 kilometer) lunar topographic features.

Lunar surface chemistry - A new imaging technique

NASA Technical Reports Server (NTRS)

Andre, C. G.; Adler, I.; Bielefeld, M. J.; Eliason, E.; Soderblom, L. A.; Philpotts, J. A.

1977-01-01

Detailed chemical maps of the lunar surface have been constructed by applying a new weighted-filter imaging technique to Apollo 15 and Apollo 16 X-ray fluorescence data. The data quality improvement is amply demonstrated by (1) modes in the frequency distribution, representing highland and mare soil suites, which are not evident before data filtering, and (2) numerous examples of chemical variations which are correlated with small-scale (about 15 kilometer) lunar topographic features.

Micromachined devices: the impact of controlled geometry from cell-targeting to bioavailability.

PubMed

Tao, Sarah L; Desai, Tejal A

2005-12-05

Advances in microelectomechanical systems (MEMS) have allowed the microfabrication of polymeric substrates and the development of a novel class of controlled delivery devices. These vehicles have specifically tailored three-dimensional physical and chemical features which, together, provide the capacity to target cells, promote unidirectional controlled release, and enhance permeation across the intestinal epithelial barrier. Examining the biological response at the microdevice biointerface may provide insight into the benefits of customized surface chemistry and structure in terms of complex drug delivery vehicle design. Therefore, the aim of this work was to determine the interfacial effects of selective surface chemistry and architecture of tomato lectin (TL)-modified poly(methyl methacrylate) (PMMA) drug delivery microdevices on the Caco-2 cell line, a model of the gastrointestinal tract.

Microtopographic and depth controls on active layer chemistry in Arctic polygonal ground

DOE PAGES

Newman, Brent D.; Throckmorton, Heather M.; Graham, David E.; ...

2015-03-24

Polygonal ground is a signature characteristic of Arctic lowlands, and carbon release from permafrost thaw can alter feedbacks to Arctic ecosystems and climate. This study describes the first comprehensive spatial examination of active layer biogeochemistry that extends across high- and low-centered, ice wedge polygons, their features, and with depth. Water chemistry measurements of 54 analytes were made on surface and active layer pore waters collected near Barrow, Alaska, USA. Significant differences were observed between high- and low-centered polygons suggesting that polygon types may be useful for landscape-scale geochemical classification. However, differences were found for polygon features (centers and troughs) formore » analytes that were not significant for polygon type, suggesting that finer-scale features affect biogeochemistry differently from polygon types. Depth variations were also significant, demonstrating important multidimensional aspects of polygonal ground biogeochemistry. These results have major implications for understanding how polygonal ground ecosystems function, and how they may respond to future change.« less

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

PubMed

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

2011-08-14

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

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

NASA Astrophysics Data System (ADS)

Petit, Camille

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

Interstellar chemistry

PubMed Central

Klemperer, William

2006-01-01

In the past half century, radioastronomy has changed our perception and understanding of the universe. In this issue of PNAS, the molecular chemistry directly observed within the galaxy is discussed. For the most part, the description of the molecular transformations requires specific kinetic schemes rather than chemical thermodynamics. Ionization of the very abundant molecular hydrogen and atomic helium followed by their secondary reactions is discussed. The rich variety of organic species observed is a challenge for complete understanding. The role and nature of reactions involving grain surfaces as well as new spectroscopic observations of interstellar and circumstellar regions are topics presented in this special feature. PMID:16894148

Interstellar chemistry.

PubMed

Klemperer, William

2006-08-15

In the past half century, radioastronomy has changed our perception and understanding of the universe. In this issue of PNAS, the molecular chemistry directly observed within the galaxy is discussed. For the most part, the description of the molecular transformations requires specific kinetic schemes rather than chemical thermodynamics. Ionization of the very abundant molecular hydrogen and atomic helium followed by their secondary reactions is discussed. The rich variety of organic species observed is a challenge for complete understanding. The role and nature of reactions involving grain surfaces as well as new spectroscopic observations of interstellar and circumstellar regions are topics presented in this special feature.

Screened hybrid density functionals for solid-state chemistry and physics.

PubMed

Janesko, Benjamin G; Henderson, Thomas M; Scuseria, Gustavo E

2009-01-21

Density functional theory incorporating hybrid exchange-correlation functionals has been extraordinarily successful in providing accurate, computationally tractable treatments of molecular properties. However, conventional hybrid functionals can be problematic for solids. Their nonlocal, Hartree-Fock-like exchange term decays slowly and incorporates unphysical features in metals and narrow-bandgap semiconductors. This article provides an overview of our group's work on designing hybrid functionals for solids. We focus on the Heyd-Scuseria-Ernzerhof screened hybrid functional [J. Chem. Phys. 2003, 118, 8207], its applications to the chemistry and physics of solids and surfaces, and our efforts to build upon its successes.

Cellular uptake: lessons from supramolecular organic chemistry.

PubMed

Gasparini, Giulio; Bang, Eun-Kyoung; Montenegro, Javier; Matile, Stefan

2015-07-04

The objective of this Feature Article is to reflect on the importance of established and emerging principles of supramolecular organic chemistry to address one of the most persistent problems in life sciences. The main topic is dynamic covalent chemistry on cell surfaces, particularly disulfide exchange for thiol-mediated uptake. Examples of boronate and hydrazone exchange are added for contrast, comparison and completion. Of equal importance are the discussions of proximity effects in polyions and counterion hopping, and more recent highlights on ring tension and ion pair-π interactions. These lessons from supramolecular organic chemistry apply to cell-penetrating peptides, particularly the origin of "arginine magic" and the "pyrenebutyrate trick," and the currently emerging complementary "disulfide magic" with cell-penetrating poly(disulfide)s. They further extend to the voltage gating of neuronal potassium channels, gene transfection, and the delivery of siRNA. The collected examples illustrate that the input from conceptually innovative chemistry is essential to address the true challenges in biology beyond incremental progress and random screening.

The surface science of nanocrystals

NASA Astrophysics Data System (ADS)

Boles, Michael A.; Ling, Daishun; Hyeon, Taeghwan; Talapin, Dmitri V.

2016-02-01

All nanomaterials share a common feature of large surface-to-volume ratio, making their surfaces the dominant player in many physical and chemical processes. Surface ligands -- molecules that bind to the surface -- are an essential component of nanomaterial synthesis, processing and application. Understanding the structure and properties of nanoscale interfaces requires an intricate mix of concepts and techniques borrowed from surface science and coordination chemistry. Our Review elaborates these connections and discusses the bonding, electronic structure and chemical transformations at nanomaterial surfaces. We specifically focus on the role of surface ligands in tuning and rationally designing properties of functional nanomaterials. Given their importance for biomedical (imaging, diagnostics and therapeutics) and optoelectronic (light-emitting devices, transistors, solar cells) applications, we end with an assessment of application-targeted surface engineering.

Multivariate classification of small order watersheds in the Quabbin Reservoir Basin, Massachusetts

USGS Publications Warehouse

Lent, R.M.; Waldron, M.C.; Rader, J.C.

1998-01-01

A multivariate approach was used to analyze hydrologic, geologic, geographic, and water-chemistry data from small order watersheds in the Quabbin Reservoir Basin in central Massachusetts. Eighty three small order watersheds were delineated and landscape attributes defining hydrologic, geologic, and geographic features of the watersheds were compiled from geographic information system data layers. Principal components analysis was used to evaluate 11 chemical constituents collected bi-weekly for 1 year at 15 surface-water stations in order to subdivide the basin into subbasins comprised of watersheds with similar water quality characteristics. Three principal components accounted for about 90 percent of the variance in water chemistry data. The principal components were defined as a biogeochemical variable related to wetland density, an acid-neutralization variable, and a road-salt variable related to density of primary roads. Three subbasins were identified. Analysis of variance and multiple comparisons of means were used to identify significant differences in stream water chemistry and landscape attributes among subbasins. All stream water constituents were significantly different among subbasins. Multiple regression techniques were used to relate stream water chemistry to landscape attributes. Important differences in landscape attributes were related to wetlands, slope, and soil type.A multivariate approach was used to analyze hydrologic, geologic, geographic, and water-chemistry data from small order watersheds in the Quabbin Reservoir Basin in central Massachusetts. Eighty three small order watersheds were delineated and landscape attributes defining hydrologic, geologic, and geographic features of the watersheds were compiled from geographic information system data layers. Principal components analysis was used to evaluate 11 chemical constituents collected bi-weekly for 1 year at 15 surface-water stations in order to subdivide the basin into subbasins comprised of watersheds with similar water quality characteristics. Three principal components accounted for about 90 percent of the variance in water chemistry data. The principal components were defined as a biogeochemical variable related to wetland density, an acid-neutralization variable, and a road-salt variable related to density of primary roads. Three subbasins were identified. Analysis of variance and multiple comparisons of means were used to identify significant differences in stream water chemistry and landscape attributes among subbasins. All stream water constituents were significantly different among subbasins. Multiple regression techniques were used to relate stream water chemistry to landscape attributes. Important differences in landscape attributes were related to wetlands, slope, and soil type.

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

Enhancement of endothelialisation of coronary stents by laser surface engineering.

PubMed

Li, Lin; Mirhosseini, Nazanin; Michael, Alun; Liu, Zhu; Wang, Tao

2013-11-01

Coronary stents have been widely used in the treatment of coronary heart disease. However, complications have hampered the long-term success of the device. Bare-metal stents (BMS) have a high rate of restenosis and poor endothelialisation. The drug-eluting stents (DES), although dramatically reduce restenosis, significantly prevent endothelialisation leading to late thrombosis and behave the same way as BMS after drug releasing. Rapid adhesion and growth of endothelial cells on the stent surface is a key process for early vascular healing after coronary stenting which contributes to the reduction of major complications. Surface properties manipulate cell growth and directly determine the success and life-span of the implants. However, the ideal surface properties of coronary stents are not yet fully understood. The objective of this research is to understand how surface micro/nano textures and associated material chemistry changes generated by a laser beam affect the behavior of endothelial cells on bare metal 316L stents. A high power laser beam was applied to modifying the surface properties of 316L coronary stent material and the commercial coronary stents, followed by examination of the adhesion and proliferation of human coronary endothelial cells that were growing on the surfaces. Surface properties were examined by scanning electron microscopy, contact angle measurement, and X-ray photoelectron spectroscopy. A novel surface with combined micro/nano features was created on stent material 316L and coronary stent with a specific surface chemistry. This surface gives rise to a threefold increase in the adhesion and eightfold increase in the proliferation of endothelial cells. Interestingly, such effects were only observed when the surface texture was produced in the nitrogen atmosphere suggesting the importance of the surface chemistry, including the dramatic increase of chromium nitride, for the interaction of endothelial cells with the material surface. This novel surface is also super-hydrophilic with close to zero water/cell culture fluid contact angles and low cytotoxicity. A novel surface created by laser surface-engineering with a combination of defined surface texture and surface chemistry was found beneficial for the improvement of coronary stent endothelialisation. The technology presented here could work with both DES and BMS with added benefit for the improvement of the biocompatibility of current coronary stents. © 2013 Wiley Periodicals, Inc.

Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces.

PubMed

Ciesielski, Artur; Samorì, Paolo

2011-04-01

Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.

Bifunctional redox tagging of carbon nanoparticles

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-02-01

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

Laser surface texturing of 316L stainless steel in air and water: A method for increasing hydrophilicity via direct creation of microstructures

NASA Astrophysics Data System (ADS)

Razi, Sepehr; Madanipour, Khosro; Mollabashi, Mahmoud

2016-06-01

Laser processing of materials in water contact is sometimes employed for improving the machining, cutting or welding quality. Here, we demonstrate surface patterning of stainless steel grade 316L by nano-second laser processing in air and water. Suitable adjustments of laser parameters offer a variety of surface patterns on the treated targets. Furthermore alterations of different surface features such as surface chemistry and wettability are investigated in various processing circumstances. More than surface morphology, remarkable differences are observed in the surface oxygen content and wettability of the samples treated in air and water at the same laser processing conditions. Mechanisms of the changes are discussed extensively.

Mapping alpha-Particle X-Ray Fluorescence Spectrometer (Map-X)

NASA Technical Reports Server (NTRS)

Blake, D. F.; Sarrazin, P.; Bristow, T.

2014-01-01

Many planetary surface processes (like physical and chemical weathering, water activity, diagenesis, low-temperature or impact metamorphism, and biogenic activity) leave traces of their actions as features in the size range 10s to 100s of micron. The Mapping alpha-particle X-ray Spectrometer ("Map-X") is intended to provide chemical imaging at 2 orders of magnitude higher spatial resolution than previously flown instruments, yielding elemental chemistry at or below the scale length where many relict physical, chemical, and biological features can be imaged and interpreted in ancient rocks.

Mineralogy, petrology, and surface features of lunar samples 10062,35, 10067,9, 10069,30, and 10085,16.

PubMed

Carter, J L; Macgregor, I D

1970-01-30

The primary rocks are a sequence of titanium-rich basic volcanics, composed of clinopyroxene, plagioclase, and ilmenite with minor olivine, troilite, and native iron. The soil and microbreccias are respectively loose and compacted mixtures of fragments and aggregates of similar rocks, minerals, and glassy fragments and spheres. Impact events are reflected by the presence of shock metamorphosed rock fragments, breccias, and glasses and their resulting compaction to form complex breccias, glass-spattered surfaces, and numerous glass-lined craters. Chemistry of the glasses formed by the impact events is highly variable, and the high iron and nickel content of a few moundlike features suggests that at least some of the projectiles are iron and nickel-rich meteorites.

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

Evaluation of mean climate in a chemistry-climate model simulation

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Tailoring nanocrystalline diamond coated on titanium for osteoblast adhesion.

PubMed

Pareta, Rajesh; Yang, Lei; Kothari, Abhishek; Sirinrath, Sirivisoot; Xiao, Xingcheng; Sheldon, Brian W; Webster, Thomas J

2010-10-01

Diamond coatings with superior chemical stability, antiwear, and cytocompatibility properties have been considered for lengthening the lifetime of metallic orthopedic implants for over a decade. In this study, an attempt to tailor the surface properties of diamond films on titanium to promote osteoblast (bone forming cell) adhesion was reported. The surface properties investigated here included the size of diamond surface features, topography, wettability, and surface chemistry, all of which were controlled during microwave plasma enhanced chemical-vapor-deposition (MPCVD) processes using CH4-Ar-H2 gas mixtures. The hardness and elastic modulus of the diamond films were also determined. H2 concentration in the plasma was altered to control the crystallinity, grain size, and topography of the diamond coatings, and specific plasma gases (O2 and NH3) were introduced to change the surface chemistry of the diamond coatings. To understand the impact of the altered surface properties on osteoblast responses, cell adhesion tests were performed on the various diamond-coated titanium. The results revealed that nanocrystalline diamond (grain sizes <100 nm) coated titanium dramatically increased surface hardness, and the introduction of O2 and NH3 during the MPCVD process promoted osteoblast adhesion on diamond and, thus, should be further studied for improving orthopedic applications. Copyright 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010.

Distinct Chemical Contrast in Adhesion Force Images of Hydrophobic-Hydrophilic Patterned Surfaces Using Multiwalled Carbon Nanotube Probe Tips

NASA Astrophysics Data System (ADS)

Azehara, Hiroaki; Kasanuma, Yuka; Ide, Koichiro; Hidaka, Kishio; Tokumoto, Hiroshi

2008-05-01

In this paper, we describe a fabrication procedure for large-diameter carbon nanotube probe tips (CNT tips) for atomic force microscopy, the tip-end chemistry of the CNT tips, and their advantage drawn from the study of adhesion force imaging in an ambient atmosphere on a patterned hydrophobic and hydrophilic self-assembled monolayer, which has been prepared by a microcontact printing method. Force titration measurements in phosphate buffer solutions reveal that the CNT tip has retained carboxyl groups at its end. In adhesion force imaging, a distinct chemical contrast is obtained for the patterned surfaces as compared to a case using a silicon nitride tip. The origin of the distinct contrast is discussed in terms of the tip-end chemistry featured by carboxyl groups and a possible weakening of capillary forces of water caused at around the tip-sample interface because of the intrinsically hydrophobic nature of CNTs.

Organic chemistry on Titan

NASA Technical Reports Server (NTRS)

Chang, S.; Scattergood, T.; Aronowitz, S.; Flores, J.

1979-01-01

Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

Integrated Affinity Biosensing Platforms on Screen-Printed Electrodes Electrografted with Diazonium Salts

PubMed Central

Yáñez-Sedeño, Paloma

2018-01-01

Adequate selection of the electrode surface and the strategies for its modification to enable subsequent immobilization of biomolecules and/or nanomaterials integration play a major role in the performance of electrochemical affinity biosensors. Because of the simplicity, rapidity and versatility, electrografting using diazonium salt reduction is among the most currently used functionalization methods to provide the attachment of an organic layer to a conductive substrate. This particular chemistry has demonstrated to be a powerful tool to covalently immobilize in a stable and reproducible way a wide range of biomolecules or nanomaterials onto different electrode surfaces. Considering the great progress and interesting features arisen in the last years, this paper outlines the potential of diazonium chemistry to prepare single or multianalyte electrochemical affinity biosensors on screen-printed electrodes (SPEs) and points out the existing challenges and future directions in this field. PMID:29495294

Integrated Affinity Biosensing Platforms on Screen-Printed Electrodes Electrografted with Diazonium Salts.

PubMed

Yáñez-Sedeño, Paloma; Campuzano, Susana; Pingarrón, José M

2018-02-24

Adequate selection of the electrode surface and the strategies for its modification to enable subsequent immobilization of biomolecules and/or nanomaterials integration play a major role in the performance of electrochemical affinity biosensors. Because of the simplicity, rapidity and versatility, electrografting using diazonium salt reduction is among the most currently used functionalization methods to provide the attachment of an organic layer to a conductive substrate. This particular chemistry has demonstrated to be a powerful tool to covalently immobilize in a stable and reproducible way a wide range of biomolecules or nanomaterials onto different electrode surfaces. Considering the great progress and interesting features arisen in the last years, this paper outlines the potential of diazonium chemistry to prepare single or multianalyte electrochemical affinity biosensors on screen-printed electrodes (SPEs) and points out the existing challenges and future directions in this field.

Io. [history of studies and current level of understanding of this satellite

NASA Technical Reports Server (NTRS)

Nash, Douglas B.; Yoder, Charles F.; Carr, Michael H.; Gradie, Jonathan; Hunten, Donald M.

1986-01-01

The present work reviews the history of Io studies and describes the current level of understanding of Io's physics, chemistry, geology, orbital dynamics, and geophysics. Consideration is given to the satellite's internal, superficial, atmospheric, plasma, and magnetospheric properties and how they interrelate. A pictorial map of Io's surface based on Voyager 1 and 2 images is presented. It is found that Io's surface color and spectra are dominated by sulfur compounds which may include various sulfur allotropes. Volcanic processes yielding three kinds of surface features (vent regions, plains, and mountains) dominate Io's surface geology. The Io plasma torus corotates with Jupiter's magnetic field in the plane of Jupiter's centrifugal equator centered at Io's orbital radius.

Integrating Epistemological Perspectives on Chemistry in Chemical Education: The Cases of Concept Duality, Chemical Language, and Structural Explanations

ERIC Educational Resources Information Center

Kaya, Ebru; Erduran, Sibel

2013-01-01

In this paper, we trace the work of some philosophers of chemistry to draw some implications for the improvement of chemical education. We examine some key features of chemical knowledge, and how these features are relevant for school chemistry teaching and learning. In particular, we examine Laszlo's ("Foundations of Chemistry"…

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.

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

The Learner Characteristics, Features of Desktop 3D Virtual Reality Environments, and College Chemistry Instruction: A Structural Equation Modeling Analysis

ERIC Educational Resources Information Center

Merchant, Zahira; Goetz, Ernest T.; Keeney-Kennicutt, Wendy; Kwok, Oi-man; Cifuentes, Lauren; Davis, Trina J.

2012-01-01

We examined a model of the impact of a 3D desktop virtual reality environment on the learner characteristics (i.e. perceptual and psychological variables) that can enhance chemistry-related learning achievements in an introductory college chemistry class. The relationships between the 3D virtual reality features and the chemistry learning test as…

What History Tells Us about the Distinct Nature of Chemistry.

PubMed

Chang, Hasok

2017-11-01

Attention to the history of chemistry can help us recognise the characteristics of chemistry that have helped to maintain it as a separate scientific discipline with a unique identity. Three such features are highlighted in this paper. First, chemistry has maintained a distinct type of theoretical thinking, independent from that of physics even in the era of quantum chemistry. Second, chemical research has always been shaped by its ineliminable practical relevance and usefulness. Third, the lived experience of chemistry, spanning the laboratory, the classroom and everyday life, is distinctive in its multidimensional sensuousness. Furthermore, I argue that the combination of these three features makes chemistry an exemplary science.

Simulation study of free-energy barriers in the wetting transition of an oily fluid on a rough surface with reentrant geometry.

PubMed

Savoy, Elizabeth S; Escobedo, Fernando A

2012-11-20

When in contact with a rough solid surface, fluids with low surface tension, such as oils and alkanes, have their lowest free energy in the fully wetted state. For applications where nonwetting by these phillic fluids is desired, some barrier must be introduced to maintain the nonwetted composite state. One way to create this free-energy barrier is to fabricate roughness with reentrant geometry, but the question remains as to whether the free-energy barrier is sufficiently high to prevent wetting. Our goal is to quantify the free-energy landscape for the wetting transition of an oily fluid on a surface of nails and identify significant surface features and conditions that maximize the wetting free-energy barrier (ΔGfwd*). This is a departure from most work on wetting, which focuses on the equilibrium composite and wetted states. We use boxed molecular dynamics (BXD) (Glowacki, D. R.; Paci, E.; Shalashilin, D. V. J. Phys. Chem. B2009, 113, 16603-16611) with a modified control scheme to evaluate both the thermodynamics and kinetics of the transition over a range of surface affinities (chemistry). We find that the reentrant geometry of the nails does create a free-energy barrier to transition for phillic chemistry whereas a corresponding system on straight posts wets spontaneously and, that doubling the nail height more than doubles ΔGfwd*. For neutral to phillic chemistry, the dewetting free-energy barrier is at least an order of magnitude higher than that for wetting, indicating an essentially irreversible wetting transition. Transition rates from BXD simulations and the associated trends agree well with those in our previous study that used forward flux sampling to compute transition rates for similar systems.

Classification of chemical substances, reactions, and interactions: The effect of expertise

NASA Astrophysics Data System (ADS)

Stains, Marilyne Nicole Olivia

2007-12-01

This project explored the strategies that undergraduate and graduate chemistry students engaged in when solving classification tasks involving microscopic (particulate) representations of chemical substances and microscopic and symbolic representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention while classifying, identifying the patterns of reasoning that they follow, and comparing the performance of students with different levels of preparation in the discipline. In general, our results suggest that advanced levels of expertise in chemical classification do not necessarily evolve in a linear and continuous way with academic training. Novice students had a tendency to reduce the cognitive demand of the task and rely on common-sense reasoning; they had difficulties differentiating concepts (conceptual undifferentiation) and based their classification decisions on only one variable (reduction). These ways of thinking lead them to consider extraneous features, pay more attention to explicit or surface features than implicit features and to overlook important and relevant features. However, unfamiliar levels of representations (microscopic level) seemed to trigger deeper and more meaningful thinking processes. On the other hand, expert students classified entities using a specific set of rules that they applied throughout the classification tasks. They considered a larger variety of implicit features and the unfamiliarity with the microscopic level of representation did not affect their reasoning processes. Consequently, novices created numerous small groups, few of them being chemically meaningful, while experts created few but large chemically meaningful groups. Novices also had difficulties correctly classifying entities in chemically meaningful groups. Finally, expert chemists in our study used classification schemes that are not necessarily traditionally taught in classroom chemistry (e.g. the structure of substances is more relevant to them than their composition when classifying substances as compounds or elements). This result suggests that practice in the field may develop different types of knowledge framework than those usually presented in chemistry textbooks.

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

2011 Dynamics at Surfaces Gordon Research Conference (August 7-12, 2011, Salve Regina University, Newport, Rhode Island)

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

Greg Sitz

2011-08-12

The 2011 Gordon Conference on Dynamics at Surfaces is the 32nd anniversary of a meeting held every two years that is attended by leading researchers in the area of experimental and theoretical dynamics at liquid and solid surfaces. The conference focuses on the dynamics of the interaction of molecules with either liquid or solid surfaces, the dynamics of the outermost layer of liquid and solid surfaces and the dynamics at the liquid-solid interface. Specific topics that are featured include state-to-state scattering dynamics, chemical reaction dynamics, non-adiabatic effects in reactive and inelastic scattering of molecules from surfaces, single molecule dynamics atmore » surfaces, surface photochemistry, ultrafast dynamics at surfaces, and dynamics at water interfaces. The conference brings together investigators from a variety of scientific disciplines including chemistry, physics, materials science, geology, biophysics, and astronomy.« less

Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991

USGS Publications Warehouse

Kolpin, Dana W.; Burkart, Michael R.; Thurman, E. Michael

1994-01-01

Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.

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.

A study of the effect of solid particle impact and particle shape on the erosion morphology of ductile metals

NASA Technical Reports Server (NTRS)

Rao, P. V.; Young, S. G.; Buckley, D. H.

1984-01-01

Impulsive versus steady jet impingement of spherical glass bead particles on metal surfaces was studied using a gas gun facility and a commercial sand blasting apparatus. Crushed glass particles were also used in the sand blasting apparatus as well as glass beads. Comparisons of the different types of erosion patterns were made. Scanning electron microscopy, surface profilometry and energy dispersive X-ray spectroscopy analysis were used to characterize erosion patterns. The nature of the wear can be divided into cutting and deformation, each with its own characteristic features. Surface chemistry analysis indicates the possiblity of complex chemical and/or mechanical interactions between erodants and target materials.

A study of the nature of solid particle impact and shape on the erosion morphology of ductile metals

NASA Technical Reports Server (NTRS)

Rao, P. V.; Young, S. G.; Buckley, D. H.

1982-01-01

Impulsive versus steady jet impingement of spherical glass bead particles on metal surfaces was studied using a gas gun facility and a commercial sand blasting apparatus. Crushed glass particles were also used in the sand blasting apparatus as well as glass beads. Comparisons of the different types of erosion patterns were made. Scanning electron microscopy, surface profilometry and energy dispersive X-ray spectroscopy analysis were used to characterize erosion patterns. The nature of the wear can be divided into cutting and deformation, each with its own characteristic features. Surface chemistry analysis indicates the possibility of complex chemical and/or mechanical interactions between erodants and target materials.

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.

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides†

PubMed Central

Hein, Jason E.

2011-01-01

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a widely utilized, reliable, and straightforward way for making covalent connections between building blocks containing various functional groups. It has been used in organic synthesis, medicinal chemistry, surface and polymer chemistry, and bioconjugation applications. Despite the apparent simplicity of the reaction, its mechanism involves multiple reversible steps involving coordination complexes of copper(i) acetylides of varying nuclearity. Understanding and controlling these equilibria is of paramount importance for channeling the reaction into the productive catalytic cycle. This tutorial review examines the history of the development of the CuAAC reaction, its key mechanistic aspects, and highlights the features that make it useful to practitioners in different fields of chemical science. PMID:20309487

Biomineralized 3-D Nanoparticle Assemblies with Micro-to-Nanoscale Features and Tailored Chemistries

DTIC Science & Technology

2008-01-07

protuberances on the pollen surface were well preserved after conversion. This hybrid approach may be applied to a variety of bio-organic templates, which are...replicas were found to be rapid, low voltage, minimally-invasive sensors of NO(g) and to exhibit photoluminescence . The kinetics of magnesiothermic...silica- organic hybrid structures via biomimetic silicification has been demonstrated. The effects of two key parameters, the polyamine content and

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

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

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.

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.

Plant Surfaces: Structures and Functions for Biomimetic Innovations

NASA Astrophysics Data System (ADS)

Barthlott, Wilhelm; Mail, Matthias; Bhushan, Bharat; Koch, Kerstin

2017-04-01

An overview of plant surface structures and their evolution is presented. It combines surface chemistry and architecture with their functions and refers to possible biomimetic applications. Within some 3.5 billion years biological species evolved highly complex multifunctional surfaces for interacting with their environments: some 10 million living prototypes (i.e., estimated number of existing plants and animals) for engineers. The complexity of the hierarchical structures and their functionality in biological organisms surpasses all abiotic natural surfaces: even superhydrophobicity is restricted in nature to living organisms and was probably a key evolutionary step with the invasion of terrestrial habitats some 350-450 million years ago in plants and insects. Special attention should be paid to the fact that global environmental change implies a dramatic loss of species and with it the biological role models. Plants, the dominating group of organisms on our planet, are sessile organisms with large multifunctional surfaces and thus exhibit particular intriguing features. Superhydrophilicity and superhydrophobicity are focal points in this work. We estimate that superhydrophobic plant leaves (e.g., grasses) comprise in total an area of around 250 million km2, which is about 50% of the total surface of our planet. A survey of structures and functions based on own examinations of almost 20,000 species is provided, for further references we refer to Barthlott et al. (Philos. Trans. R. Soc. A 374: 20160191, 1). A basic difference exists between aquatic non-vascular and land-living vascular plants; the latter exhibit a particular intriguing surface chemistry and architecture. The diversity of features is described in detail according to their hierarchical structural order. The first underlying and essential feature is the polymer cuticle superimposed by epicuticular wax and the curvature of single cells up to complex multicellular structures. A descriptive terminology for this diversity is provided. Simplified, the functions of plant surface characteristics may be grouped into six categories: (1) mechanical properties, (2) influence on reflection and absorption of spectral radiation, (3) reduction of water loss or increase of water uptake, moisture harvesting, (4) adhesion and non-adhesion (lotus effect, insect trapping), (5) drag and turbulence increase, or (6) air retention under water for drag reduction or gas exchange (Salvinia effect). This list is far from complete. A short overview of the history of bionics and the impressive spectrum of existing and anticipated biomimetic applications are provided. The major challenge for engineers and materials scientists, the durability of the fragile nanocoatings, is also discussed.

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

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

PubMed

Mohideen, M Infas H; Xiao, Bo; Wheatley, Paul S; McKinlay, Alistair C; Li, Yang; Slawin, Alexandra M Z; Aldous, David W; Cessford, Naomi F; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K Mark; Griffin, John M; Ashbrook, Sharon E; Morris, Russell E

2011-04-01

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

Surface and Active Layer Pore Water Chemistry from Ice Wedge Polygons, Barrow, Alaska, 2013-2014

DOE Data Explorer

David E. Graham; Baohua Gu; Elizabeth M. Herndon; Stan D. Wullschleger; Ziming Yang; Liyuan Liang

2016-11-10

This data set reports the results of spatial surveys of aqueous geochemistry conducted at Intensive Site 1 of the Barrow Environmental Observatory in 2013 and 2014 (Herndon et al., 2015). Surface water and soil pore water samples were collected from multiple depths within the tundra active layer of different microtopographic features (troughs, ridges, center) of a low-centered polygon (area A), high-centered polygon (area B), flat-centered polygon (area C), and transitional polygon (area D). Reported analytes include dissolved organic and inorganic carbon, dissolved carbon dioxide and methane, major inorganic anions, and major and minor cations.

Soft Lithography

NASA Astrophysics Data System (ADS)

Xia, Younan; Whitesides, George M.

1998-08-01

Soft lithography represents a non-photolithographic strategy based on selfassembly and replica molding for carrying out micro- and nanofabrication. It provides a convenient, effective, and low-cost method for the formation and manufacturing of micro- and nanostructures. In soft lithography, an elastomeric stamp with patterned relief structures on its surface is used to generate patterns and structures with feature sizes ranging from 30 nm to 100 mum. Five techniques have been demonstrated: microcontact printing (muCP), replica molding (REM), microtransfer molding (muTM), micromolding in capillaries (MIMIC), and solvent-assisted micromolding (SAMIM). In this chapter we discuss the procedures for these techniques and their applications in micro- and nanofabrication, surface chemistry, materials science, optics, MEMS, and microelectronics.

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

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.

Why the dish makes a difference: quantitative comparison of polystyrene culture surfaces.

PubMed

Zeiger, Adam S; Hinton, Benjamin; Van Vliet, Krystyn J

2013-07-01

There is wide anecdotal recognition that biological cell viability and behavior can vary significantly as a function of the source of commercial tissue culture polystyrene (TCPS) culture vessels to which those cells adhere. However, this marked material dependency is typically resolved by selecting and then consistently using the same manufacturer's product - following protocol - rather than by investigating the material properties that may be responsible for such experimental variation. Here, we quantified several physical properties of TCPS surfaces obtained from a wide range of commercial sources and processing steps, through the use of atomic force microscopy (AFM)-based imaging and analysis, goniometry and protein adsorption quantification. We identify qualitative differences in surface features, as well as quantitative differences in surface roughness and wettability that cannot be attributed solely to differences in surface chemistry. We also find significant differences in cell morphology and proliferation among cells cultured on different TCPS surfaces, and resolve a correlation between nanoscale surface roughness and cell proliferation rate for both cell types considered. Interestingly, AFM images of living adherent cells on these nanotextured surfaces demonstrate direct interactions between cellular protrusions and topographically distinct features. These results illustrate and quantify the significant differences in material surface properties among these ubiquitous materials, allowing us to better understand why the dish can make a difference in biological experiments. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

ERIC Educational Resources Information Center

Hathaway, Brian

1979-01-01

Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

LiNbO3 surfaces from a microscopic perspective

NASA Astrophysics Data System (ADS)

Sanna, Simone; Gero Schmidt, Wolf

2017-10-01

A large number of oxides has been investigated in the last twenty years as possible new materials for various applications ranging from opto-electronics to heterogeneous catalysis. In this context, ferroelectric oxides are particularly promising. The electric polarization plays a crucial role at many oxide surfaces, and it largely determines their physical and chemical properties. Ferroelectrics offer in addition the possibility to control/switch the electric polarization and hence the surface chemistry, allowing for the realization of domain-engineered nanoscale devices such as molecular detectors or highly efficient catalysts. Lithium niobate (LiNbO3) is a ferroelectric with a high spontaneous polarization, whose surfaces have a huge and largely unexplored potential. Owing to recent advances in experimental techniques and sample preparation, peculiar and exclusive properties of LiNbO3 surfaces could be demonstrated. For example, water films freeze at different temperatures on differently polarized surfaces, and the chemical etching properties of surfaces with opposite polarization are strongly different. More important, the ferroelectric domain orientation affects temperature dependent surface stabilization mechanisms and molecular adsorption phenomena. Various ab initio theoretical investigations have been performed in order to understand the outcome of these experiments and the origin of the exotic behavior of the lithium niobate surfaces. Thanks to these studies, many aspects of their surface physics and chemistry could be clarified. Yet other puzzling features are still not understood. This review gives a résumé on the present knowledge of lithium niobate surfaces, with a particular view on their microscopic properties, explored in recent years by means of ab initio calculations. Relevant aspects and properties of the surfaces that need further investigation are briefly discussed. The review is concluded with an outlook of challenges and potential payoff for LiNbO3 based applications.

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

PubMed

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

2015-03-26

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

A Systematic Framework and Nanoperiodic Concept for Unifying Nanoscience: Hard/Soft Nanoelements, Superatoms, Meta-Atoms, New Emerging Properties, Periodic Property Patterns, and Predictive Mendeleev-like Nanoperiodic Tables.

PubMed

Tomalia, Donald A; Khanna, Shiv N

2016-02-24

Development of a central paradigm is undoubtedly the single most influential force responsible for advancing Dalton's 19th century atomic/molecular chemistry concepts to the current maturity enjoyed by traditional chemistry. A similar central dogma for guiding and unifying nanoscience has been missing. This review traces the origins, evolution, and current status of such a critical nanoperiodic concept/framework for defining and unifying nanoscience. Based on parallel efforts and a mutual consensus now shared by both chemists and physicists, a nanoperiodic/systematic framework concept has emerged. This concept is based on the well-documented existence of discrete, nanoscale collections of traditional inorganic/organic atoms referred to as hard and soft superatoms (i.e., nanoelement categories). These nanometric entities are widely recognized to exhibit nanoscale atom mimicry features reminiscent of traditional picoscale atoms. All unique superatom/nanoelement physicochemical features are derived from quantized structural control defined by six critical nanoscale design parameters (CNDPs), namely, size, shape, surface chemistry, flexibility/rigidity, architecture, and elemental composition. These CNDPs determine all intrinsic superatom properties, their combining behavior to form stoichiometric nanocompounds/assemblies as well as to exhibit nanoperiodic properties leading to new nanoperiodic rules and predictive Mendeleev-like nanoperiodic tables, and they portend possible extension of these principles to larger quantized building blocks including meta-atoms.

Mesoporous inorganic nanoscale particles for drug adsorption and controlled release.

PubMed

Cavallaro, Giuseppe; Lazzara, Giuseppe; Fakhrullin, Rawil

2018-03-01

The review provides an overview of the mesoporous inorganic particles employed as drug delivery systems for controlled and sustained release of drugs. We have classified promising nanomaterials for drug delivery on the basis of their natural or synthetic origin. Nanoclays are available in different morphologies (nanotubes, nanoplates and nanofibers) and they are typically available at low cost from natural resources. The surface chemistry of nanoclays is versatile for targeted modifications to control loading and release properties. Synthetic nanomaterials (imogolite, laponite and mesoporous silica) present the advantages of well-established purity and availability with size features that are finely controlled. Both nanoclays and inorganic synthetic nanoparticles can be functionalized forming organic/inorganic architectures with stimuli-responsive features.

Surface charge features of kaolinite particles and their interactions

NASA Astrophysics Data System (ADS)

Gupta, Vishal

Kaolinite is both a blessing and a curse. As an important industrial mineral commodity, kaolinite clays are extensively used in the paper, ceramic, paint, plastic and rubber industries. In all these applications the wettability, aggregation, dispersion, flotation and thickening of kaolinite particles are affected by its crystal structure and surface properties. It is therefore the objective of this research to investigate selected physical and surface chemical properties of kaolinite, specifically the surface charge of kaolinite particles. A pool of advanced analytical techniques such as XRD, XRF, SEM, AFM, FTIR and ISS were utilized to investigate the morphological and surface chemistry features of kaolinite. Surface force measurements revealed that the silica tetrahedral face of kaolinite is negatively charged at pH>4, whereas the alumina octahedral face of kaolinite is positively charged at pH<6, and negatively charged at pH>8. Based on electrophoresis measurements, the apparent iso-electric point for kaolinite particles was determined to be less than pH 3. In contrast, the point of zero charge was determined to be pH 4.5 by titration techniques, which corresponds to the iso-electric point of between pH 4 and 5 as determined by surface force measurements. Results from kaolinite particle interactions indicate that the silica face--alumina face interaction is dominant for kaolinite particle aggregation at low and intermediate pH values, which explains the maximum shear yield stress at pH 5-5.5. Lattice resolution images reveal the hexagonal lattice structure of these two face surfaces of kaolinite. Analysis of the silica face of kaolinite showed that the center of the hexagonal ring of oxygen atoms is vacant, whereas the alumina face showed that the hexagonal surface lattice ring of hydroxyls surround another hydroxyl in the center of the ring. High resolution transmission electron microscopy investigation of kaolinite has indicated that kaolinite is indeed composed of silica/alumina bilayers with a c-spacing of 7.2 A. The surface charge densities of the silica face, the alumina face and the edge surface of kaolinite all influence particle interactions, and thereby affect the mechanical properties of kaolinite suspensions. The improved knowledge of kaolinite surface chemistry from this dissertation research provides a foundation for the development of improved process strategies for both the use and disposal of clay particles such as kaolinite.

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

Multiphoton writing of three-dimensional fluidic channels within a porous matrix.

PubMed

Lee, Jyh-Tsung; George, Matthew C; Moore, Jeffrey S; Braun, Paul V

2009-08-19

We demonstrate a facile method for fabricating novel 3D microfluidic channels by using two-photon-activated chemistry to locally switch the interior surface of a porous host from a hydrophobic state to a hydrophilic state. The 3D structures can be infilled selectively with water and/or hydrophobic oil with a minimum feature size of only a few micrometers. We envision that this approach may enable the fabrication of complex microfluidic structures that cannot be easily formed via current technologies.

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.

New insights into the effects of biomaterial chemistry and topography on the morphology of kidney epithelial cells.

PubMed

Hulshof, Frits; Schophuizen, Carolien; Mihajlovic, Milos; van Blitterswijk, Clemens; Masereeuw, Rosalinde; de Boer, Jan; Stamatialis, Dimitrios

2018-02-01

Increasing incidence of renal pathology in the western world calls for innovative research for the development of cell-based therapies such as a bioartificial kidney (BAK) device. To fulfil the multitude of kidney functions, the core component of the BAK is a living membrane consisting of a tight kidney cell monolayer with preserved functional organic ion transporters cultured on a polymeric membrane surface. This membrane, on one side, is in contact with blood and therefore should have excellent blood compatibility, whereas the other side should facilitate functional monolayer formation. This work investigated the effect of membrane chemistry and surface topography on kidney epithelial cells to improve the formation of a functional monolayer. To achieve this, microtopographies were fabricated with high resolution and reproducibility on polystyrene films and on polyethersulfone-polyvinyl pyrrolidone (PES-PVP) porous membranes. A conditionally immortalized proximal tubule epithelial cell line (ciPTEC) was cultured on both, and subsequently, the cell morphology and monolayer formation were assessed. Our results showed that L-dopamine coating of the PES-PVP was sufficient to support ciPTEC monolayer formation. The polystyrene topographies with large features were able to align the cells in various patterns without significantly disruption of monolayer formation; however, the PES-PVP topographies with large features disrupted the monolayer. In contrast, the PES-PVP membranes with small features and with large spacing supported well the ciPTEC monolayer formation. In addition, the topographical PES-PVP membranes were compatible as a substrate membrane to measure organic cation transporter activity in Transwell® systems. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Protein Adsorption in Three Dimensions

PubMed Central

Vogler, Erwin A.

2011-01-01

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

The meteorology and chemistry of high nitrogen oxide concentrations in the stable boundary layer at the South Pole

NASA Astrophysics Data System (ADS)

Neff, William; Crawford, Jim; Buhr, Marty; Nicovich, John; Chen, Gao; Davis, Douglas

2018-03-01

Four summer seasons of nitrogen oxide (NO) concentrations were obtained at the South Pole (SP) during the Sulfur Chemistry in the Antarctic Troposphere (ISCAT) program (1998 and 2000) and the Antarctic Tropospheric Chemistry Investigation (ANTCI) in (2003, 2005, 2006-2007). Together, analyses of the data collected from these studies provide insight into the large- to small-scale meteorology that sets the stage for extremes in NO and the significant variability that occurs day to day, within seasons, and year to year. In addition, these observations reveal the interplay between physical and chemical processes at work in the stable boundary layer of the high Antarctic plateau. We found a systematic evolution of the large-scale wind system over the ice sheet from winter to summer that controls the surface boundary layer and its effect on NO: initially in early spring (Days 280-310) the transport of warm air and clouds over West Antarctica dominates the environment over the SP; in late spring (Days 310-340), the winds at 300 hPa exhibit a bimodal behavior alternating between northwest and southeast quadrants, which is of significance to NO; in early summer (Days 340-375), the flow aloft is dominated by winds from the Weddell Sea; and finally, during late spring, winds aloft from the southeast are strongly associated with clear skies, shallow stable boundary layers, and light surface winds from the east - it is under these conditions that the highest NO occurs. Examination of the winds at 300 hPa from 1961 to 2013 shows that this seasonal pattern has not changed significantly, although the last twenty years have seen an increasing trend in easterly surface winds at the SP. What has also changed is the persistence of the ozone hole, often into early summer. With lower total ozone column density and higher sun elevation, the highest actinic flux responsible for the photolysis of snow nitrate now occurs in late spring under the shallow boundary layer conditions optimum for high accumulation of NO. This may occur via the non-linear HOX-NOx chemistry proposed after the first ISCAT field programs and NOx recycling to the surface where quantum yields may be large under the low-snow-accumulation regime of the Antarctic plateau. During the 2003 field program a sodar made direct measurements of the stable boundary layer depth (BLD), a key factor in explaining the chemistry of the high NO concentrations. Because direct measurements were not available in the other years, we developed an estimator for BLD using direct observations obtained in 2003 and step-wise linear regression with meteorological data from a 22 m tower (that was tested against independent data obtained in 1993). These data were then used with assumptions about the column abundance of NO to estimate surface fluxes of NOx. These results agreed in magnitude with results at Concordia Station and confirmed significant daily, intraseasonal and interannual variability in NO and its flux from the snow surface. Finally, we found that synoptic to mesoscale eddies governed the boundary layer circulation and accumulation pathways for NO at the SP rather than katabatic forcing. It was the small-scale features of the circulation including the transition from cloudy to clear conditions that set the stage for short-term extremes in NO, whereas larger-scale features were associated with more moderate concentrations.

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

Features of Representations in General Chemistry Textbooks: A Peek through the Lens of the Cognitive Load Theory

ERIC Educational Resources Information Center

Nyachwaya, James M.; Gillaspie, Merry

2016-01-01

The goals of this study were (1) determine the prevalence of various features of representations in five general chemistry textbooks used in the United States, and (2) use cognitive load theory to draw implications of the various features of analyzed representations. We adapted the Graphical Analysis Protocol (GAP) (Slough et al., 2010) to look at…

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.

Co-crystal formation between two organic solids on the surface of Titan

NASA Astrophysics Data System (ADS)

Cable, M. L.; Vu, T. H.; Maynard-Casely, H. E.; Hodyss, R. P.

2017-12-01

Laboratory experiments of Titan molecular materials, informed by modeling, can help us to understand the complex and dynamic surface processes occurring on this moon at cryogenic temperatures. We previously demonstrated that two common organic materials on Titan, ethane and benzene, form a unique and stable co-crystalline structure at Titan surface temperatures. We have now characterized a second co-crystal that is stable on Titan, this time between two solids: acetylene and ammonia. The co-crystal forms within minutes at Titan surface temperature, as evidenced by new Raman spectral features in the lattice vibration and C-H bending regions. In addition, a red shift of the C-H stretching mode suggests that the acetylene-ammonia co-crystal is stabilized by a network of C-H···N interactions. Thermal stability studies indicate that this co-crystal remains intact to >110 K, and experiments with liquid methane and ethane reveal the co-crystal to be resistant to fluvial or pluvial exposure. Non-covalently bound structures such as these co-crystals point to far more complex surface interactions than previously believed on Titan. New physical and mechanical properties (deformation, plasticity, density, etc.), differences in storage of key species (i.e., ethane versus methane), variations in surface transport and new chemical gradients can all result in diverse surface features and chemistries of astrobiological interest.

Chemistry in the Dusty Coma of Comet Hale-Bopp

NASA Astrophysics Data System (ADS)

Boice, D. C.; Cochran, A. L.; Disanti, M. A.; Huebner, W. F.

1998-09-01

Recent progress on a multifluid, hydrodynamic model is presented for the dusty gas flow in the inner coma of comet Hale-Bopp at several heliocentric distances. The simulations are based on a 1-D neutral coma model with detailed photo and gas-phase chemistry and dust entrainment by the gas, a separate energy balance for the electrons, separate flow of the neutral gas, fast neutral atomic and molecular hydrogen, and dust entrainment with fragmentation. The model accounts for three sources of gas release: sublimation from surface ices, transport of gas from subsurface regions through the surface, and release of gas from dust in the coma. This permits a consistent study of the importance and strength of each possible source for a variety of gas-phase species. The simulations allow a study of the changes with heliocentric distance of features within a cometary coma, e.g., spatial distributions of gas-phase species and dust of various sizes and the velocity and temperature profiles. In particular, the model is used to probe spatial distributions of gas-phase species (e.g., CN, CH, C_3, C_2, HCN, HNC, CO) and dust, and the velocity and temperature structure to understand the complex gas-phase chemistry that occurs in the inner coma. Comparisons with observations are made where available to characterize the environment surrounding comet Hale-Bopp and to aid in assimilating a variety of diverse observations of this unique comet.

Lightning chemistry on Earth-like exoplanets

NASA Astrophysics Data System (ADS)

Ardaseva, Aleksandra; Rimmer, Paul B.; Waldmann, Ingo; Rocchetto, Marco; Yurchenko, Sergey N.; Helling, Christiane; Tennyson, Jonathan

2017-09-01

We present a model for lightning shock-induced chemistry that can be applied to atmospheres of arbitrary H/C/N/O chemistry, hence for extrasolar planets and brown dwarfs. The model couples hydrodynamics and the STAND2015 kinetic gas-phase chemistry. For an exoplanet analogue to the contemporary Earth, our model predicts NO and NO2 yields in agreement with observation. We predict height-dependent mixing ratios during a storm soon after a lightning shock of NO ≈10-3 at 40 km and NO2 ≈10-4 below 40 km, with O3 reduced to trace quantities (≪10-10). For an Earth-like exoplanet with a CO2/N2 dominated atmosphere and with an extremely intense lightning storm over its entire surface, we predict significant changes in the amount of NO, NO2, O3, H2O, H2 and predict a significant abundance of C2N. We find that, for the Early Earth, O2 is formed in large quantities by lightning but is rapidly processed by the photochemistry, consistent with previous work on lightning. The chemical effect of persistent global lightning storms are predicted to be significant, primarily due to NO2, with the largest spectral features present at ˜3.4 and ˜6.2 μm. The features within the transmission spectrum are on the order of 1 ppm and therefore are not likely detectable with the James Webb Space Telescope. Depending on its spectral properties, C2N could be a key tracer for lightning on Earth-like exoplanets with a N2/CO2 bulk atmosphere, unless destroyed by yet unknown chemical reactions.

A review of the surface features and properties, surfactant adsorption and floatability of four key minerals of diasporic bauxite resources.

PubMed

Zhang, Ningning; Nguyen, Anh V; Zhou, Changchun

2018-04-01

Diasporic bauxite represents one of the major aluminum resources. Its upgrading for further processing involves a separation of diaspore (the valuable mineral) from aluminosilicates (the gangue minerals) such as kaolinite, illite, and pyrophyllite. Flotation is one of the most effective ways to realize the upgrading. Since flotation is a physicochemical process based on the difference in the surface hydrophobicity of different components, determining the adsorption characteristics of various flotation surfactants on the mineral surfaces is critical. The surfactant adsorption properties of the minerals, in turn, are controlled by the surface chemistry of the minerals, while the latter is related to the mineral crystal structures. In this paper, we first discuss the crystal structures of the four key minerals of diaspore, kaolinite, illite, and pyrophyllite as well as the broken bonds on their exposed surfaces after grinding. Next, we summarize the surface chemistry properties such as surface wettability and surface electrical properties of the four minerals, and the differences in these properties are explained from the perspective of mineral crystal structures. Then we review the adsorption mechanism and adsorption characteristics of surfactants such as collectors (cationic, anionic, and mixed surfactants), depressants (inorganic and organic), dispersants, and flocculants on these mineral surfaces. The separation of diaspore and aluminosilicates by direct flotation and reverse flotation are reviewed, and the collecting properties of different types of collectors are compared. Furthermore, the abnormal behavior of the cationic flotation of kaolinite is also explained in this section. This review provides a strong theoretical support for the optimization of the upgrading of diaspore bauxite ore by flotation and the early industrialization of the reverse flotation process. Copyright © 2018 Elsevier B.V. All rights reserved.

Directional motion of impacting drops on dual-textured surfaces.

PubMed

Vaikuntanathan, V; Sivakumar, D

2012-09-01

In this work, we analyze the directional movement of impacting liquid drops on dual-textured solid surfaces comprising two different surface morphologies: a textured surface and a smooth surface. The dynamics of liquid drops impacting onto the junction line between the two parts of the dual-textured surfaces is studied experimentally for varying drop impact velocity. The dual-textured surfaces used here featured a variation in their textures' geometrical parameters as well as their surface chemistry. Two types of liquid drop differing in their surface tension were used. The impact process develops a net horizontal drop velocity towards the higher-wettability surface portion and results in a bulk movement of the impacting drop liquid. The final distance moved by the impacting drop from the junction line decreases with increasing impacting drop Weber number We. A fully theoretical model, employing a balance of forces acting at the drop contact line as well as energy conservation, is formulated to determine the variation, with We, of net horizontal drop velocity and subsequent movement of the impacting drop on the dual-textured surfaces.

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.

Development and functional evaluation of biomimetic silicone surfaces with hierarchical micro/nano-topographical features demonstrates favourable in vitro foreign body response of breast-derived fibroblasts.

PubMed

Kyle, Daniel J T; Oikonomou, Antonios; Hill, Ernie; Bayat, Ardeshir

2015-06-01

Reproducing extracellular matrix topographical cues, such as those present within acellular dermal matrix (ADM), in synthetic implant surfaces, may augment cellular responses, independent of surface chemistry. This could lead to enhanced implant integration and performance while reducing complications. In this work, the hierarchical micro and nanoscale features of ADM were accurately and reproducibly replicated in polydimethylsiloxane (PDMS), using an innovative maskless 3D grayscale fabrication process not previously reported. Human breast derived fibroblasts (n=5) were cultured on PDMS surfaces and compared to commercially available smooth and textured silicone implant surfaces, for up to one week. Cell attachment, proliferation and cytotoxicity, in addition to immunofluorescence staining, SEM imaging, qRT-PCR and cytokine array were performed. ADM PDMS surfaces promoted cell adhesion, proliferation and survival (p=<0.05), in addition to increased focal contact formation and spread fibroblast morphology when compared to commercially available implant surfaces. PCNA, vinculin and collagen 1 were up-regulated in fibroblasts on biomimetic surfaces while IL8, TNFα, TGFβ1 and HSP60 were down-regulated (p=<0.05). A reduced inflammatory cytokine response was also observed (p=<0.05). This study represents a novel approach to the development of functionalised biomimetic prosthetic implant surfaces which were demonstrated to significantly attenuate the acute in vitro foreign body reaction to silicone. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

Development and Implementation of a Two-Semester Introductory Organic-Bioorganic Chemistry Sequence: Conclusions from the First Six Years

ERIC Educational Resources Information Center

Goess, Brian C.

2014-01-01

A two-semester second-year introductory organic chemistry sequence featuring one semester of accelerated organic chemistry followed by one semester of bioorganic chemistry is described. Assessment data collected over a six-year period reveal that such a course sequence can facilitate student mastery of fundamental organic chemistry in the first…

Chemistry Outreach Project to High Schools Using a Mobile Chemistry Laboratory, ChemKits, and Teacher Workshops

ERIC Educational Resources Information Center

Long, Gary L.; Bailey, Carol A.; Bunn, Barbara B.; Slebodnick, Carla; Johnson, Michael R.; Derozier, Shad

2012-01-01

The Chemistry Outreach Program (ChOP) of Virginia Tech was a university-based outreach program that addressed the needs of high school chemistry classes in underfunded rural and inner-city school districts. The primary features of ChOP were a mobile chemistry laboratory (MCL), a shipping-based outreach program (ChemKits), and teacher workshops.…

Interaction of gases with lunar materials. [surface properties of lunar fines, especially on exposure to water vapor

NASA Technical Reports Server (NTRS)

Holmes, H. F.; Gammage, R. B.

1975-01-01

The surface properties of lunar fines were investigated. Results indicate that, for the most part, these properties are independent of the chemical composition and location of the samples on the lunar surface. The leaching of channels and pores by adsorbed water vapor is a distinguishing feature of their surface chemistry. The elements of air, if adsorbed in conjunction with water vapor or liquid water, severely impedes the leaching process. In the absence of air, liquid water is more effective than water vapor in attacking the grains. The characteristics of Apollo 17 orange fines were evaluated and compared with those of other samples. The interconnecting channels produced by water vapor adsorption were found to be wider than usual for other types of fines. Damage tracks caused by heavy cosmic ray nuclei and an unusually high halogen content might provide for stronger etching conditions upon exposure to water vapor.

Chemistry of americium

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

Schulz, W.W.

1976-01-01

Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

Chemistry and dynamics of the lower troposphere over North America and the North Atlantic Ocean in fall 1997 observed using an airborne UV DIAL system

NASA Technical Reports Server (NTRS)

Grant, William B.; Butler, Carolyn F.; Fenn, Marta A.; Kooi, Susan A.; Browell, Edward V.; Fuelberg, Henry

1998-01-01

The NASA Langley Research Center's airborne UV Differential Absorption Lidar (DIAL) system participated in the Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) mission from October 13 to November 12, 1997. The purpose of the mission was to study the upper troposphere/lower stratosphere in and near the North Atlantic flight corridor to better understand this region of the atmosphere and how civilian air travel in the corridor might be affecting the atmospheric chemistry. Bases of operations included NASA Ames, California (37.4 deg N, 122.1 deg W); Bangor, Maine (44.8 deg N, 68.8 deg W); Shannon, Ireland (52.7 deg N, 8.9 deg W); and Lajes, Terceira Island, Azores (38.8 deg N, 27.1 deg W). Since the UV DIAL system observes in the nadir as well as the zenith, aerosol and ozone data were obtained from near the Earth's surface to the lower stratosphere. A number of interesting features were noted relating to both chemistry and dynamics of the troposphere, which are reported here.

Structural Chemistry of Human RNA Methyltransferases.

PubMed

Schapira, Matthieu

2016-03-18

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

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

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

2017-05-02

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

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

PubMed

Chang, E; Lee, T M

2002-07-01

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

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

DOE PAGES

Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.; ...

2015-07-30

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H 2 reduction of Cu 2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changesmore » are accompanied by a reduction in the proportion of strong CO binding sites. Here, we propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.« less

Synthesis and patterning of polymers for biomedical applications

NASA Astrophysics Data System (ADS)

He, Wei

The goal of this dissertation is to synthesize and characterize novel polymers, as well as to explore alternative techniques for biomedical applications. Although significant progress has been achieved in the design and preparation of new biomaterials over the past years, much remains to be accomplished. The interactions between biomaterials and cells are very important, especially in the emerging field of tissue engineering. The focus of this research is to improve such interactions via several different approaches. One way to engineer cellular interaction is by modifying surface topography through micro-patterning. Although photolithography is widely used for patterning, it is not suitable for direct cell and protein patterning because of the usage of organic solvent for feature development. To address this issue, a biocompatible chemically amplified resist derived from N-vinyl-2-pyrrolidone (NVP) was prepared. The results have shown that no organic solvent development was required to reveal the patterns and cells can be cultured on these patterned surfaces directly. Strong cell alignment was observed. The other issue addressed in this research is to develop a technique that can modify surface morphology and surface chemistry simultaneously. Such a technique is called masked ion beam lithography (MIBL). By implanting phosphorous ions on polymeric substrates through masks, not only micron/nano size patterns were generated on the surface, but also the phosphorous ions were incorporated. Incubation of bone forming osteoblast cells on these ion beam processed samples has shown that osteoblast cell attachment to the substrate was enhanced, as a consequence of the increased surface roughness as well as the implanted phosphorous ions. This indicates that MIBL can not only generate micro/nanostructures on the surface of a biocompatible polymer, but can also selectively modify the surface chemistry by implanting with specific ions. These factors can contribute to an osteogenic environment.

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.

Teaching Lab Report Writing through Inquiry: A Green Chemistry Stoichiometry Experiment for General Chemistry

ERIC Educational Resources Information Center

Cacciatore, Kristen L.; Sevian, Hannah

2006-01-01

We present an alternative to a traditional first-year chemistry laboratory experiment. This experiment has four key features: students utilize stoichiometry, learn and apply principles of green chemistry, engage in authentic scientific inquiry, and discover why each part of a scientific lab report is necessary. The importance and essential…

The effect of nanoparticle size on in vivo pharmacokinetics and cellular interaction

PubMed Central

Hoshyar, Nazanin; Gray, Samantha; Han, Hongbin; Bao, Gang

2016-01-01

Nanoparticle-based technologies offer exciting new approaches to disease diagnostics and therapeutics. To take advantage of unique properties of nanoscale materials and structures, the size, shape and/or surface chemistry of nanoparticles need to be optimized, allowing their functionalities to be tailored for different biomedical applications. Here we review the effects of nanoparticle size on cellular interaction and in vivo pharmacokinetics, including cellular uptake, biodistribution and circulation half-life of nanoparticles. Important features of nanoparticle probes for molecular imaging and modeling of nanoparticle size effects are also discussed. PMID:27003448

Characteristics of the Shuttle Orbiter Leeside Flow During A Reentry Condition

NASA Technical Reports Server (NTRS)

Kleb, William L.; Weilmuenster, K. James

1992-01-01

A study of the leeside flow characteristics of the Shuttle Orbiter is presented for a reentry flight condition. The flow is computed using a point-implicit, finite-volume scheme known as the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA). LAURA is a second-order accurate, laminar Navier-Stokes solver, incorporating finite-rate chemistry with a radiative equilibrium wall temperature distribution and finite-rate wall catalysis. The resulting computational solution is analyzed in terms of salient flow features and the surface quantities are compared with flight data.

Imaging experiment: The Viking Lander

USGS Publications Warehouse

Mutch, T.A.; Binder, A.B.; Huck, F.O.; Levinthal, E.C.; Morris, E.C.; Sagan, C.; Young, A.T.

1972-01-01

The Viking Lander Imaging System will consist of two identical facsimile cameras. Each camera has a high-resolution mode with an instantaneous field of view of 0.04??, and survey and color modes with instantaneous fields of view of 0.12??. Cameras are positioned one meter apart to provide stereoscopic coverage of the near-field. The Imaging Experiment will provide important information about the morphology, composition, and origin of the Martian surface and atmospheric features. In addition, lander pictures will provide supporting information for other experiments in biology, organic chemistry, meteorology, and physical properties. ?? 1972.

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.

Stochastic and Deterministic Approaches to Gas-grain Modeling of Interstellar Sources

NASA Astrophysics Data System (ADS)

Vasyunin, Anton; Herbst, Eric; Caselli, Paola

During the last decade, our understanding of the chemistry on surfaces of interstellar grains has been significantly enchanced. Extensive laboratory studies have revealed complex structure and dynamics in interstellar ice analogues, thus making our knowledge much more detailed. In addition, the first qualitative investigations of new processes were made, such as non-thermal chemical desorption of species from dust grains into the gas. Not surprisingly, the rapid growth of knowledge about the physics and chemistry of interstellar ices led to the development of a new generation of astrochemical models. The models are typically characterized by more detailed treatments of the ice physics and chemistry than previously. The utilized numerical approaches vary greatly from microscopic models, in which every single molecule is traced, to ``mean field'' macroscopic models, which simulate the evolution of averaged characteristics of interstellar ices, such as overall bulk composition. While microscopic models based on a stochastic Monte Carlo approach are potentially able to simulate the evolution of interstellar ices with an account of most subtle effects found in a laboratory, their use is often impractical due to limited knowledge about star-forming regions and huge computational demands. On the other hand, deterministic macroscopic models that often utilize kinetic rate equations are computationally efficient but experience difficulties in incorporation of such potentially important effects as ice segregation or discreteness of surface chemical reactions. In my talk, I will review the state of the art in the development of gas-grain astrochemical models. I will discuss how to incorporate key features of ice chemistry and dynamics in the gas-grain astrochemical models, and how the incorporation of recent laboratory findings into gas-grain models helps to better match observations.

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.

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

USGS Publications Warehouse

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

1998-01-01

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

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Micro- and nanofluidic systems in devices for biological, medical and environmental research

NASA Astrophysics Data System (ADS)

Evstrapov, A. A.

2017-11-01

The use of micro- and nanofluidic systems in modern analytical instruments allow you to implement a number of unique opportunities and achieve ultra-high measurement sensitivity. The possibility of manipulation of the individual biological objects (cells, bacteria, viruses, proteins, nucleic acids) in a liquid medium caused the development of devices on microchip platform for methods: chromatographic and electrophoretic analyzes; polymerase chain reaction; sequencing of nucleic acids; immunoassay; cytometric studies. Development of micro and nano fabrication technologies, materials science, surface chemistry, analytical chemistry, cell engineering have led to the creation of a unique systems such as “lab-on-a-chip”, “human-on-a-chip” and other. This article discusses common in microfluidics materials and methods of making functional structures. Examples of integration of nanoscale structures in microfluidic devices for the implementation of new features and improve the technical characteristics of devices and systems are shown.

A general strategy to synthesize chemically and topologically anisotropic Janus particles

PubMed Central

Fan, Jun-Bing; Song, Yongyang; Liu, Hong; Lu, Zhongyuan; Zhang, Feilong; Liu, Hongliang; Meng, Jingxin; Gu, Lin; Wang, Shutao; Jiang, Lei

2017-01-01

Emulsion polymerization is the most widely used synthetic technique for fabricating polymeric particles. The interfacial tension generated with this technique limits the ability to tune the topology and chemistry of the resultant particles. We demonstrate a general emulsion interfacial polymerization approach that involves introduction of additional anchoring molecules surrounding the microdroplets to synthesize a large variety of Janus particles with controllable topological and chemical anisotropy. This strategy is based on interfacial polymerization mediated by an anchoring effect at the interface of microdroplets. Along the interface of the microdroplets, the diverse topology and surface chemistry features of the Janus particles can be precisely tuned by regulating the monomer type and concentration as well as polymerization time. This method is applicable to a wide variety of monomers, including positively charged, neutrally charged, and negatively charged monomers, thereby enriching the community of Janus particles. PMID:28691089

Porous silicon in drug delivery devices and materials☆

PubMed Central

Anglin, Emily J.; Cheng, Lingyun; Freeman, William R.; Sailor, Michael J.

2009-01-01

Porous Si exhibits a number of properties that make it an attractive material for controlled drug delivery applications: The electrochemical synthesis allows construction of tailored pore sizes and volumes that are controllable from the scale of microns to nanometers; a number of convenient chemistries exist for the modification of porous Si surfaces that can be used to control the amount, identity, and in vivo release rate of drug payloads and the resorption rate of the porous host matrix; the material can be used as a template for organic and biopolymers, to prepare composites with a designed nanostructure; and finally, the optical properties of photonic structures prepared from this material provide a self-reporting feature that can be monitored in vivo. This paper reviews the preparation, chemistry, and properties of electrochemically prepared porous Si or SiO2 hosts relevant to drug delivery applications. PMID:18508154

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.

Mussel-Inspired Adhesives and Coatings

PubMed Central

Lee, Bruce P.; Messersmith, P.B.; Israelachvili, J.N.; Waite, J.H.

2011-01-01

Mussels attach to solid surfaces in the sea. Their adhesion must be rapid, strong, and tough, or else they will be dislodged and dashed to pieces by the next incoming wave. Given the dearth of synthetic adhesives for wet polar surfaces, much effort has been directed to characterizing and mimicking essential features of the adhesive chemistry practiced by mussels. Studies of these organisms have uncovered important adaptive strategies that help to circumvent the high dielectric and solvation properties of water that typically frustrate adhesion. In a chemical vein, the adhesive proteins of mussels are heavily decorated with Dopa, a catecholic functionality. Various synthetic polymers have been functionalized with catechols to provide diverse adhesive, sealant, coating, and anchoring properties, particularly for critical biomedical applications. PMID:22058660

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

3D DNA origami as programmable anchoring points for bioreceptors in fiber optic surface plasmon resonance biosensing.

PubMed

Daems, Devin; Pfeifer, Wolfgang; Rutten, Iene; Sacca, Barbara; Spasic, Dragana; Lammertyn, Jeroen

2018-06-27

Many challenges in biosensing originate from the fact that the all-important nano-architecture of the biosensor's surface, including precise density and orientation of bioreceptors, is not entirely comprehended. Here we introduced a 3D DNA origami as bioreceptor carrier to functionalize the fiber optic surface plasmon resonance (FO-SPR) sensor with nanoscale precision. Starting from a 24-helix bundle, two distinct DNA origami structures were designed to position thrombin-specific aptamers with different density and distance (27 and 113 nm) from the FO-SPR surface. The origami-based biosensors proved to be not only capable of reproducible, label-free thrombin detection, but revealed also valuable innovative features: (1) a significantly better performance in the absence of backfilling, known as essential in biosensing field, suggesting improved bioreceptor orientation and accessibility and (2) a wider linear range compared to previously reported thrombin biosensors. We envisage that our method will be beneficial both for scientists and clinicians looking for new surface (bio)chemistry and improved diagnostics.

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.

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

USGS Publications Warehouse

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

1996-01-01

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

Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

ERIC Educational Resources Information Center

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

1980-01-01

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

Characteristics of the surface chemistry of linden pyrochar after removal of labile organic matter

NASA Astrophysics Data System (ADS)

Valeeva, A. A.; Smirnova, E. V.; Giniyatullin, K. G.; Vorobev, V. V.; Biktasheva, L. R.; Grachev, A. N.

2018-01-01

The changes of chemical properties of the pyrochar surface were studied in the laboratory experiment that simulated pedogenic transformation of pyrochar under the influence of soil biota. The native pyrochar samples were obtained by pyrolysis of linden wood residues at the temperature of 250°C, 450°C and 650°C. Their modified samples were obtained by removing an easily degradable pool of organic substances that can be used by microorganisms during the first months after application to the soil. In low-temperature linden pyrochar (250°C and 450°C) dominated carboxylic and phenolic surface groups, in high-temperature (650°C) - lactonic groups. After removal of readily decomposable organic substances the acidity of the phenolic and lactonic groups in pyrochar of low-temperature pyrolysis sharply decreased. Characteristic feature of all studied samples is the presence in IR spectra of absorption bands of gyroxyl, carbonyl, methylene groups and organosilicon polymers. The feature of IR spectra of linden pyrochar (250°C and 450°C) is the presence of absorption bands of the stretching vibrations of the tertiary alcohols and phenols C-O group.

High density plasma etching of magnetic devices

NASA Astrophysics Data System (ADS)

Jung, Kee Bum

Magnetic materials such as NiFe (permalloy) or NiFeCo are widely used in the data storage industry. Techniques for submicron patterning are required to develop next generation magnetic devices. The relative chemical inertness of most magnetic materials means they are hard to etch using conventional RIE (Reactive Ion Etching). Therefore ion milling has generally been used across the industry, but this has limitations for magnetic structures with submicron dimensions. In this dissertation, we suggest high density plasmas such as ECR (Electron Cyclotron Resonance) and ICP (Inductively Coupled Plasma) for the etching of magnetic materials (NiFe, NiFeCo, CoFeB, CoSm, CoZr) and other related materials (TaN, CrSi, FeMn), which are employed for magnetic devices like magnetoresistive random access memories (MRAM), magnetic read/write heads, magnetic sensors and microactuators. This research examined the fundamental etch mechanisms occurring in high density plasma processing of magnetic materials by measuring etch rate, surface morphology and surface stoichiometry. However, one concern with using Cl2-based plasma chemistry is the effect of residual chlorine or chlorinated etch residues remaining on the sidewalls of etched features, leading to a degradation of the magnetic properties. To avoid this problem, we employed two different processing methods. The first one is applying several different cleaning procedures, including de-ionized water rinsing or in-situ exposure to H2, O2 or SF6 plasmas. Very stable magnetic properties were achieved over a period of ˜6 months except O2 plasma treated structures, with no evidence of corrosion, provided chlorinated etch residues were removed by post-etch cleaning. The second method is using non-corrosive gas chemistries such as CO/NH3 or CO2/NH3. There is a small chemical contribution to the etch mechanism (i.e. formation of metal carbonyls) as determined by a comparison with Ar and N2 physical sputtering. The discharge should be NH3-rich to achieve the highest etch rates. Several different mask materials were investigated, including photoresist, thermal oxide and deposited oxide. Photoresist etches very rapidly in CO/NH 3 and use of a hard mask is necessary to achieve pattern transfer. Due to its physically dominated nature, the CO/NH3 chemistry appears suited to shallow etch depth (≤0.5mum) applications, but mask erosion leads to sloped feature sidewalls for deeper features.

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 Nobel Legacy: A Journey through Chemistry Inspired by the Achievements of Nobel Laureates.

PubMed

Novara, Francesca Rita; Ross, Haymo

2018-03-15

The Prize is right! Chemistry-A European Journal will start an exciting journey exploring the significance of Nobel Prize awards in Chemistry in the corresponding contemporary chemistry fields. In this new journal feature called "The Nobel Legacy", a recurring series of invited Review-type articles each one connected to a particular Nobel Prize in Chemistry will be published. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

NASA Technical Reports Server (NTRS)

Montgomery, Christopher J.; Kosaly, George; Riley, James J.

1993-01-01

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Beyond Academic Tracking: Using Cluster Analysis and Self-Organizing Maps to Investigate Secondary Students' Chemistry Self-Concept

ERIC Educational Resources Information Center

Nielsen, Sara E.; Yezierski, Ellen J.

2016-01-01

Academic tracking, placing students in different classes based on past performance, is a common feature of the American secondary school system. A longitudinal study of secondary students' chemistry self-concept scores was conducted, and one feature of the study was the presence of academic tracking. Though academic tracking is one way to group…

The Role of Water Chemistry in Marine Aquarium Design: A Model System for a General Chemistry Class

ERIC Educational Resources Information Center

Keaffaber, Jeffrey J.; Palma, Ramiro; Williams, Kathryn R.

2008-01-01

Water chemistry is central to aquarium design, and it provides many potential applications for discussion in undergraduate chemistry and engineering courses. Marine aquaria and their life support systems feature many chemical processes. A life support system consists of the entire recirculation system, as well as the habitat tank and all ancillary…

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)

Toward 4D Nanoprinting with Tip-Induced Organic Surface Reactions.

PubMed

Carbonell, Carlos; Braunschweig, Adam B

2017-02-21

Future nanomanufacturing tools will prepare organic materials with complex four-dimensional (4D) structure, where the position (x, y, z) and chemical composition within a volume is controlled with sub-1 μm spatial resolution. Such tools could produce substrates that mimic biological interfaces, like the cell surface or the extracellular matrix, whose topology and chemical complexity combine to direct some of the most sophisticated biological events. The control of organic materials at the nanoscale-level of spatial resolution could revolutionize the assembly of next generation optical and electronic devices or substrates for tissue engineering or enable fundamental biological or material science investigations. Organic chemistry provides the requisite control over the orientation and position of matter within a nanoscale reference frame through the formation of new covalent bonds. Several challenges however preclude the integration of organic chemistry with conventional nanomanufacturing approaches, namely most nanolithography platforms would denature or destroy delicate organic and biologically active matter, confirming covalent bond formation at interfaces remains difficult, and finally, only a small handful of the reactions used to transform molecules in solution have been validated on surfaces. Thus, entirely new approaches, where organic transformations and spatial control are considered equally important contributors, are needed to create 4D organic nanoprinting platforms. This Account describes efforts from our group to reconcile nanolithography, and specifically massively parallel scanning probe lithography (SPL), with organic chemistry to further the goal of 4D organic nanoprinting. Massively parallel SPL involves arrays of elastomeric pyramids mounted onto piezoelectric actuators, and creates patterns with feature diameters below 50 nm by using the pyramidal tips for either the direct deposition of ink or the localized delivery of energy to a surface. While other groups have focused on tip and array architetctures, our efforts have been on exploring their use for localizing organic chemistry on surfaces with nanoscale spatial resolution in 3D. Herein we describe the use of massively parallel SPL to create covalently immobilized patterns of organic materials using thermal, catalytic, photochemical, and force-accelerated reactions. In doing so, we have developed a high-throughput protocol for confirming interfacial bond formation. These efforts have resulted in new opportunities for the preparation of glycan arrays, novel approaches for covalently patterning graphene, and a 3D nanoprinter by combining photochemical brush polymerizations with SPL. Achieving true 4D nanoprinting involves advances in surface chemistry and instrumentation development, and to this end 4D micropatterns were produced in a microfluidic photoreactor that can position polymers composed of different monomers within micrometer proximity. A substantial gap remains, however, between these current technologies and the future's 4D nanomanufacturing tools, but the marriage of SPL with organic chemistry is an important step toward this goal. As this field continues to mature we can expect bottom-up 4D nanomanufacturing to begin supplanting conventional top-down strategies for preparing electronics, bioarrays, and functional substrates. In addition, these new printing technologies may enable the preparation of synthetic targets, such as artificial biological interfaces, with a level of organic sophistication that is entirely unachievable using existing technologies.

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

Multifunctional clickable and protein-repellent magnetic silica nanoparticles

NASA Astrophysics Data System (ADS)

Estupiñán, Diego; Bannwarth, Markus B.; Mylon, Steven E.; Landfester, Katharina; Muñoz-Espí, Rafael; Crespy, Daniel

2016-01-01

Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the introduced surface functionality. Herein, organosilane chemistry is employed to produce magnetic silica nanoparticles bearing differing amounts of amino and alkene functional groups on their surface as orthogonally addressable chemical functionalities. Simultaneously, a short-chain zwitterion is added to decrease the non-specific adsorption of biomolecules on the nanoparticles surface. The multifunctional particles display reduced protein adsorption after incubation in undiluted fetal bovine serum as well as in single protein solutions (serum albumin and lysozyme). Besides, the particles retain their capacity to selectively react with biomolecules. Thus, they can be covalently bio-functionalized with an antibody by means of orthogonal click reactions. These features make the described multifunctional silica nanoparticles a promising system for the study of surface interactions with biomolecules, targeting, and bio-sensing.Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the introduced surface functionality. Herein, organosilane chemistry is employed to produce magnetic silica nanoparticles bearing differing amounts of amino and alkene functional groups on their surface as orthogonally addressable chemical functionalities. Simultaneously, a short-chain zwitterion is added to decrease the non-specific adsorption of biomolecules on the nanoparticles surface. The multifunctional particles display reduced protein adsorption after incubation in undiluted fetal bovine serum as well as in single protein solutions (serum albumin and lysozyme). Besides, the particles retain their capacity to selectively react with biomolecules. Thus, they can be covalently bio-functionalized with an antibody by means of orthogonal click reactions. These features make the described multifunctional silica nanoparticles a promising system for the study of surface interactions with biomolecules, targeting, and bio-sensing. Electronic supplementary information (ESI) available: Detailed synthetic procedures and additional experimental light scattering and zeta-potential data. See DOI: 10.1039/c5nr08258g

750 Reasons To Celebrate Chemistry!

PubMed

Compton, Neville

2017-06-12

Time to reflect: This issue marks the 750th issue of Chemistry-A European Journal. The journal has played a significant role in changing chemistry. Its history has featured top papers from top authors for more than 20 years. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

Dendrimeric coating of glass slides for sensitive DNA microarrays analysis

PubMed Central

Le Berre, Véronique; Trévisiol, Emmanuelle; Dagkessamanskaia, Adilia; Sokol, Serguei; Caminade, Anne-Marie; Majoral, Jean Pierre; Meunier, Bernard; François, Jean

2003-01-01

Successful use and reliability of microarray technology is highly dependent on several factors, including surface chemistry parameters and accessibility of cDNA targets to the DNA probes fixed onto the surface. Here, we show that functionalisation of glass slides with homemade dendrimers allow production of more sensitive and reliable DNA microarrays. The dendrimers are nanometric structures of size-controlled diameter with aldehyde function at their periphery. Covalent attachment of these spherical reactive chemical structures on amino-silanised glass slides generates a reactive ∼100 Å layer onto which amino-modified DNA probes are covalently bound. This new grafting chemistry leads to the formation of uniform and homogenous spots. More over, probe concentration before spotting could be reduced from 0.2 to 0.02 mg/ml with PCR products and from 20 to 5 µM with 70mer oligonucleotides without affecting signal intensities after hybridisation with Cy3- and Cy5-labelled targets. More interestingly, while the binding capacity of captured probes on dendrimer-activated glass surface (named dendrislides) is roughly similar to other functionalised glass slides from commercial sources, detection sensitivity was 2-fold higher than with other available DNA microarrays. This detection limit was estimated to 0.1 pM of cDNA targets. Altogether, these features make dendrimer-activated slides ideal for manufacturing cost-effective DNA arrays applicable for gene expression and detection of mutations. PMID:12907740

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

Petkov, Valeri; Hessel, Colin M.; Ovtchinnikoff, Justine

High-energy synchrotron X-ray diffraction coupled to atomic pair distribution function analysis and computer simulations is used to determine the atomic-scale structure of silicon (Si) nanoparticles obtained by two different synthetic routes. Results show that Si nanoparticles may have significant structural differences depending on the synthesis route and surface chemistry. In this case, one method produced Si nanoparticles that are highly crystalline but surface oxidized, whereas a different method yields organic ligand-passivated nanoparticles without surface oxide but that are structurally distorted at the atomic scale. Particular structural features of the oxide-free Si nanoparticles such as average first coordination numbers, length ofmore » structural coherence, and degree of local distortions are compared to their optical properties such as photoluminescence emission energy, quantum yield, and Raman spectra. A clear structure–properties correlation is observed indicating that the former may need to be taken into account when considering the latter.« less

S-layers: principles and applications

PubMed Central

Sleytr, Uwe B; Schuster, Bernhard; Egelseer, Eva-Maria; Pum, Dietmar

2014-01-01

Monomolecular arrays of protein or glycoprotein subunits forming surface layers (S-layers) are one of the most commonly observed prokaryotic cell envelope components. S-layers are generally the most abundantly expressed proteins, have been observed in species of nearly every taxonomical group of walled bacteria, and represent an almost universal feature of archaeal envelopes. The isoporous lattices completely covering the cell surface provide organisms with various selection advantages including functioning as protective coats, molecular sieves and ion traps, as structures involved in surface recognition and cell adhesion, and as antifouling layers. S-layers are also identified to contribute to virulence when present as a structural component of pathogens. In Archaea, most of which possess S-layers as exclusive wall component, they are involved in determining cell shape and cell division. Studies on structure, chemistry, genetics, assembly, function, and evolutionary relationship of S-layers revealed considerable application potential in (nano)biotechnology, biomimetics, biomedicine, and synthetic biology. PMID:24483139

Modulators of heterogeneous protein surface water dynamics

NASA Astrophysics Data System (ADS)

Han, Songi

The hydration water that solvates proteins is a major factor in driving or enabling biological events, including protein-protein and protein-ligand interactions. We investigate the role of the protein surface in modulating the hydration water fluctuations on both the picosecond and nanosecond timescale with an emerging experimental NMR technique known as Overhauser Dynamic Nuclear Polarization (ODNP). We carry out site-specific ODNP measurements of the hydration water fluctuations along the surface of Chemotaxis Y (CheY), and correlate the measured fluctuations to hydropathic and topological properties of the CheY surface as derived from molecular dynamics (MD) simulation. Furthermore, we compare hydration water fluctuations measured on the CheY surface to that of other globular proteins, as well as intrinsically disordered proteins, peptides, and liposome surfaces to systematically test characteristic effects of the biomolecular surface on the hydration water dynamics. Our results suggest that the labile (ps) hydration water fluctuations are modulated by the chemical nature of the surface, while the bound (ns) water fluctuations are present on surfaces that feature a rough topology and chemical heterogeneity such as the surface of a folded and structured protein. In collaboration with: Ryan Barnes, Dept of Chemistry and Biochemistry, University of California Santa Barbara

Effect of Pore Structure and Chemistry on the Performance of Activated Oil Sands Petroleum Coke Electrodes for use in Electrochemical Double-Layer Capacitors

NASA Astrophysics Data System (ADS)

Zuliani, Jocelyn Ellen

Electrical energy storage is a limiting barrier to widespread usage and commercialization of sustainable and renewable energy sources, such as wind and solar energy, as well as integration of electric vehicles. Electrochemical double-layer capacitors (EDLCs) are a promising energy storage technology that offers the benefits of high power density, long cycle life, rapid charging rates, and moderate energy density. The energy storage mechanism of EDLCs is physical ion adsorption on the surface of porous carbon electrodes. This thesis is an investigation of three different sections relating to EDLCs: 1) techniques to properly characterize novel porous carbon electrode materials, 2) investigation of activated oil sands petroleum coke (APC) as the electrode material for EDLCs, and 3) a systematic study of the effects of porous carbon structure and chemistry on EDLC performance. In the first section, it was shown that variations in operating conditions and testing techniques can lead to discrepancies in measured and reported capacitance. Therefore, it was concluded that a standardized approach is necessary in order to properly compare different porous carbon electrodes. In the second section, APC was investigated as a novel electrode material for EDLCs. PetCoke is a carbon dense material that can be activated with potassium hydroxide to generate high surface area porous carbon materials. These materials show promising electrochemical performance in EDLCs, with capacitance values up to 400 Fg-1 in 4M potassium hydroxide aqueous electrolytes, depending on the operating conditions. Additionally, the power density of these materials is comparable to that of other carbon nanomaterials, which are more costly and challenging to produce. Finally, the third section investigates the relationship between measured capacitance, and carbon macrostructure, meso-structure, microstructure, and oxygen content. In each of these studies, the desired parameter was varied, while all others (surface area, pore size, chemistry) were maintained constant. Through this systematic approach, this thesis investigates and quantifies the relationship between EDLC performance and important characteristic parameters through isolation of each individual parameter. By understanding the key structural and chemical features that improve EDLC performance, focus can be placed on engineering a sustainable and economic porous carbon material that has these desired features.

Jao Van De Lagemaat | NREL

Science.gov Websites

Jao Van De Lagemaat Photo of Jao Vandelagemaat. Jao Van De Lagemaat Center Director: Chemistry and Lagemaat is currently the Center Director of the Chemistry and Nanoscience Center at NREL. He received his university. Education Ph.D. Physical Chemistry, University of Utrecht Featured Publications View all NREL

Nuclear Overhauser Effect Spectroscopy: An Advanced Undergraduate Experiment

ERIC Educational Resources Information Center

Huggins, Michael T.; Billimoria, Freida

2007-01-01

The stereochemical features of molecules can have far reaching effects in many areas of science including medicinal chemistry, materials chemistry, and supramolecular chemistry. There have been many techniques developed over the years to determine the absolute configuration of alkenes: the R,S configuration of chiral centers and the most stable…

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

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

Tait, Steven L.

Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desiredmore » overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also serve as easily tuned model systems for exploring the chemistry of single-site transition metals and tandem catalysts that could then be developed into a zeolite or other stable support structures. In this final technical report, three major advances our described that further these goals. The first is a study demonstrating the ability to tune the oxidation state of V single-site centers on a surface by design of the surrounding ligand field. The synthesis of the single-site centers was developed in a previous reporting period of this project and this new advance shows a distinct new ability of the systems to have a designed oxidation state of the metal center. Second, we demonstrate metal complexation at surfaces using vibrational spectroscopy and also show a metal replacement reaction on Ag surfaces. Third, we demonstrate a surface-catalyzed dehydrocyclization reaction important for metal-organic catalyst design at surfaces.« less

The Feature of Scientific Explanation in the Teaching of Chemistry in the Environment of New Information of School Students' Developmental Education

ERIC Educational Resources Information Center

Gilmanshina, Suriya I.; Gilmanshin, Iskander R.; Sagitova, Rimma N.; Galeeva, Asiya I.

2016-01-01

The aim of this article is to disclose features of scientific explanation in teaching of chemistry in the environment of new information of school students' developmental education. The leading approach to the study of this problem is the information and environmental approach that comprehensively address the problem of scientific explanation in…

JCE Resources for Chemistry and Art.

ERIC Educational Resources Information Center

Jacobsen, Erica K.

2001-01-01

Includes an annotated bibliography of articles featured in this journal on art, dyes, glass, pottery and ceramics, interdisciplinary courses in art and chemistry, light and color, metalwork, and music. (YDS)

Recurrent filmwise and dropwise condensation on a beetle mimetic surface.

PubMed

Hou, Youmin; Yu, Miao; Chen, Xuemei; Wang, Zuankai; Yao, Shuhuai

2015-01-27

Vapor condensation plays a key role in a wide range of industrial applications including power generation, thermal management, water harvesting and desalination. Fast droplet nucleation and efficient droplet departure as well as low interfacial thermal resistance are important factors that determine the thermal performances of condensation; however, these properties have conflicting requirements on the structural roughness and surface chemistry of the condensing surface or condensation modes (e.g., filmwise vs dropwise). Despite intensive efforts over the past few decades, almost all studies have focused on the dropwise condensation enabled by superhydrophobic surfaces. In this work, we report the development of a bioinspired hybrid surface with high wetting contrast that allows for seamless integration of filmwise and dropwise condensation modes. We show that the synergistic cooperation in the observed recurrent condensation modes leads to improvements in all aspects of heat transfer properties including droplet nucleation density, growth rate, and self-removal, as well as overall heat transfer coefficient. Moreover, we propose an analytical model to optimize the surface morphological features for dramatic heat transfer enhancement.

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.

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…

LARGE—A Plasma Torch for Surface Chemistry Applications and CVD Processes—A Status Report

NASA Astrophysics Data System (ADS)

Zimmermann, Stephan; Theophile, Eckart; Landes, Klaus; Schein, Jochen

2008-12-01

The LARGE ( LONG ARG GENERATOR) is a new generation DC-plasma torch featuring an extended arc which is operated with a perpendicular gas flow to create a wide (up to 45 cm) plasma jet well suited for large area plasma processing. Using plasma diagnostic systems like high speed imaging, enthalpy probe, emission spectroscopy, and tomography, the LARGE produced plasma jet characteristics have been measured and sources of instability have been identified. With a simple model/simulation of the system LARGE III-150 and numerous experimental results, a new nozzle configuration and geometry (LARGE IV-150) has been designed, which produces a more homogenous plasma jet. These improvements enable the standard applications of the LARGE plasma torch (CVD coating process and surface activation process) to operate with higher efficiency.

Localized aliphatic organic material on the surface of Ceres

NASA Astrophysics Data System (ADS)

De Sanctis, M. C.; Ammannito, E.; McSween, H. Y.; Raponi, A.; Marchi, S.; Capaccioni, F.; Capria, M. T.; Carrozzo, F. G.; Ciarniello, M.; Fonte, S.; Formisano, M.; Frigeri, A.; Giardino, M.; Longobardo, A.; Magni, G.; McFadden, L. A.; Palomba, E.; Pieters, C. M.; Tosi, F.; Zambon, F.; Raymond, C. A.; Russell, C. T.

2017-02-01

Organic compounds occur in some chondritic meteorites, and their signatures on solar system bodies have been sought for decades. Spectral signatures of organics have not been unambiguously identified on the surfaces of asteroids, whereas they have been detected on cometary nuclei. Data returned by the Visible and InfraRed Mapping Spectrometer on board the Dawn spacecraft show a clear detection of an organic absorption feature at 3.4 micrometers on dwarf planet Ceres. This signature is characteristic of aliphatic organic matter and is mainly localized on a broad region of ~1000 square kilometers close to the ~50-kilometer Ernutet crater. The combined presence on Ceres of ammonia-bearing hydrated minerals, water ice, carbonates, salts, and organic material indicates a very complex chemical environment, suggesting favorable environments to prebiotic chemistry.

Sensitivity of WRF-Chem model to land surface schemes: Assessment in a severe dust outbreak episode in the Central Mediterranean (Apulia Region)

NASA Astrophysics Data System (ADS)

Rizza, Umberto; Miglietta, Mario Marcello; Mangia, Cristina; Ielpo, Pierina; Morichetti, Mauro; Iachini, Chiara; Virgili, Simone; Passerini, Giorgio

2018-03-01

The Weather Research and Forecasting model with online coupled chemistry (WRF-Chem) is applied to simulate a severe Saharan dust outbreak event that took place over Southern Italy in March 2016. Numerical experiments have been performed applying a physics-based dust emission model, with soil properties generated from three different Land Surface Models, namely Noah, RUC and Noah-MP. The model performance in reproducing the severe desert dust outbreak is analysed using an observational dataset of aerosol and desert dust features that includes optical properties from satellite and ground-based sun-photometers, and in-situ particulate matter mass concentration (PM) data. The results reveal that the combination of the dust emission model with the RUC Land Surface Model significantly over-predicts the emitted mineral dust; on the other side, the combination with Noah or Noah-MP Land Surface Model (LSM) gives better results, especially for the daily averaged PM10.

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.

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.

Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

PubMed

Lehn, Jean-Marie

2012-01-01

Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

American Chemical Society. 23rd Great Lakes Regional Meeting. Program and abstracts

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

Not Available

1990-01-01

The technical program includes some 250 papers in 38 sessions, featuring 16 symposia with 99 invited speakers. Program highlights include a plenary lecture, The Origin and Consequences of Scientific Illiteracy, by Jon D. Miller. Sessions for general technical papers are scheduled in the following categories: analytical chemistry; biochemistry; inorganic chemistry; organic chemistry; and physical chemistry. Papers have been processed for inclusion on the data base.

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

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.

Introduction of Entropy via the Boltzmann Distribution in Undergraduate Physical Chemistry: A Molecular Approach

ERIC Educational Resources Information Center

Kozliak, Evguenii I.

2004-01-01

A molecular approach for introducing entropy in undergraduate physical chemistry course and incorporating the features of Davies' treatment that meets the needs of the students but ignores the complexities of statistics and upgrades the qualitative, intuitive approach of Lambert for general chemistry to a semiquantitative treatment using Boltzmann…

ChemApproach: Validation of a Questionnaire to Assess the Learning Approaches of Chemistry Students

ERIC Educational Resources Information Center

Lastusaari, Mika; Laakkonen, Eero; Murtonen, Mari

2016-01-01

The theory of learning approaches has proven to be one of the most powerful theories explaining university students' learning. However, learning approaches are sensitive to the situation and the content of learning. Chemistry has its own specific features that should be considered when exploring chemistry students' learning habits, specifically…

Exploring the effectiveness of engagement in a broad range of disciplinary practices on learning of Turkish high-school chemistry students

NASA Astrophysics Data System (ADS)

Seda Cetin, Pinar; Eymur, Guluzar; Southerland, Sherry A.; Walker, Joi; Whittington, Kirby

2018-03-01

This study examines the influence of laboratory instruction that engages students in a wide range of the practices of science on Turkish high-school students' chemistry learning. In this mixed methods study, student learning in two different laboratory settings was compared, one that featured an instruction that engaged students in a wide range of disciplinary practices (through Argument-driven Inquiry - ADI) and similar laboratories in which a more traditional Structured Inquiry (SI) approach was employed. The data sources included a Chemistry Concept test, an Argumentative Writing Assessment, and Semi-structured interviews. After seven weeks of chemistry instruction, students experiencing ADI instruction scored higher on the Chemistry Concept test and the Argumentative Writing Assessment than students experiencing SI instruction. Furthermore, girls who experienced ADI instruction scored higher on the assessments than their majority peers in the same class. The results suggest that Turkish students can substantially improve their chemistry proficiency if they have an opportunity to engage in instruction featuring a broad array of the practices of science.

Mechanism of amino acid interaction with silicon nitride surface during chemical mechanical planarization

NASA Astrophysics Data System (ADS)

America, William George

Chemical-Mechanical Planarization (CMP) has become an essential technology for making modern semiconductor devices. This technique was originally applied to overcome the depth of focus limitations of lithography tools during pattern development of metal and dielectric films. As features of the semiconductor device became smaller the lithographic process shifted to shorter exposure wavelengths and the useable depth of focus became smaller. The topography differences on the wafer's surface from all of the previous processing steps became greater than the exposure tools could properly project. CMP helped solve this problem by bringing the features of the wafer surface to the same plane. As semiconductor fabrication technology progressed further, CMP was applied to other areas of the process, including shallow trench isolation and metal line Damascene processing. In its simplest application, CMP polishes on features projecting upward and higher than the average surface. These projections experience more work and are polished faster. Given sufficient time the surface becomes essentially flat, on a micro-scale, and the lithographic projection tools has the same plane onto which to focus. Thus, the pattern is properly and uniformly exposed and subsequent reactive ion etching (RIE) steps are executed. This technique was initially applied to later steps in the wafer processing scheme to render a new flat surface at each metal layer. Building on this success, CMP has been applied to a broad range of steps in the wafer processing particularly where surface topography warrants and when RIE of dielectric or metallic films is not practical. CMP has seen its greatest application in semiconductor logic and memory devices and most recently, a Damascene processing for copper lines and shallow trench isolation. This pattern dependent CMP issue is explored in this thesis as it pertains primarily to shallow trench isolation CMP coupled with a highly selective slurry chemistry.

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.

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

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.

Surface phenomena related to mirror degradation in extreme ultraviolet (EUV) lithography

NASA Astrophysics Data System (ADS)

Madey, Theodore E.; Faradzhev, Nadir S.; Yakshinskiy, Boris V.; Edwards, N. V.

2006-12-01

One of the most promising methods for next generation device manufacturing is extreme ultraviolet (EUV) lithography, which uses 13.5 nm wavelength radiation generated from freestanding plasma-based sources. The short wavelength of the incident illumination allows for a considerable decrease in printed feature size, but also creates a range of technological challenges not present for traditional optical lithography. Contamination and oxidation form on multilayer reflecting optics surfaces that not only reduce system throughput because of the associated reduction in EUV reflectivity, but also introduce wavefront aberrations that compromise the ability to print uniform features. Capping layers of ruthenium, films ∼2 nm thick, are found to extend the lifetime of Mo/Si multilayer mirrors used in EUV lithography applications. However, reflectivities of even the Ru-coated mirrors degrade in time during exposure to EUV radiation. Ruthenium surfaces are chemically reactive and are very effective as heterogeneous catalysts. In the present paper we summarize the thermal and radiation-induced surface chemistry of bare Ru exposed to gases; the emphasis is on H2O vapor, a dominant background gas in vacuum processing chambers. Our goal is to provide insights into the fundamental physical processes that affect the reflectivity of Ru-coated Mo/Si multilayer mirrors exposed to EUV radiation. Our ultimate goal is to identify and recommend practices or antidotes that may extend mirror lifetimes.

Radiation Chemistry and the Radiation Preservation of Food.

ERIC Educational Resources Information Center

Taub, Irwin A.

1981-01-01

Describes common features in the radiation chemistry of food components, and illustrates how product yields are predicted. Presents data that pertain to the radiolysis of the nitrate ion, metmyoglobin, myosin, and tripalmitin. (CS)

Exploring the Surface of Titan with Cassini-Huygens

NASA Astrophysics Data System (ADS)

Turtle, E. P.; Barnes, J.; Buratti, B. J.; Collins, G.; Fussner, S.; Lopes, R.; Lorenz, R. D.; Lunine, J. I.; McCord, T. B.; McEwen, A. S.; Nelson, R.; Perry, J.; Porco, C. C.; Soderblom, L.; Sotin, C.; Wall, S. D.

2005-12-01

Over the past year, the Cassini-Huygens mission has returned a wealth of data about the surface of Saturn's satellite Titan. Cassini's Imaging Science Subsystem (ISS), RADAR, and Visual and Infrared Mapping Spectrometer (VIMS), and Huygens' Descent Imaging Spectral Radiometer (DISR) have revealed an intriguing surface that is at once familiar and alien. Although water-ice and liquid hydrocarbons play the roles that rock and water play on Earth, the surface appears to have been worked by a wide variety of processes resulting in a seemingly Earth-like balance of fluvial, aeolian, and volcanic features, with relatively few impact craters. There seem to be at least two classes of surface material: dark areas (at visible-IR wavelengths) that are spectrally consistent with contaminated water ice, and brighter areas of unknown composition which show greater variations. The expected bodies of liquids have yet to be definitively identified; however, circumstantial evidence for liquids having acted upon the surface in Titan's past is abundant, primarily in the form of channels, and possible ponds or lakes, which have been observed by multiple instruments. Other features suggest that wind redistributes some surface materials, most likely the detritus of the complex atmospheric chemistry, creating diffuse IR-bright deposits and long, narrow, radar-dark (2.2-cm) stripes, all of which trend generally east-west. Only two impact structures have been identified to date, although several other suspiciously circular features have been documented. A variety of the morphologies observed bear strong resemblances to volcanic structures. A number of other features remain mysterious and further co-analysis of these data sets, as well as the anticipated acquisition of more data, will be needed to fully understand the nature of Titan's surface, the albedo variations observed at different wavelengths, and the processes that have acted upon it (and may continue to). In addition to the Huygens descent, the Cassini orbiter has observed Titan on six close passes to date, and two more are planned for Fall 2005 which will increase both the spatial coverage, at various wavelengths, and the time base over which observations have been made as northern-hemisphere spring approaches. We will present observations of Titan's surface acquired by the complementary suite of instruments on board Cassini-Huygens, the combination of which is proving essential to interpreting Titan's geology.

Surface chemistry driven actuation in nanoporous gold

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

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

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

Molecular Rotors

DTIC Science & Technology

2006-10-31

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

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

Treesearch

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

2003-01-01

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

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

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

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

2015-02-02

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

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

Teaching social responsibility in analytical chemistry.

PubMed

Valcárcel, M; Christian, G D; Lucena, R

2013-07-02

Analytical chemistry is key to the functioning of a modern society. From early days, ethics in measurements have been a concern and that remains today, especially as we have come to rely more on the application of analytical science in many aspects of our lives. The main aim of this Feature is to suggest ways of introducing the topic of social responsibility and its relation to analytical chemistry in undergraduate or graduate chemistry courses.

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

Water soluble nanoporous nanoparticle for in vivo targeted drug delivery and controlled release in B cells tumor context

NASA Astrophysics Data System (ADS)

de Angelis, F.; Pujia, A.; Falcone, C.; Iaccino, E.; Palmieri, C.; Liberale, C.; Mecarini, F.; Candeloro, P.; Luberto, L.; de Laurentiis, A.; Das, G.; Scala, G.; di Fabrizio, E.

2010-10-01

Multitasking nanoparticles are gaining great attention for smart drug delivery systems. The exploration of the nano-scale opens new concrete opportunities for revealing new properties and undiscovered cell-particle interactions. Here we present a biodegradable nanoporous silicon nanoparticle that can be successfully employed for in vivo targeted drug delivery and sustained release. The bare nanoporous nanocarriers can be accurately designed and fabricated with an effective control of porosity, surface chemistry and particle size, up to a few nm. The proposed nanoparticles exhibit several remarkable features including high payload, biodegradability, no toxicity, and multiple loading in water without the need of additional chemical reagents at room temperature. The targeting strategy is based on phage display technology that was successfully used to discover cell surface binding peptide for murine B lymphoma A20 cell line. The peptide used in combination with the nanoporous nanoparticles allows an efficient in vivo targeting, a sustained release and a sensible therapeutic effect.Multitasking nanoparticles are gaining great attention for smart drug delivery systems. The exploration of the nano-scale opens new concrete opportunities for revealing new properties and undiscovered cell-particle interactions. Here we present a biodegradable nanoporous silicon nanoparticle that can be successfully employed for in vivo targeted drug delivery and sustained release. The bare nanoporous nanocarriers can be accurately designed and fabricated with an effective control of porosity, surface chemistry and particle size, up to a few nm. The proposed nanoparticles exhibit several remarkable features including high payload, biodegradability, no toxicity, and multiple loading in water without the need of additional chemical reagents at room temperature. The targeting strategy is based on phage display technology that was successfully used to discover cell surface binding peptide for murine B lymphoma A20 cell line. The peptide used in combination with the nanoporous nanoparticles allows an efficient in vivo targeting, a sustained release and a sensible therapeutic effect. Electronic supplementary information (ESI) available: Nanoparticles fabrication; payload evaluation; dissolution and release profiles; multivalent loading; targeting specifity on A20 Cells; cell cycle analysis; in vitro cytotoxicity assay; in vivo cytotoxicity assay. See DOI: 10.1039/c0nr00161a

Saturn's satellites: Predictions for Cassini

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Hibbitts, C. A.

2004-11-01

Saturn's satellites are subjected to a variety of energy inputs (from photons, magnetospheric and solar ions and electrons) which will affect their surface composition. The Saturn magnetosphere contains an assortment of ions, including O+ and H+ from sputtering of water ice on the inner satellites and N+ from sputtering of Titan's atmosphere. Implantation of these ions onto the surfaces of the satellites may produce compounds possibly detectable by Cassini instruments. The satellites contain water ice and carbon dioxide ice (and possibly organics, on Phoebe). In Delitsky and Lane (2002), chemistry resulting from nitrogen ion implantation into water ice and carbon dioxide ice was outlined. From deposition of N+ ions into H2O/CO2, a complicated C-H-N-O chemistry may result, including formation of isocyanates, nitriles, nitrogen oxides and amino acids. Upon irradiation, H2O/CO2 mixtures will yield esters, ketones, alcohols, carboxylic acids and other interesting compounds. Cassini's infrared instruments CIRS and VIMS have spectral ranges that can detect many bands of these compounds. VIMS spectral range is 0.35 - 5.1 microns; CIRS covers the spectral range 7 - 100 microns, although its Mid-IR interferometer portion (7 -16 microns) is where organic materials are particularly spectrally active. Weak features are present in the short IR for NO (1.91 microns), NO2 (1.95), NH3 (2.00, 2.24), CH3OH (2.27, 2.34), and CO2 (1.965, 2.01) [Quirico et al.,1999]. Some molecules have stronger absorption features at these wavelengths: [CO2: 4.25 - 4.27 microns; NH3: 3 microns and 9.2 microns (important because the 3 micron band can be masked by water); H2CO3: 3.88 microns (weak); HCOOH: 8.2 microns; O2: 9.7 microns]. These molecules may exist as ices, or as molecules trapped in the surface. CH- and CN-containing molecules absorb at 3.2 - 3.4 microns, and 4.6 microns, respectively. H2O2, detected on Europa by its 3.5 micron band, may exist in the icy surfaces of the Saturn satellites as well.

Nanostructured silicon via metal assisted catalyzed etch (MACE): chemistry fundamentals and pattern engineering

NASA Astrophysics Data System (ADS)

Toor, Fatima; Miller, Jeffrey B.; Davidson, Lauren M.; Nichols, Logan; Duan, Wenqi; Jura, Michael P.; Yim, Joanne; Forziati, Joanne; Black, Marcie R.

2016-10-01

There are a range of different methods to generate a nanostructured surface on silicon (Si) but the most cost effective and optically interesting is the metal assisted wet chemical etching (MACE) (Koynov et al 2006 Appl. Phys. Lett. 88 203107). MACE of Si is a controllable, room-temperature wet-chemical technique that uses a thin layer of metal to etch the surface of Si, leaving behind various nano- and micro-scale surface features or ‘black silicon’. MACE-fabricated nanowires (NWs) provide improved antireflection and light trapping functionality (Toor et al 2016 Nanoscale 8 15448-66) compared with the traditional ‘iso-texturing’ (Campbell and Green 1987 J. Appl. Phys. 62 243-9). The resulting lower reflection and improved light trapping can lead to higher short circuit currents in NW solar cells (Toor et al 2011 Appl. Phys. Lett. 99 103501). In addition, NW cells can have higher fill factors and voltages than traditionally processed cells, thus leading to increased solar cell efficiencies (Cabrera et al 2013 IEEE J. Photovolt. 3 102-7). MACE NW processing also has synergy with next generation Si solar cell designs, such as thin epitaxial-Si and passivated emitter rear contact (Toor et al 2016 Nanoscale 8 15448-66). While several companies have begun manufacturing black Si, and many more are researching these techniques, much of the work has not been published in traditional journals and is publicly available only through conference proceedings and patent publications, which makes learning the field challenging. There have been three specialized review articles published recently on certain aspects of MACE or black Si, but do not present a full review that would benefit the industry (Liu et al 2014 Energy Environ. Sci. 7 3223-63 Yusufoglu et al 2015 IEEE J. Photovolt. 5 320-8 Huang et al 2011 Adv. Mater. 23 285-308). In this feature article, we review the chemistry of MACE and explore how changing parameters in the wet etch process effects the resulting texture on the Si surface. Then we review efforts to increase the uniformity and reproducibility of the MACE process, which is critical for commercializing the black Si technology.

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.

Magnetorheological finishing with chemically modified fluids for studying material removal of single-crystal ZnS

NASA Astrophysics Data System (ADS)

Salzman, S.; Romanofsky, H. J.; Clara, Y. I.; Giannechini, L. J.; West, Garrett J.; Lambropoulos, J. C.; Jacobs, S. D.

2013-09-01

Magnetorheological finishing (MRF) of polycrystalline, chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and zinc selenide (ZnSe) can leave millimeter-size artifacts on the part surface. These pebble-like features come from the anisotropic mechanical and chemical properties of the ceramic material and from the CVD growth process itself. The resulting surface texture limits the use of MRF for polishing aspheric and other complex shapes using these important infrared (IR) ceramics. An investigation of the individual contributions of chemistry and mechanics to polishing of other polycrystalline ceramics has been employed in the past to overcome similar material anisotropy problems. The approach taken was to study the removal process for the different single-crystal orientations that comprise the ceramic, making adjustments to mechanics (polishing abrasive type and concentration) and polishing slurry chemistry (primarily pH) to equalize the removal rate for all crystal orientations. Polishing with the modified slurry was shown to prevent the development of surface texture. Here we present mechanical (microhardness testing) and chemical (acid etching) studies performed on the four single-crystal orientations of ZnS: 100, 110, 111, and 311. We found that the (111) plane is 35% to 55% harder and 30% to 40% more resistant to chemical etching than the other three planes. This relatively high degree of variation in these properties can help to explain the surface texture developed from MRF of the polycrystalline material. Theoretical calculations of microhardness, planar, and bond densities are presented and compared with the experimental data. Here surface characterization of these single-crystal orientations of ZnS for material removal and roughness with chemically modified MR fluids at various pH levels between pH 4 and pH 6 are presented for the first time.

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)

Osteoinductive peptide-functionalized nanofibers with highly ordered structure as biomimetic scaffolds for bone tissue engineering.

PubMed

Gao, Xiang; Zhang, Xiaohong; Song, Jinlin; Xu, Xiao; Xu, Anxiu; Wang, Mengke; Xie, Bingwu; Huang, Enyi; Deng, Feng; Wei, Shicheng

2015-01-01

The construction of functional biomimetic scaffolds that recapitulate the topographical and biochemical features of bone tissue extracellular matrix is now of topical interest in bone tissue engineering. In this study, a novel surface-functionalized electrospun polycaprolactone (PCL) nanofiber scaffold with highly ordered structure was developed to simulate the critical features of native bone tissue via a single step of catechol chemistry. Specially, under slightly alkaline aqueous solution, polydopamine (pDA) was coated on the surface of aligned PCL nanofibers after electrospinning, followed by covalent immobilization of bone morphogenetic protein-7-derived peptides onto the pDA-coated nanofiber surface. Contact angle measurement, Raman spectroscopy, and X-ray photoelectron spectroscopy confirmed the presence of pDA and peptides on PCL nanofiber surface. Our results demonstrated that surface modification with osteoinductive peptides could improve cytocompatibility of nanofibers in terms of cell adhesion, spreading, and proliferation. Most importantly, Alizarin Red S staining, quantitative real-time polymerase chain reaction, immunostaining, and Western blot revealed that human mesenchymal stem cells cultured on aligned nanofibers with osteoinductive peptides exhibited enhanced osteogenic differentiation potential than cells on randomly oriented nanofibers. Furthermore, the aligned nanofibers with osteoinductive peptides could direct osteogenic differentiation of human mesenchymal stem cells even in the absence of osteoinducting factors, suggesting superior osteogenic efficacy of biomimetic design that combines the advantages of osteoinductive peptide signal and highly ordered nanofibers on cell fate decision. The presented peptide-decorated bone-mimic nanofiber scaffolds hold a promising potential in the context of bone tissue engineering.

The distribution of organic material and its contribution to the micro-topography of particles from wettable and water repellent soils

NASA Astrophysics Data System (ADS)

Bryant, Rob; Cheng, Shuying; Doerr, Stefan H.; Wright, Chris J.; Bayer, Julia V.; Williams, Rhodri P.

2010-05-01

Organic coatings on mineral particles will mask the physic-chemical properties of the underlying mineral surface. Surface images and force measurements obtained using atomic force microscopy (AFM) provide information about the nature of and variability in surfaces properties at the micro- to nano-scale. As AFM technology and data processing advance it is anticipated that a significant amount of information will be obtained simultaneously from individual contacts made at high frequency in non-contact or tapping mode operation. For present purposes the surfaces of model materials (smooth glass surfaces and acid-washed sand (AWS)) provide an indication of the dependency of the so-called AFM phase image on the topographic image (which is obtained synoptically). Pixel wise correlation of these images reveals how the modulation of an AFM probe is affected when topographic features are encountered. Adsorption of soil-derived humic acid (HA) or lecithin (LE), used here as an example for natural organic material, on these surfaces provides a soft and compliant, albeit partial, covering on the mineral which modifies the topography and the response of an AFM tip as it partially indents the soft regions (which contributes depth to the phase image). This produces a broadening on the data domain in the topographic/phase scatter diagram. Two dimensional classifications of these data, together with those obtained from sand particles drawn from water repellent and wettable soils, suggest that these large adsorbate molecules appear to have little preference to attach to particular topographic features or elevations. It appears that they may effectively remain on the surface at the point of initial contact. If organic adsorbates present a hydrophobic outer surface, then it seems possible that elevated features will not be immune from this and provide scope for a local, albeit, small contribution to the expression of super-hydrophobicity. It is therefore speculated here that the water repellency of a soil is the result of not only of particle surface chemistry and soil pore space geometry, but also of the micro-topography generated by organic material adsorbed on particle surfaces.

Synergistic effect of topography, surface chemistry and conductivity of the electrospun nanofibrous scaffold on cellular response of PC12 cells.

PubMed

Tian, Lingling; Prabhakaran, Molamma P; Hu, Jue; Chen, Menglin; Besenbacher, Flemming; Ramakrishna, Seeram

2016-09-01

Electrospun nanofibrous nerve implants is a promising therapy for peripheral nerve injury, and its performance can be tailored by chemical cues, topographical features as well as electrical properties. In this paper, a surface modified, electrically conductive, aligned nanofibrous scaffold composed of poly (lactic acid) (PLA) and polypyrrole (Ppy), referred to as o-PLAPpy_A, was fabricated for nerve regeneration. The morphology, surface chemistry and hydrophilicity of nanofibers were characterized by Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and water contact angle, respectively. The effects of these nanofibers on neuronal differentiation using PC12 cells were evaluated. A hydrophilic surface was created by Poly-ornithine coating, which was able to provide a better environment for cell attachment, and furthermore aligned fibers were proved to be able to guide PC12 cells grow along the fiber direction and be beneficial for neurite outgrowth. The cellular response of PC12 cells to pulsed electrical stimulation was evaluated by NF 200 and alpha tubulin expression, indicating that electrical stimulation with a voltage of 40mV could enhance the neurite outgrowth. The PC12 cells stimulated with electrical shock showed greater level of neurite outgrowth and smaller cell body size. Moreover, the PC12 cells under electrical stimulation showed better viability. In summary, the o-PLAPpy_A nanofibrous scaffold supported the attachment, proliferation and differentiation of PC12 cells in the absence of electrical stimulation, which could be potential candidate for nerve regeneration applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanical Stress in InP Structures Etched in an Inductively Coupled Plasma Reactor with Ar/Cl2/CH4 Plasma Chemistry

NASA Astrophysics Data System (ADS)

Landesman, Jean-Pierre; Cassidy, Daniel T.; Fouchier, Marc; Pargon, Erwine; Levallois, Christophe; Mokhtari, Merwan; Jimenez, Juan; Torres, Alfredo

2018-02-01

We investigated the crystal lattice deformation that can occur during the etching of structures in bulk InP using SiNx hard masks with Ar/Cl2/CH4 chemistries in an inductively coupled plasma reactor. Two techniques were used: degree of polarization (DOP) of the photo-luminescence, which gives information on the state of mechanical stress present in the structures, and spectrally resolved cathodo-luminescence (CL) mapping. This second technique also provides elements on the mechanical stress in the samples through analysis of the spectral shift of the CL intrinsic emission lines. Preliminary DOP mapping experiments have been conducted on the SiNx hard mask patterns without etching the underlying InP. This preliminary study demonstrated the potential of DOP to map mechanical stress quantitatively in the structures. In a second step, InP patterns with various widths between 1 μm and 20 μm, and various depths between 1 μm and 6 μm, were analyzed by the 2 techniques. DOP measurements were made both on the (100) top surface of the samples and on the (110) cleaved cross section. CL measurements were made only from the (100) surface. We observed that inside the etched features, close to the vertical etched walls, there is always some compressive deformation, while it is tensile just outside the etched features. The magnitude of these effects depends on the lateral and depth dimensions of the etched structures, and on the separation between them (the tensile deformation increases between them due to some kind of proximity effect when separation decreases).

Exploring the Information Literacy Needs and Values of High School Chemistry Teachers

ERIC Educational Resources Information Center

Zane, Marci; Tucci, Valerie Karvey

2016-01-01

To meet the information literacy (IL) needs of chemistry students, The College of New Jersey's (TCNJ) Library and Chemistry Departments have created a three-year seminar with a strong IL component. The program focuses on IL skills necessary for success in industry and graduate or professional education, but may lack features specific to those…

Femtosecond laser structuring of silver-containing glass: Silver redistribution, selective etching, and surface topology engineering

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

Desmoulin, Jean-Charles; Petit, Yannick; Cardinal, Thierry, E-mail: thierry.cardinal@icmcb.cnrs.fr

2015-12-07

Femtosecond direct laser writing in silver-containing phosphate glasses allows for the three-dimensional (3D) implementation of complex photonic structures. Sample translation along or perpendicular to the direction of the beam propagation has been performed, which led to the permanent formation of fluorescent structures, either corresponding to a tubular shape or to two parallel planes at the vicinity of the interaction voxel, respectively. These optical features are related to significant modifications of the local material chemistry. Indeed, silver depletion areas with a diameter below 200 nm were evidenced at the center of the photo-produced structures while photo-produced luminescence properties are attributed to themore » formation of silver clusters around the multiphoton interaction voxel. The laser-triggered oxidation-reduction processes and the associated photo-induced silver redistribution are proposed to be at the origin of the observed original 3D luminescent structures. Thanks to such material structuring, surface engineering has been also demonstrated. Selective surface chemical etching of the glass has been obtained subsequently to laser writing at the location of the photo-produced structures, revealing features with nanometric depth profiles and radial dimensions strongly related to the spatial distributions of the silver clusters.« less

The Significance of Interfacial Water Structure in Soluble Salt Flotation Systems.

PubMed

Hancer, M.; Celik, M. S.; Miller, J. D.

2001-03-01

Flotation of soluble salts with dodecyl amine hydrochloride (DAH) and sodium dodecyl sulfate (SDS) collectors has demonstrated that the interfacial water structure and hydration states of soluble salt surfaces together with the precipitation tendency of the corresponding collector salts are of considerable importance in explaining their flotation behavior. In particular, the high concentration of ions in these soluble salt brines and their hydration appear to modify the bulk and interfacial structure of water as revealed by contact angle measurements and this effect is shown to be an important feature in the flotation chemistry of soluble salt minerals including alkali halide and alkali oxyanion salts. Depending on characteristic chemical features (salt type), the salt can serve either as a structure maker, in which intermolecular hydrogen bonding between water molecules is facilitated, or as a structure breaker, in which intermolecular hydrogen bonding between water molecules is disrupted. For structure making salts the brine completely wets the salt surface and no contact angle can be measured. For structure breaking salts the brine does not completely wet the salt surface and a finite contact angle is measured. In this regard it has been found that soluble salt flotation either with the cationic DAH or anionic SDS collector is possible only if the salt is a structure breaker. Copyright 2001 Academic Press.

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.

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.

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

PubMed

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

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.

Titan's Surface Composition from the Cassini Visual and Infrared Mapping Spectrometer (VIMS) Investigation

NASA Astrophysics Data System (ADS)

McCord, T. B.; Griffith, C. A.; Hansen, G. B.; Lunine, J. I.; Baines, K. H.; Brown, R. H.; Buratti, B.; Clark, R. N.; Cruikshank, D. P.; Filacchione, G.; Jaumann, R.; Hibbitts, C. A.; Sotine, C.; Cassini VIMS

2004-11-01

Titan, the largest satellite of Saturn, has a thick atmosphere containing methane with high altitude haze that obscures the surface except for windows in the methane absorption bands at some IR wavelengths where scattering also is reduced. Chemistry models of the atmosphere suggest deep deposits of organic liquids and solids (1). Groundbased telescopic observations of Titan's integral disk suggest the presence of water ice (2). The Cassini VIMS obtained spectra in the 0.35 to 5.1 μm range that include narrow windows in the methane spectrum near 1.6, 2.0, 2.8, and 5.0 μm where the surface might have been observed with spatial resolution up to about 100 x 200 km during the Saturn orbit insertion phase on June 30 2004. Surface albedo features seem to appear in these windows. We have analyzed Titan's spectra in an attempt to identity the surface material(s). The VIMS spectra were averaged for several pixels for each of six regions on Titan corresponding to apparent bright and dark surface features. The spectra were calibrated to I/F as seen by VIMS and then were analyzed using radiative transfer models to remove the effects of the atmosphere (2) to estimate surface I/F values. These were then compared with candidate material reflectance at each of the spectral windows. Preliminary analysis suggests that the average results will agree with previous groundbased data analyses (2) and there is the suggestion of differences in reflectance among the surface regions analyzed so far. This work was supported by the NASA Cassini Project. (1) Lunine et al., Science, 222, 1229, 1983. (2) Coustenis et al., Icarus 118, 87, 1995; Griffith et al., Science 300, 628, 2003.

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

NASA Astrophysics Data System (ADS)

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

2008-08-01

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

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

PubMed Central

2016-01-01

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

Large-area one-step assembly of three-dimensional porous metal micro/nanocages by ethanol-assisted femtosecond laser irradiation for enhanced antireflection and hydrophobicity.

PubMed

Li, Guoqiang; Li, Jiawen; Zhang, Chenchu; Hu, Yanlei; Li, Xiaohong; Chu, Jiaru; Huang, Wenhao; Wu, Dong

2015-01-14

The capability to realize 2D-3D controllable metallic micro/nanostructures is of key importance for various fields such as plasmonics, electronics, bioscience, and chemistry due to unique properties such as electromagnetic field enhancement, catalysis, photoemission, and conductivity. However, most of the present techniques are limited to low-dimension (1D-2D), small area, or single function. Here we report the assembly of self-organized three-dimensional (3D) porous metal micro/nanocages arrays on nickel surface by ethanol-assisted femtosecond laser irradiation. The underlying formation mechanism was investigated by a series of femtosecond laser irradiation under exposure time from 5 to 30 ms. We also demonstrate the ability to control the size of micro/nanocage arrays from 0.8 to 2 μm by different laser pulse energy. This method features rapidness (∼10 min), simplicity (one-step process), and ease of large-area (4 cm(2) or more) fabrication. The 3D cagelike micro/nanostructures exhibit not only improved antireflection from 80% to 7% but also enhanced hydrophobicity from 98.5° to 142° without surface modification. This simple technique for 3D large-area controllable metal microstructures will find great potential applications in optoelectronics, physics, and chemistry.

Nanoporous carbon for electric double layer supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Garcia, Betzaida Batalla

The subject of this study is the synthesis, characterization, chemical composition, and tuning of the porous structure of organic and carbon cryogels for electrochemical applications, particularly supercapacitors. Alternate methods such as an improved synthesis using a reactive catalyst, surface chemical modifications and an electrochemical characterization that takes into account the pore morphology are discussed. Impedance spectroscopy, complex capacitance and power were used to identify key energy losses in the capacitor; an optimal pore size of ca. 2 nm and other features were found. Also, synthesis modification and surface chemistry were used to improve the chemistry and structure of the electrodes reducing metal impurities and removing detrimental functional groups. First, carbon cryogels produced without metal ion impurities were synthesized using hexamine (an amine base catalyst), resorcinol, furaldehyde and solvent mixtures. These metal ion free amine-catalyzed gels also produced strong cryogels that can be machined. The carbon cryogels produced using the amine catalyst have cycle stability performances that exceed that of commercial samples. Carbon cryogels were also doped using ammonia borane to promote boron and nitrogen esters and improved the capacitance up to 30% due to faradaic reactions. Furthermore, nitrogen esters were also introduced into the carbon (via pyrolysis of hexamine) with yields of up to 14 at%. These new esters have low content of oxygen and increased the capacitance up to 50%.

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.

Current status and future prospects for enabling chemistry technology in the drug discovery process.

PubMed

Djuric, Stevan W; Hutchins, Charles W; Talaty, Nari N

2016-01-01

This review covers recent advances in the implementation of enabling chemistry technologies into the drug discovery process. Areas covered include parallel synthesis chemistry, high-throughput experimentation, automated synthesis and purification methods, flow chemistry methodology including photochemistry, electrochemistry, and the handling of "dangerous" reagents. Also featured are advances in the "computer-assisted drug design" area and the expanding application of novel mass spectrometry-based techniques to a wide range of drug discovery activities.

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

PubMed

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

2016-12-07

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

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.

Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.; Jackman, Charles H.; Kaye, Jack A.

1986-01-01

Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

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

Sun, Ying-Sui; Yang, Wei-En; Zhang, Lan

In nasal reconstruction, the response of cells to titanium (Ti) implants is mainly determined by surface features of the implant. In a pilot study, the authors applied electrochemical anodization to Ti surfaces in an alkaline solution to create a network of nanoscale surface structures. This nanonetwork was intended to enhance the responses of primary human nasal epithelial cell (HNEpC) to the Ti surface. In this study, the authors then treated the anodized, nanonetwork-structured Ti surface using nitrogen plasma immersion ion implantation (NPIII) in order to further improve the HNEpC response to the Ti surface. Subsequently, surface characterization was performed tomore » elucidate morphology, roughness, wettability, and chemistry of specimens. Cytotoxicity, blood, and HNEpC responses were also evaluated. Our results demonstrate that NPIII treatment led to the formation of a noncytotoxic TiN-containing thin film (thickness <100 nm) on the electrochemically anodized Ti surface with a nanonetwork-structure. NPIII treatment was shown to improve blood clotting and the adhesion of platelets to the anodized Ti surface as well as the adhesion and proliferation of hNEpC. This research spreads our understanding of the fact that a TiN-containing thin film, produced using NPIII treatment, could be used to improve blood and HNEpC responses to anodized, nanonetwork-structured Ti surfaces in nasal implant applications.« less

Selective host molecules obtained by dynamic adaptive chemistry.

PubMed

Matache, Mihaela; Bogdan, Elena; Hădade, Niculina D

2014-02-17

Up till 20 years ago, in order to endow molecules with function there were two mainstream lines of thought. One was to rationally design the positioning of chemical functionalities within candidate molecules, followed by an iterative synthesis-optimization process. The second was the use of a "brutal force" approach of combinatorial chemistry coupled with advanced screening for function. Although both methods provided important results, "rational design" often resulted in time-consuming efforts of modeling and synthesis only to find that the candidate molecule was not performing the designed job. "Combinatorial chemistry" suffered from a fundamental limitation related to the focusing of the libraries employed, often using lead compounds that limit its scope. Dynamic constitutional chemistry has developed as a combination of the two approaches above. Through the rational use of reversible chemical bonds together with a large plethora of precursor libraries, one is now able to build functional structures, ranging from quite simple molecules up to large polymeric structures. Thus, by introduction of the dynamic component within the molecular recognition processes, a new perspective of deciphering the world of the molecular events has aroused together with a new field of chemistry. Since its birth dynamic constitutional chemistry has continuously gained attention, in particular due to its ability to easily create from scratch outstanding molecular structures as well as the addition of adaptive features. The fundamental concepts defining the dynamic constitutional chemistry have been continuously extended to currently place it at the intersection between the supramolecular chemistry and newly defined adaptive chemistry, a pivotal feature towards evolutive chemistry. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

NASA Astrophysics Data System (ADS)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

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

NIAC Phase 1 Final Study Report on Titan Aerial Daughtercraft

NASA Technical Reports Server (NTRS)

Matthies, Larry

2017-01-01

Saturns giant moon Titan has become one of the most fascinating bodies in the Solar System. Even though it is a billion miles from Earth, data from the Cassini mission reveals that Titan has a very diverse, Earth-like surface, with mountains, fluvial channels, lakes, evaporite basins, plains, dunes, and seas [Lopes 2010] (Figure 1). But unlike Earth, Titans surface likely is composed of organic chemistry products derived from complex atmospheric photochemistry [Lorenz 2008]. In addition, Titan has an active meteorological system with observed storms and precipitation-induced surface darkening suggesting a hydrocarbon cycle analogous to Earths water cycle [Turtle 2011].Titan is the richest laboratory in the solar system for studying prebiotic chemistry, which makes studying its chemistry from the surface and in the atmosphere one of the most important objectives in planetary science [Decadal 2011]. The diversity of surface features on Titan related to organic solids and liquids makes long-range mobility with surface access important [Decadal 2011]. This has not been possible to date, because mission concepts have had either no mobility (landers), no surface access (balloons and airplanes), or low maturity, high risk, and/or high development costs for this environment (e,g. large, self-sufficient, long-duration helicopters). Enabling in situ mobility could revolutionize Titan exploration, similarly to the way rovers revolutionized Mars exploration. Recent progress on several fronts has suggested that small-scale rotorcraft deployed as daughtercraft from a lander or balloon mothercraft may be an effective, affordable approach to expanding Titan surface access. This includes rapid progress on autonomous navigation capabilities of such aircraft for terrestrial applications and on miniaturization, driven by the consumer mobile electronics market, of high performance of sensors, processors, and other avionics components needed for such aircraft. Chemical analysis, for example with a mass spectrometer, will be important to any Titan surface mission. Anticipating that it may be more practical to host chemical analysis instruments on a mothership than a daughtercraft, we defined system and mission concepts that deploy a small rotorcraft, termed a Titan Aerial Daughtercraft (TAD), from a lander or balloon to perform high-resolution imaging and mapping, potentially land to acquire microscopic images or other in situ measurements, and acquire samples to return to analytical instruments on the mothership. In principle, the ability to recharge batteries in TAD from a radioisotope or other long-lived power source on the mothership could enable multiple sorties. For a lander-based mission, a variety of landing sites is conceivable, including near lake margins, in dry lake beds, or in regions of plains, dunes, or putative cryovolanic or impact melt features. Such missions may require landing with greater precision than in previous missions (Huygens) and mission studies; this could also enhance the ability of TAD to reach interesting terrain from the landing site. Precision descent may also benefit balloon missions, with or without a daughtercraft, by increasing the probability that the balloon will drift over desired terrain early in its mission. Given these potential benefits, the overall concept studied here includes brief consideration of precision descent for landing or balloon deployment, followed by one or more sorties by a rotorcraft deployed from the mothership, with the ability to return to the mothership.

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)

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.

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.

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

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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.

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

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

2005-01-01

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

Chemistry Modeling for Aerothermodynamics and TPS

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

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.

Current status and future prospects for enabling chemistry technology in the drug discovery process

PubMed Central

Djuric, Stevan W.; Hutchins, Charles W.; Talaty, Nari N.

2016-01-01

This review covers recent advances in the implementation of enabling chemistry technologies into the drug discovery process. Areas covered include parallel synthesis chemistry, high-throughput experimentation, automated synthesis and purification methods, flow chemistry methodology including photochemistry, electrochemistry, and the handling of “dangerous” reagents. Also featured are advances in the “computer-assisted drug design” area and the expanding application of novel mass spectrometry-based techniques to a wide range of drug discovery activities. PMID:27781094

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

Far-infrared study of tracers of oxygen chemistry in diffuse clouds

NASA Astrophysics Data System (ADS)

Wiesemeyer, H.; Güsten, R.; Heyminck, S.; Hübers, H. W.; Menten, K. M.; Neufeld, D. A.; Richter, H.; Simon, R.; Stutzki, J.; Winkel, B.; Wyrowski, F.

2016-01-01

Context. The chemistry of the diffuse interstellar medium rests upon three pillars: exothermic ion-neutral reactions ("cold chemistry"), endothermic neutral-neutral reactions with significant activation barriers ("warm chemistry"), and reactions on the surfaces of dust grains. While warm chemistry becomes important in the shocks associated with turbulent dissipation regions, the main path for the formation of interstellar OH and H2O is that of cold chemistry. Aims: The aim of this study is to observationally confirm the association of atomic oxygen with both atomic and molecular gas phases, and to understand the measured abundances of OH and OH+ as a function of the available reservoir of H2. Methods: We obtained absorption spectra of the ground states of OH, OH+ and O I with high-velocity resolution, with GREAT onboard SOFIA, and with the THz receiver at the APEX. We analyzed them along with ancillary spectra of HF and CH from HIFI. To deconvolve them from the hyperfine structure and to separate the blend that is due to various velocity components on the sightline, we fit model spectra consisting of an appropriate number of Gaussian profiles using a method combining simulated annealing with downhill simplex minimization. Together with HF and/or CH as a surrogate for H2, and H I λ21 cm data, the molecular hydrogen fraction fNH2 = N(H2)/(N(H) + 2N(H2)) can be determined. We then investigated abundance ratios as a function of fNH2. Results: The column density of O I is correlated at a high significance with the amount of available molecular and atomic hydrogen, with an atomic oxygen abundance of 3 × 10-4 relative to H nuclei. While the velocities of the absorption features of OH and OH+ are loosely correlated and reflect the spiral arm crossings on the sightline, upon closer inspection they display an anticorrespondence. The arm-to-interarm density contrast is found to be higher in OH than in OH+. While both species can coexist, with a higher abundance in OH than in OH+, the latter is found less frequently in absence of OH than the other way around, which is a direct consequence of the rapid destruction of OH+ by dissociative recombination when not enough H2 is available. This conjecture has been substantiated by a comparison between the OH/OH+ ratio with fNH2, showing a clear correlation. The hydrogen abstraction reaction chain OH+(H2,H)H2O+(H2,H)H3O+ is confirmed as the pathway for the production of OH and H2O. Our estimate of the branching ratio of the dissociative recombination of H3O+ to OH and H2O is confined within the interval of 84 to 91%, which matches laboratory measurements (74 to 83%). - A correlation between the linewidths and column densities of OH+ features is found to be significant with a false-alarm probability below 5%. Such a correlation is predicted by models of interstellar MHD turbulence. For OH the same correlation is found to be insignificant because there are more narrow absorption features. Conclusions: While it is difficult to assess the contributions of warm neutral-neutral chemistry to the observed abundances, it seems fair to conclude that the predictions of cold ion-neutral chemistry match the abundance patterns we observed.

Quantification of air plasma chemistry for surface disinfection

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

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

USGS Publications Warehouse

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

2009-01-01

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

Molecular Composition and Chemistry of Isolated Dense Cores

NASA Astrophysics Data System (ADS)

Cook, Amanda; Boogert, A.

2009-01-01

The composition of molecular clouds and the envelopes and disks surrounding low mass protostars within them is still poorly known. There is little doubt that a large fraction of the molecules is frozen on grains, but the abundance of several crucial species (e.g. ammonia, methanol, ions) in the ices is still uncertain. In addition, prominent spectral features discovered decades ago are still not securely identified (e.g. the 6.85-micron absorption band). Gas phase and grain surface chemistry play pivotal roles in molecule formation, but numerous other processes could have significant impacts as well: shocks, thermal heating, irradiation of ices by ultraviolet photons and cosmic rays. Complex species could be formed this way, profoundly influencing cloud, disk and planetary/cometary chemistry. We have obtained Spitzer/IRS spectra of an unprecedented sample of sight-lines tracing 25 dense isolated cores. These cores physically differ from the large, cluster-forming molecular clouds (e.g. Ophiuchus, Perseus) that are commonly studied: they are less turbulent, colder, less dense, and likely longer lived. These IRS spectra of isolated cores thus provide unique information on ice formation and destruction mechanisms. Toward the same cores, we observed 33 highly extincted background stars as well, tracing the quiescent cloud medium against which the ices around protostars can be contrasted.

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability

PubMed Central

Bsat, Suzan; Amin Yavari, Saber; Munsch, Maximilian; Valstar, Edward R.; Zadpoor, Amir A.

2015-01-01

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200–300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface. PMID:28788021

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability.

PubMed

Bsat, Suzan; Yavari, Saber Amin; Munsch, Maximilian; Valstar, Edward R; Zadpoor, Amir A

2015-04-08

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200-300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface.

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...

Dynamic combinatorial libraries: new opportunities in systems chemistry.

PubMed

Hunt, Rosemary A R; Otto, Sijbren

2011-01-21

Combinatorial chemistry is a tool for selecting molecules with special properties. Dynamic combinatorial chemistry started off aiming to be just that. However, unlike ordinary combinatorial chemistry, the interconnectedness of dynamic libraries gives them an extra dimension. An understanding of these molecular networks at systems level is essential for their use as a selection tool and creates exciting new opportunities in systems chemistry. In this feature article we discuss selected examples and considerations related to the advanced exploitation of dynamic combinatorial libraries for their originally conceived purpose of identifying strong binding interactions. Also reviewed are examples illustrating a trend towards increasing complexity in terms of network behaviour and reversible chemistry. Finally, new applications of dynamic combinatorial chemistry in self-assembly, transport and self-replication are discussed.

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.

Transepithelial and endothelial transport of poly (amidoamine) dendrimers.

PubMed

Kitchens, Kelly M; El-Sayed, Mohamed E H; Ghandehari, Hamidreza

2005-12-14

This article summarizes our efforts to evaluate the potential of poly (amidoamine) (PAMAM) dendrimers as carriers for oral drug delivery. Specifically, the permeability of a series of cationic PAMAM-NH2 (G0-G4) dendrimers across Caco-2 cell monolayers was evaluated as a function of dendrimer generation, concentration, and incubation time. The influence of dendrimer surface charge on the integrity, paracellular permeability, and viability of Caco-2 cell monolayers was monitored by measuring the transepithelial electrical resistance (TEER), 14C-mannitol permeability, and leakage of lactate dehydrogenase (LDH) enzyme, respectively. Microvascular extravasation of PAMAM-NH2 dendrimers in relation to their size, molecular weight, and molecular geometry is also discussed. Results of these studies show that transepithelial transport and microvascular extravasation of PAMAM dendrimers are dependent on their structural features including molecular size, molecular geometry, and surface chemistry. These results suggest that by optimizing the size and surface charge of PAMAM dendrimers, it is possible to develop oral delivery systems based on these carriers for targeted drug delivery.

Wetting hysteresis induced by nanodefects

PubMed Central

Giacomello, Alberto; Schimmele, Lothar; Dietrich, Siegfried

2016-01-01

Wetting of actual surfaces involves diverse hysteretic phenomena stemming from ever-present imperfections. Here, we clarify the origin of wetting hysteresis for a liquid front advancing or receding across an isolated defect of nanometric size. Various kinds of chemical and topographical nanodefects, which represent salient features of actual heterogeneous surfaces, are investigated. The most probable wetting path across surface heterogeneities is identified by combining, within an innovative approach, microscopic classical density functional theory and the string method devised for the study of rare events. The computed rugged free-energy landscape demonstrates that hysteresis emerges as a consequence of metastable pinning of the liquid front at the defects; the barriers for thermally activated defect crossing, the pinning force, and hysteresis are quantified and related to the geometry and chemistry of the defects allowing for the occurrence of nanoscopic effects. The main result of our calculations is that even weak nanoscale defects, which are difficult to characterize in generic microfluidic experiments, can be the source of a plethora of hysteretical phenomena, including the pinning of nanobubbles. PMID:26721395

Nano-assembly of nanodiamonds by conjugation to actin filaments.

PubMed

Bradac, Carlo; Say, Jana M; Rastogi, Ishan D; Cordina, Nicole M; Volz, Thomas; Brown, Louise J

2016-03-01

Fluorescent nanodiamonds (NDs) are remarkable objects. They possess unique mechanical and optical properties combined with high surface areas and controllable surface reactivity. They are non-toxic and hence suited for use in biological environments. NDs are also readily available and commercially inexpensive. Here, the exceptional capability of controlling and tailoring their surface chemistry is demonstrated. Small, bright diamond nanocrystals (size ˜30 nm) are conjugated to protein filaments of actin (length ˜3-7 µm). The conjugation to actin filaments is extremely selective and highly target-specific. These unique features, together with the relative simplicity of the conjugation-targeting method, make functionalised nanodiamonds a powerful and versatile platform in biomedicine and quantum nanotechnologies. Applications ranging from using NDs as superior biological markers to, potentially, developing novel bottom-up approaches for the fabrication of hybrid quantum devices that would bridge across the bio/solid-state interface are presented and discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of contaminant removal by an optical strip material

NASA Astrophysics Data System (ADS)

Hamilton, James P.; Frigo, S. P.; Caroll, Brenden J.; Assoufidyen, L.; Lewis, Matthew S.; Cook, Russell E.; de Carlo, F.

2001-03-01

Department of Chemistry and Engineering Physics, University of Wisconsin-Platteville, Platteville, WI 53818 Advanced Photon Source, X-Ray Facilities Division, Argonne National Laboratory, Advanced Photon Source, User Program Division, Argonne National Laboratory, *Electron Microscopy Center, Materials Science Division, Argonne National Laboratory, Argonne National Laboratory, 9700 S. Cass Ave., Argonne IL 60439-4856 USA A novel optical strip coating material, Opticlean, has been shown to safely remove fingerprints, particles and contamination from a variety of optical surfaces including coated glass, Si and first surface mirrors. Contaminant removal was monitored by Nomarski, Atomic Force and Scanning Electron Microscopy. Sub-micron features on diffraction gratings and silicon wafers were also cleaned without leaving light scattering particles on the surface. **This work was supported in part by the U.S. Department of Energy, Basic Energy Sciences-Materials Sciences, under contract no. W-31-109-ENG-38. The authors acknowledge the support and facilities provided by the Advanced Photon Source and the Electron Microscopy Center at Argonne National Laboratory.

Chemically activated carbon from lignocellulosic wastes for heavy metal wastewater remediation: Effect of activation conditions.

PubMed

Nayak, Arunima; Bhushan, Brij; Gupta, Vartika; Sharma, P

2017-05-01

Chemical activation is known to induce specific surface features of porosity and functionality which play a definite role in enhancing the adsorptive potential of the developed activated carbons. Different conditions of temperature, time, reagent type and impregnation ratio were applied on sawdust precursor and their effect on the physical, surface chemical features and finally on the adsorption potential of the developed activated carbons were analysed. Under activation conditions of 600°C, 1hr, 1:0.5 ratio, ZnCl 2 impregnated carbon (CASD_ZnCl 2 ) resulted in microporosity while KOH impregnation (CASD_KOH) yielded a carbon having a wider pore size distribution. The surface chemistry revealed similar functionalities. At same pH, temperature and adsorbate concentrations, CASD_KOH demonstrated better adsorption potential (1.06mmoles/g for Cd 2+ and 1.61mmoles/g for Ni 2+ ) in comparison to CASD_ZnCl 2 (0.23mmoles/g and 0.33mmoles/g for Cd 2+ and Ni 2+ respectively). Other features were a short equilibrium time of 60mins and an adsorbent dose of 0.2g/L for the CASD_KOH in comparison to CASD_ZnCl 2 (equilibrium time of 150min and dosage of 0.5g/L). The nature of interactions was physical for both adsorbents and pore diffusion mechanisms were operative. The results reveal the potentiality of chemical activation so as to achieve the best physico-chemical properties suited for energy efficient, economical and eco-friendly water treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Connecting Acids and Bases with Encapsulation... and Chemistry with Nanotechnology

ERIC Educational Resources Information Center

Criswell, Brett

2007-01-01

The features and the development of various new acids and bases activity sets that combines chemistry with nanotechnology are being described. These sets lead to the generation of many nanotechnology-based pharmaceuticals for the treatment of various diseases.

A Modern Approach to College Analytical Chemistry.

ERIC Educational Resources Information Center

Neman, R. L.

1983-01-01

Describes a course which emphasizes all facets of analytical chemistry, including sampling, preparation, interference removal, selection of methodology, measurement of a property, and calculation/interpretation of results. Includes special course features (such as cooperative agreement with an environmental protection center) and course…

News: Green Chemistry & Technology

EPA Science Inventory

A series of 21 articles focused on different features of green chemistry in a recent issue of Chemical Reviews. Topics extended over a wide range to include the design of sustainable synthetic processes to biocatalysis. A selection of perspectives follows as part of this colu

Chemistry by Computer.

ERIC Educational Resources Information Center

Garmon, Linda

1981-01-01

Describes the features of various computer chemistry programs. Utilization of computer graphics, color, digital imaging, and other innovations are discussed in programs including those which aid in the identification of unknowns, predict whether chemical reactions are feasible, and predict the biological activity of xenobiotic compounds. (CS)

Identification of a BrOOO- intermediate species in the ozonolysis of bromide at the liquid/vapor interface from liquid jet XPS

NASA Astrophysics Data System (ADS)

Chen, Shuzhen; Artiglia, Luca; Orlando, Fabrizio; Corral-Arroyo, Pablo; Edebeli, Jacinta; Ammann, Markus

2017-04-01

Oxidation of bromide by gas phase ozone (O3) in the absence of photochemistry is believed to be one of the important dark reactions to produce HOBr as the starting point of the multiphase cycling reaction mechanisms that release bromide out of sea water, sea spray or marine aerosols from aqueous solution that later drive O3 depleting chemistry in the troposphere [1]. The reaction of bromide with O3 occurs through an acid catalyzed mechanism involving a BrOOO- complex as an intermediate [2]. Slow oxidation of bromide by O3 in the bulk aqueous phase is of limited relevance; previous kinetic experiments have suspected the reaction to be enhanced at the surface of aqueous solutions. Thus, identifying BrOOO- at the interface would be a major step to understanding the multiphase oxidation of bromide with O3. Here, we provide a direct experimental evidence for the formation of a BrOOO- reaction intermediate at the surface by investigating the reaction of aqueous solutions NaBr with gas phase O3 after millisecond time scale exposure using the surface sensitive in situ liquid jet X-ray photoelectron spectroscopy (XPS) at the Swiss Light Source (SLS). We acquired Br 3d core level spectra of 0.125 M NaBr solution in presence and absence of ozone in the gas phase. We found a new feature with a peak position shifted towards higher binding energy (by ˜0.7 eV) compared to Br-, which was clearly different from the Br 3d core levels spectra of hypobromite and bromate measured with reference solutions. Our results suggest the appearance of the formation of the BrOOO- reaction intermediate as a new component, in agreement with theoretical calculations of the Br- ozonolysis mechanism [3]. Additionally, by varying the photoelectron kinetic energy and thus probe depth via variation of the probing photon energy, the new feature appears to be present near the liquid/vapor interface. Besides, kinetic experiments for the reaction of O3 with bromide are ongoing to investigate the dependence on the temperature, ozone concentration, which may give further information such as the relative oxidation rate at the liquid/vapor interface versus that in the bulk phase. [1] S. Wang, et al., Proceedings of the National Academy of Sciences, 2015, 112, 9281-9286. [2] Q. Liu, et al., Inorganic Chemistry, 2001, 40, 4436-4442. [3] I. Gladich, et al., The Journal of Physical Chemistry A, 2015, 119, 4482-4488.

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.

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.

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.

Selective layer-free blood serum ionogram based on ion-specific interactions with a nanotransistor

NASA Astrophysics Data System (ADS)

Sivakumarasamy, R.; Hartkamp, R.; Siboulet, B.; Dufrêche, J.-F.; Nishiguchi, K.; Fujiwara, A.; Clément, N.

2018-05-01

Despite being ubiquitous in the fields of chemistry and biology, the ion-specific effects of electrolytes pose major challenges for researchers. A lack of understanding about ion-specific surface interactions has hampered the development and application of materials for (bio-)chemical sensor applications. Here, we show that scaling a silicon nanotransistor sensor down to 25 nm provides a unique opportunity to understand and exploit ion-specific surface interactions, yielding a surface that is highly sensitive to cations and inert to pH. The unprecedented sensitivity of these devices to Na+ and divalent ions can be attributed to an overscreening effect via molecular dynamics. The surface potential of multi-ion solutions is well described by the sum of the electrochemical potentials of each cation, enabling selective measurements of a target ion concentration without requiring a selective organic layer. We use these features to construct a blood serum ionogram for Na+, K+, Ca2+ and Mg2+, in an important step towards the development of a versatile, durable and mobile chemical or blood diagnostic tool.

Searching the Sinus Amoris: Using profiles of geological units, impact and volcanic features to characterize a major terrane interface on the Moon

NASA Technical Reports Server (NTRS)

Clark, P.; Joerg, S.; Dehon, R.

1994-01-01

Geochemical profiles of surface units, impact, and volcanic features are studied in detail to determine the underlying structure in an area of extensive mare/highland interface, Sinus Amoris. This study region includes and surrounds the northeastern embayment of Mare Tranquillitatis. The concentrations of two major rock-forming elements (Mg and Al), which were derived from the Apollo 15 orbital geochemical measurements, were used in this study. Mapped units and deposits associated with craters in the northwestern part of the region tend to have correlated low Mg and Al concentrations, indicating the presence of Potassium (K)-Rare Earth Elements (REE)-Phosphorus (P) (KREEP)-enriched basalt. Found along the northeastern rim of Tranquillitatis were areas with correlated high Mg and Al concentration, indicating the presence of troctolite. Distinctive west/east and north/south trends were observed in the concentrations of Mg and Al, and, by implication, in the distribution of major rock components on the surface. Evidence for a systematic geochemical transition in highland or basin-forming units may be observed here in the form of distinctive differences in chemistry in otherwise similar units in the western and eastern portions of the study region.

Long-lasting antifog plasma modification of transparent plastics.

PubMed

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

2014-10-08

Antifog surfaces are necessary for any application requiring optical efficiency of transparent materials. Surface modification methods aimed toward increasing solid surface energy, even when supposed to be permanent, in fact result in a nondurable effect due to the instability in air of highly hydrophilic surfaces. We propose the strategy of combining a hydrophilic chemistry with a nanotextured topography, to tailor a long-lasting antifog modification on commercial transparent plastics. In particular, we investigated a two-step process consisting of self-masked plasma etching followed by plasma deposition of a silicon-based film. We show that the deposition of the silicon-based coatings on the flat (pristine) substrates allows a continuous variation of wettability from hydrophobic to superhydrophilic, due to a continuous reduction of carbon-containing groups, as assessed by Fourier transform infrared and X-ray photoelectron spectroscopies. By depositing these different coatings on previously nanotextured substrates, the surface wettability behavior is changed consistently, as well as the condensation phenomenon in terms of microdroplets/liquid film appearance. This variation is correlated with advancing and receding water contact angle features of the surfaces. More importantly, in the case of the superhydrophilic coating, though its surface energy decreases with time, when a nanotextured surface underlies it, the wetting behavior is maintained durably superhydrophilic, thus durably antifog.

Uni-directional liquid spreading on asymmetric nanostructured surfaces

NASA Astrophysics Data System (ADS)

Chu, Kuang-Han; Xiao, Rong; Wang, Evelyn N.

2010-05-01

Controlling surface wettability and liquid spreading on patterned surfaces is of significant interest for a broad range of applications, including DNA microarrays, digital lab-on-a-chip, anti-fogging and fog-harvesting, inkjet printing and thin-film lubrication. Advancements in surface engineering, with the fabrication of various micro/nanoscale topographic features, and selective chemical patterning on surfaces, have enhanced surface wettability and enabled control of the liquid film thickness and final wetted shape. In addition, groove geometries and patterned surface chemistries have produced anisotropic wetting, where contact-angle variations in different directions resulted in elongated droplet shapes. In all of these studies, however, the wetting behaviour preserves left-right symmetry. Here, we demonstrate that we can harness the design of asymmetric nanostructured surfaces to achieve uni-directional liquid spreading, where the liquid propagates in a single preferred direction and pins in all others. Through experiments and modelling, we determined that the spreading characteristic is dependent on the degree of nanostructure asymmetry, the height-to-spacing ratio of the nanostructures and the intrinsic contact angle. The theory, based on an energy argument, provides excellent agreement with experimental data. The insights gained from this work offer new opportunities to tailor advanced nanostructures to achieve active control of complex flow patterns and wetting on demand.

The spectroscopic chemical and photophysical properties of Martian soils and their analogs

NASA Technical Reports Server (NTRS)

Coyne, Lelia M.

1987-01-01

The program of research outlined should advance significantly the understanding of the spectral signal of montmorillonites in general and the variations produced in it by structural and surface ferric and ferrous iron and interlayer water as a function of several environmental conditions that are different between Earth and Mars. In addition, an extensive data base was collected providing spectral characterization of several features (iron, both surface and structural, OH-groups, both structural and from adsorbed water and O(-) centers) that are known, or thought to be, influential in directing the surface activity of these important materials. With this data base with which to assess the results of the Viking labeled release simulation studies, it should be possible to gain important insights into the mechanisms of surface reactivity for this important chemical reaction. The results to be gained from these studies will provide a significant body of ground base truth from which to assess: the presence of smectite clays on Mars; the mineralogical form in which the Martian iron is bound; establish upper limits on the present surface water content of Martian soils; perhaps provide insights on the Martian surface radiation history; and to make strong predictions about the nature of surface chemistry on Mars, if iron-bearing clays are a significant component of the surface mineralogical assemblage.

The effects of surface topography control using liquid crystal elastomers on bodies in flow

NASA Astrophysics Data System (ADS)

Settle, Michael; Guin, Tyler; Beblo, Richard; White, Timothy; Reich, Gregory

2018-03-01

Surface topography control has use across many applications including delayed separation of flow via selective boundary-layer tripping. Recently, advances with liquid crystal elastomers (LCE) have been leveraged for controlled, repeatable, out-of-plane deformations that could enable these topographical changes. An aligned LCE deforms when heated, associated with a loss in order. Circumferential patterns fabricated through the thickness of the LCE film yield a predictable conical out-of-plane deformation that can control surface topography. This study focuses on the experimental investigation of LCE behavior for flow control. Initially, the deformations of LCE samples 1/2" in diameter and 50 µm thick were characterized using Digital Image Correlation under uniform positive and negative gauge pressures at various temperatures. Surface topography showed strong dependence on boundary conditions, sample dimensions, and pattern location relative to the applied boundary conditions, informing adjustment of the LCE of the chemistry to produce higher modulus and glassy materials. As an initial demonstration of the ability to control flow, Then, to demonstrate the potential for flow control, 3D printed cylinders with varying arrangements of representative topographical features were characterized in a wind tunnel with Particle Image Velocimetry. Results showed that features with a maximum deflection height of 1.5 mm in a two-row arrangement can form an asymmetric wake about a 73 mm diameter cylinder that reduces drag while generating lift. These results inform subsequent investigation of active LCE elements on a cylinder that are currently under examination.

From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry.

PubMed

Lehn, Jean-Marie

2007-02-01

Supramolecular chemistry has developed over the last forty years as chemistry beyond the molecule. Starting with the investigation of the basis of molecular recognition, it has explored the implementation of molecular information in the programming of chemical systems towards self-organisation processes, that may occur either on the basis of design or with selection of their components. Supramolecular entities are by nature constitutionally dynamic by virtue of the lability of non-covalent interactions. Importing such features into molecular chemistry, through the introduction of reversible bonds into molecules, leads to the emergence of a constitutional dynamic chemistry, covering both the molecular and supramolecular levels. It considers chemical objects and systems capable of responding to external solicitations by modification of their constitution through component exchange or reorganisation. It thus opens the way towards an adaptive and evolutive chemistry, a further step towards the chemistry of complex matter.

Part C: Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

USGS Publications Warehouse

Van Gosen, Bradley S.; Wenrich, Karen J.

1991-01-01

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

Part B: Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

USGS Publications Warehouse

Van Gosen, Bradley S.; Wenrich, Karen J.

1991-01-01

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

USGS Publications Warehouse

Van Gosen, Bradley S.; Wenrich, Karen J.

1991-01-01

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

Part D: Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

USGS Publications Warehouse

Van Gosen, Bradley S.; Wenrich, Karen J.

1991-01-01

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

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

Coordinated Analyses of Antarctic Sediments as Mars Analog Materials Using Reflectance Spectroscopy and Current Flight-Like Instruments for CheMin, SAM and MOMA

NASA Technical Reports Server (NTRS)

Bishop, Janice L.; Franz, Heather B.; Goetz, Walter; Blake, David F.; Freissinet, Caroline; Steininger, Harald; Goesmann, Fred; Brinckerhoff, William B.; Getty, Stephanie; Pinnick, Veronica T.;

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.

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.

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

PubMed

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

2015-12-06

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

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

PubMed

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

2016-06-22

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

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.

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

PubMed

Collins, Gillian; Holmes, Justin D

2016-07-01

Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Campaign 1.7 Pu Aging. Development of Time of Flight Secondary Ion Mass Spectroscopy

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

Venhaus, Thomas J.

2015-09-09

The first application of Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) to an aged plutonium surface has resulted in a rich set of surface chemistry data, as well as some unexpected results. FY15 was highlighted by not only the first mapping of hydrogen-containing features within the metal, but also a prove-in series of experiments using the system’s Sieverts Reaction Cell. These experiments involved successfully heating the sample to ~450 oC for nearly 24 hours while the sample was dosed several times with hydrogen, followed by an in situ ToF-SIMS analysis. During this year, the data allowed for better and more consistentmore » identification of the myriad peaks that result from the SIMS sputter process. In collaboration with the AWE (U.K), the system was also fully aligned for sputter depth profiling for future experiments.« less

Heat pipe systems using new working fluids

NASA Technical Reports Server (NTRS)

Chao, David F. (Inventor); Zhang, Nengli (Inventor)

2004-01-01

The performance of a heat pipe system is greatly improved by the use of a dilute aqueous solution of about 0.0005 and about 0.005 moles per liter of a long chain alcohol as the working fluid. The surface tension-temperature gradient of the long-chain alcohol solutions turns positive as the temperature exceeds a certain value, for example about 40.degree. C. for n-heptanol solutions. Consequently, the Marangoni effect does not impede, but rather aids in bubble departure from the heating surface. Thus, the bubble size at departure is substantially reduced at higher frequencies and, therefore, increases the boiling limit of heat pipes. This feature is useful in microgravity conditions. In addition to microgravity applications, the heat pipe system may be used for commercial, residential and vehicular air conditioning systems, micro heat pipes for electronic devices, refrigeration and heat exchangers, and chemistry and cryogenics.

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

Li, Chen; Metzler, Dominik; Oehrlein, Gottlieb S., E-mail: oehrlein@umd.edu

Angstrom-level plasma etching precision is required for semiconductor manufacturing of sub-10 nm critical dimension features. Atomic layer etching (ALE), achieved by a series of self-limited cycles, can precisely control etching depths by limiting the amount of chemical reactant available at the surface. Recently, SiO{sub 2} ALE has been achieved by deposition of a thin (several Angstroms) reactive fluorocarbon (FC) layer on the material surface using controlled FC precursor flow and subsequent low energy Ar{sup +} ion bombardment in a cyclic fashion. Low energy ion bombardment is used to remove the FC layer along with a limited amount of SiO{sub 2} frommore » the surface. In the present article, the authors describe controlled etching of Si{sub 3}N{sub 4} and SiO{sub 2} layers of one to several Angstroms using this cyclic ALE approach. Si{sub 3}N{sub 4} etching and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4} were studied and evaluated with regard to the dependence on maximum ion energy, etching step length (ESL), FC surface coverage, and precursor selection. Surface chemistries of Si{sub 3}N{sub 4} were investigated by x-ray photoelectron spectroscopy (XPS) after vacuum transfer at each stage of the ALE process. Since Si{sub 3}N{sub 4} has a lower physical sputtering energy threshold than SiO{sub 2}, Si{sub 3}N{sub 4} physical sputtering can take place after removal of chemical etchant at the end of each cycle for relatively high ion energies. Si{sub 3}N{sub 4} to SiO{sub 2} ALE etching selectivity was observed for these FC depleted conditions. By optimization of the ALE process parameters, e.g., low ion energies, short ESLs, and/or high FC film deposition per cycle, highly selective SiO{sub 2} to Si{sub 3}N{sub 4} etching can be achieved for FC accumulation conditions, where FC can be selectively accumulated on Si{sub 3}N{sub 4} surfaces. This highly selective etching is explained by a lower carbon consumption of Si{sub 3}N{sub 4} as compared to SiO{sub 2}. The comparison of C{sub 4}F{sub 8} and CHF{sub 3} only showed a difference in etching selectivity for FC depleted conditions. For FC accumulation conditions, precursor chemistry has a weak impact on etching selectivity. Surface chemistry analysis shows that surface fluorination and FC reduction take place during a single ALE cycle for FC depleted conditions. A fluorine rich carbon layer was observed on the Si{sub 3}N{sub 4} surface after ALE processes for which FC accumulation takes place. The angle resolved-XPS thickness calculations confirmed the results of the ellipsometry measurements in all cases.« 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.

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.

Analysis of the electrodeposition and surface chemistry of CdTe, CdSe, and CdS thin films through substrate-overlayer surface-enhanced Raman spectroscopy.

PubMed

Gu, Junsi; Fahrenkrug, Eli; Maldonado, Stephen

2014-09-02

The substrate-overlayer approach has been used to acquire surface enhanced Raman spectra (SERS) during and after electrochemical atomic layer deposition (ECALD) of CdSe, CdTe, and CdS thin films. The collected data suggest that SERS measurements performed with off-resonance (i.e. far from the surface plasmonic wavelength of the underlying SERS substrate) laser excitation do not introduce perturbations to the ECALD processes. Spectra acquired in this way afford rapid insight on the quality of the semiconductor film during the course of an ECALD process. For example, SERS data are used to highlight ECALD conditions that yield crystalline CdSe and CdS films. In contrast, SERS measurements with short wavelength laser excitation show evidence of photoelectrochemical effects that were not germane to the intended ECALD process. Using the semiconductor films prepared by ECALD, the substrate-overlayer SERS approach also affords analysis of semiconductor surface adsorbates. Specifically, Raman spectra of benzenethiol adsorbed onto CdSe, CdTe, and CdS films are detailed. Spectral shifts in the vibronic features of adsorbate bonding suggest subtle differences in substrate-adsorbate interactions, highlighting the sensitivity of this methodology.

Electrostatic Properties of Polymers Subjected to Atmospheric Pressure Plasma Treatment; Correlation of Experimental Results with Atomistic Modeling

NASA Technical Reports Server (NTRS)

Trigwell, S.; Boucher, D.; Calle, C. I.

2007-01-01

this study, PE, PTFE, PS and PMMA were exposed to a He+O2, APGD and pre and post treatment surface chemistries were analyzed by X-ray photoelectron spectroscopy and contact angle measurements. Semi-empirical and ab-initio calculations were performed to correlate the experimental results with sonic plausible molecular and electronic structure features of the oxidation process. For the PE and PS, significant surface oxidation showing C-O, C=O, and O-C=O bonding, and a decrease in the surface contact angles was observed. For the PTFE and PM MA, little change in the surface composition was observed. The molecular modeling calculations were performed on single and multiple oligomers and showed regardless of oxidation mechanism, e.g. -OH, =O or a combination thereof, experimentally observed levels of surface oxidation were unlikely to lead to a significant change in the electronic structure of PE and PS, and that the increased hydrophilic properties are the primary reason for the observed changes in its electrostatic behavior. Calculations for PTFE and PMMA argue strongly against significant oxidation of those materials, as confirmed by the XPS results.

Surface Plasmon Resonance: New Biointerface Designs and High-Throughput Affinity Screening

NASA Astrophysics Data System (ADS)

Linman, Matthew J.; Cheng, Quan Jason

Surface plasmon resonance (SPR) is a surface optical technique that measures minute changes in refractive index at a metal-coated surface. It has become increasingly popular in the study of biological and chemical analytes because of its label-free measurement feature. In addition, SPR allows for both quantitative and qualitative assessment of binding interactions in real time, making it ideally suited for probing weak interactions that are often difficult to study with other methods. This chapter presents the biosensor development in the last 3 years or so utilizing SPR as the principal analytical technique, along with a concise background of the technique itself. While SPR has demonstrated many advantages, it is a nonselective method and so, building reproducible and functional interfaces is vital to sensing applications. This chapter, therefore, focuses mainly on unique surface chemistries and assay approaches to examine biological interactions with SPR. In addition, SPR imaging for high-throughput screening based on microarrays and novel hyphenated techniques involving the coupling of SPR to other analytical methods is discussed. The chapter concludes with a commentary on the current state of SPR biosensing technology and the general direction of future biosensor research.

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.

Cosmogenic nuclides in the Martian surface: Constraints for sample recovery and transport

NASA Technical Reports Server (NTRS)

Englert, Peter A. J.

1988-01-01

Stable and radioactive cosmogenic nuclides and radiation damage effects such as cosmic ray tracks can provide information on the surface history of Mars. A recent overview on developments in cosmogenic nuclide research for historical studies of predominantly extraterrestrial materials was published previously. The information content of cosmogenic nuclides and radiation damage effects produced in the Martian surface is based on the different ways of interaction of the primary galactic and solar cosmic radiation (GCR, SCR) and the secondary particle cascade. Generally the kind and extent of interactions as seen in the products depend on the following factors: (1) composition, energy and intensity of the primary SCR and GCR; (2) composition, energy and intensity of the GCR-induced cascade of secondary particles; (3) the target geometry, i.e., the spatial parameters of Martian surface features with respect to the primary radiation source; (4) the target chemistry, i.e., the chemical composition of the Martian surface at the sampling location down to the minor element level or lower; and (5) duration of the exposure. These factors are not independent of each other and have a major influence on sample taking strategies and techniques.

Multifunctional clickable and protein-repellent magnetic silica nanoparticles.

PubMed

Estupiñán, Diego; Bannwarth, Markus B; Mylon, Steven E; Landfester, Katharina; Muñoz-Espí, Rafael; Crespy, Daniel

2016-02-07

Silica nanoparticles are versatile materials whose physicochemical surface properties can be precisely adjusted. Because it is possible to combine several functionalities in a single carrier, silica-based materials are excellent candidates for biomedical applications. However, the functionality of the nanoparticles can get lost upon exposure to biological media due to uncontrolled biomolecule adsorption. Therefore, it is important to develop strategies that reduce non-specific protein-particle interactions without losing the introduced surface functionality. Herein, organosilane chemistry is employed to produce magnetic silica nanoparticles bearing differing amounts of amino and alkene functional groups on their surface as orthogonally addressable chemical functionalities. Simultaneously, a short-chain zwitterion is added to decrease the non-specific adsorption of biomolecules on the nanoparticles surface. The multifunctional particles display reduced protein adsorption after incubation in undiluted fetal bovine serum as well as in single protein solutions (serum albumin and lysozyme). Besides, the particles retain their capacity to selectively react with biomolecules. Thus, they can be covalently bio-functionalized with an antibody by means of orthogonal click reactions. These features make the described multifunctional silica nanoparticles a promising system for the study of surface interactions with biomolecules, targeting, and bio-sensing.

Surface modification of model hydrogel contact lenses with hyaluronic acid via thiol-ene "click" chemistry for enhancing surface characteristics.

PubMed

Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

2017-10-01

Discontinuation of contact lens wear as a result of ocular dryness and discomfort is extremely common; as many as 26% of contact lens wearers discontinue use within the first year. While patients are generally satisfied with conventional hydrogel lenses, improving on-eye comfort continues to remain a goal. Surface modification with a biomimetic, ocular friendly hydrophilic layer of a wetting agent is hypothesized to improve the interfacial interactions of the contact lens with the ocular surface. In this work, the synthesis and characterization of poly(2-hydroxyethyl methacrylate) surfaces grafted with a hydrophilic layer of hyaluronic acid are described. The immobilization reaction involved the covalent attachment of thiolated hyaluronic acid (20 kDa) on acrylated poly(2-hydroxyethyl methacrylate) via nucleophile-initiated Michael addition thiol-ene "click" chemistry. The surface chemistry of the modified surfaces was analyzed by Fourier transform infrared spectroscopy-attenuated total reflectance and X-ray photoelectron spectroscopy. The appearance of N (1s) and S (2p) peaks on the low resolution X-ray photoelectron spectroscopy spectra confirmed successful immobilization of hyaluronic acid. Grafting hyaluronic acid to the poly(2-hydroxyethyl methacrylate) surfaces decreased the contact angle, the dehydration rate, and the amount of nonspecific sorption of lysozyme and albumin in comparison to pristine hydrogel materials, suggesting the development of more wettable surfaces with improved water-retentive and antifouling properties, while maintaining optical transparency (>92%). In vitro testing also showed excellent viability of human corneal epithelial cells with the hyaluronic acid-grafted poly(2-hydroxyethyl methacrylate) surfaces. Hence, surface modification with hyaluronic acid via thiol-ene "click" chemistry could be useful in improving contact lens surface properties, potentially alleviating symptoms of contact lens related dryness and discomfort during wear.

Challenges in Teaching "Colloid and Surface Chemistry"--A Danish Experience

ERIC Educational Resources Information Center

Kontogeorgis, Georgios M.; Vigild, Martin E.

2009-01-01

Seven years ago we were asked, as one of our first teaching duties at the Technical University of Denmark (DTU), to teach a 5 ECTS point course on "Colloid and Surface Chemistry". The topic is itself at the same time exciting and demanding, largely due to its multidisciplinary nature. Several "local" requirements posed…

Trends in Surface Water Chemistry in Acidified Areas in Europe and North America from 1990 to 2008

EPA Science Inventory

Acidification of lakes and rivers is still an environmental concern despite reduced emissions of acidifying compounds. We analyzed trends in surface water chemistry of 173 acid-sensitive sites from 12 regions in Europe and North America. In 11 of 12 regions, non-marine sulphate (...

The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry

NASA Astrophysics Data System (ADS)

Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R.; Vasilev, Krasimir; Hayball, John D.

2016-05-01

Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes.

Environmental chemistry at vapor/water interfaces: insights from vibrational sum frequency generation spectroscopy.

PubMed

Jubb, Aaron M; Hua, Wei; Allen, Heather C

2012-01-01

The chemistry that occurs at surfaces has been an intense area of study for many years owing to its complexity and importance in describing a wide range of physical phenomena. The vapor/water interface is particularly interesting from an environmental chemistry perspective as this surface plays host to a wide range of chemistries that influence atmospheric and geochemical interactions. The application of vibrational sum frequency generation (VSFG), an inherently surface-specific, even-order nonlinear optical spectroscopy, enables the direct interrogation of various vapor/aqueous interfaces to elucidate the behavior and reaction of chemical species within the surface regime. In this review we discuss the application of VSFG to the study of a variety of atmospherically important systems at the vapor/aqueous interface. Chemical systems presented include inorganic ionic solutions prevalent in aqueous marine aerosols, small molecular solutes, and long-chain fatty acids relevant to fat-coated aerosols. The ability of VSFG to probe both the organization and reactions that may occur for these systems is highlighted. A future perspective toward the application of VSFG to the study of environmental interfaces is also provided.

The effects of parametric changes in electropolishing process on surface properties of 316L stainless steel

NASA Astrophysics Data System (ADS)

ur Rahman, Zia; Deen, K. M.; Cano, Lawrence; Haider, Waseem

2017-07-01

Corrosion resistance and biocompatibility of 316L stainless steel implants depend on the surface features and the nature of the passive film. The influence of electropolishing on the surface topography, surface free energy and surface chemistry was determined by atomic force microscopy, contact angle meter and X-ray photoelectron spectroscopy, respectively. The electropolishing of 316L stainless steel was conducted at the oxygen evolution potential (EPO) and below the oxygen evolution potential (EPBO). Compared to mechanically polished (MP) and EPO, the EPBO sample depicted lower surface roughness (Ra = 6.07 nm) and smaller surface free energy (44.21 mJ/m2). The relatively lower corrosion rate (0.484 mpy) and smaller passive current density (0.619 μA/cm2) as determined from cyclic polarization scans was found to be related with the presence of OH, Cr(III), Fe(0), Fe(II) and Fe(III) species at the surface. These species assured the existence of relatively uniform passive oxide film over EPBO surface. Moreover, the relatively large charge transfer (Rct) and passive film resistance (Rf) registered by EPBO sample from impedance spectroscopy analysis confirmed its better electrochemical performance. The in vitro response of these polished samples toward MC3T3 pre-osteoblast cell proliferation was determined to be directly related with their surface and electrochemical properties.

Characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems.

PubMed

Bryant, M; Ward, M; Farrar, R; Freeman, R; Brummitt, K; Nolan, J; Neville, A

2014-04-01

This study presents the characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems. Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FI-IR) were utilised in order to assess the surface morphology of retrieved Metal-on-Metal Total Hip Replacements and surface chemistry of the films found on the surface. Gross slip, plastic deformation and directionality of the surface were extensively seen on the proximal surfaces of the retrievals. A more corrosive phenomenon was observed in the distal regions of the stem, demonstrating a seemingly intergranular attack. Tribochemical reactions were seen to occur within the stem-cement interfaces with tribofilms being observed on the femoral stem and counterpart PMMA bone cement. XPS, TEM-EDX and FT-IR analyses demonstrated that the films present in the stem surfaces were a complex mixture of chromium oxide and amorphous organic material. A comparison between current experimental and clinical literature has been conducted and findings from this study demonstrate that the formation and chemistry of films are drastically influenced by the type of wear or degradation mechanism. Films formed in the stem-cement interface are thought to further influence the biological environment outside the stem-cement interface due to the formation of Cr and O rich films within the interface whilst Co is free to migrate away. © 2013 Elsevier Ltd. All rights reserved.

Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films

DOE PAGES

Hong, Wesley T.; Stoerzinger, Kelsey; Crumlin, Ethan J.; ...

2016-02-11

Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr 2Co 2O 5 (SCO) epitaxial thin films with different crystallographic orientations. Detailedmore » analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La 0.8Sr 0.2CoO 3-δ thin films by SCO surface particles observed previously.« less

Feature Masking in Computer Game Promotes Visual Imagery

ERIC Educational Resources Information Center

Smith, Glenn Gordon; Morey, Jim; Tjoe, Edwin

2007-01-01

Can learning of mental imagery skills for visualizing shapes be accelerated with feature masking? Chemistry, physics fine arts, military tactics, and laparoscopic surgery often depend on mentally visualizing shapes in their absence. Does working with "spatial feature-masks" (skeletal shapes, missing key identifying portions) encourage people to…

Silica-Based, Hyper-Crosslinked Acid Stable Stationary Phases for High Performance Liquid Chromatography

PubMed Central

Zhang, Yu; Luo, Hao; Carr, Peter W.

2011-01-01

A new family of Hyper-Crosslinked (HC) phases has been recently introduced for use under very aggressive acid conditions including those encountered in ultra-fast, high temperature Two-Dimensional Liquid Chromatography (2DLC). This type of stationary phase showed significantly enhanced acid and thermal stability compared to the most acid stable, commercial RPLC phases. In addition, the use of “orthogonal” chemistry to make surface-confined polymer networks ensures good reproducibility and high efficiency. One of the most interesting features of the HC phases is the ability to derivatize the surface aromatic groups with various functional groups. This led to the development of a family of hyper-crosslinked phases possessing a wide variety of chromatographic selectivities by attaching hydrophobic (e.g. –C8), ionizable (e.g. -COOH, -SO3H), aromatic (e.g. –toluene) or polar (e.g. -OH) species to the aromatic polymer network. HC reversed phases with various degrees of hydrophobicity and mixed-mode HC phases with added strong and weak cation exchange sites have been synthesized, characterized and applied. These silica-based acid-stable HC phases, with their attractive chromatographic properties, should be very useful in the separations of bases or biological analytes in acidic media, especially at elevated temperatures. This work reviews the prior research on HC phases and introduces a novel HC phase made by alternative chemistry. PMID:21906745

I. Developing Methods for the Analysis of Chemistry Students' Inscriptions, II. Exploring the Regioselectivity of 1,3-Dipolar Cycloadditions of Munchnones, III. Stereochemical Investigations of C-H Activation Reactions Involving Germylene and Stannylene/Aryl Iodide Reagents

ERIC Educational Resources Information Center

Kiste, Alan L.

2009-01-01

I. Analyzing and comparing student-generated inscriptions in chemistry is crucial to gaining insight into students' understanding about chemistry concepts. Thus, we developed two methods of analyzing student-generated inscriptions: features analysis and thematic analysis. We have also demonstrated how these methods are able to discern differences…

Interfacing Nanoparticles and Biology: New Strategies for Biomedicine

PubMed Central

Tonga, Gulen Yesilbag; Saha, Krishnendu; Rotello, Vincent M.

2014-01-01

The exterior surface of nanoparticles (NPs) dictates the behavior of these systems with the outside world. Understanding the interactions of NP surface functionality with biosystems enables the design and fabrication of effective platforms for therapeutics, diagnostics, and imaging agents. In this review, we highlight the role of chemistry in the engineering of nanomaterials, focusing on the fundamental role played by surface chemistry in controlling the interaction of NPs with proteins and cells. PMID:24105763

Biocompatible Surface Chemistry Manipulation of Gold Nanorods Preserves Optical Properties for Bio-Imaging Applications

DTIC Science & Technology

2015-12-18

3. DATES COVERED (From - To) March 2014 – Sept 2014 4. TITLE AND SUBTITLE Biocompatible surface chemistry manipulation of gold nanorods preserves...Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable...intracellular aggregation of MTAB-TA GNRs, and identify them as prime andidates for use in nanobased bio-imaging applications. 15. SUBJECT TERMS Gold

Mars Atmospheric Chemistry and Astrobiology Workshop Summary

NASA Astrophysics Data System (ADS)

Allen, M.; Wennberg, P.

2002-09-01

The Mars Atmospheric Chemistry and Astrobiology (MACA) Workshop was held on the California Institute of Technology campus December 17-18, 2001. The prime objective of the workshop was to consider whether extant life beneath the surface, if it exists, would be in contact with the atmosphere and introduce a detectable signature in the atmosphere. To answer this question, the workshop also explored how well we understood the abiotic chemistry of the current atmosphere and other drivers of atmospheric composition (volcanoes, surface-atmosphere interactions, escape). The conclusions from this workshop will be presented.

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.

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides HnRhn[P(OR)3]2n

PubMed Central

Brown, R. K.; Williams, J. M.; Fredrich, M. F.; Day, V. W.; Sivak, A. J.; Muetterties, E. L.

1979-01-01

Crystallographic analyses of x-ray and neutron diffraction data have provided a definitive structural representation of {HRh[P(O-i-C3H7)3]2}2 and {HRh[P(OCH3)3]2}3. These polynuclear hydrides are generated from square planar H2Rh[P(OR)3]2 units by edge (hydrogen atom) sharing and by vertex (hydrogen atom) sharing to form the dimeric and trimeric structures, respectively. The square-planar units are held together through four-center and three-center two-electron Rh—H—Rh bonds in the dimer and trimer, respectively. The dimer and trimer molecules each add one molecule of hydrogen to form H[(i-C3H7O)3P]2RhH3Rh [P(O-i-C3H7)3]2 and H5Rh3[P(OCH3)3]6, respectively. NMR spectral information has served to define the stereochemical features of these polyhydrides. The significance of this chemistry in the metal cluster-metal surface analogy is described. PMID:16592645

Hydrogen peroxide in the marine boundary layer over the South Atlantic during the OOMPH cruise in March 2007

NASA Astrophysics Data System (ADS)

Fischer, H.; Pozzer, A.; Schmitt, T.; Jöckel, P.; Klippel, T.; Taraborrelli, D.; Lelieveld, J.

2015-06-01

In the OOMPH (Ocean Organics Modifying Particles in both Hemispheres) project a ship measurement cruise took place in the late austral summer from 01 to 23 March 2007. The French research vessel Marion Dufresne sailed from Punta Arenas, Chile (70.85° W, 53.12° S), to Réunion island (55.36° E, 21.06° S) across the South Atlantic Ocean. In situ measurements of hydrogen peroxide, methylhydroperoxide and ozone were performed and are compared to simulations with the atmospheric chemistry global circulation model EMAC (ECHAM/MESSy Atmospheric Chemistry). The model generally reproduces the measured trace gas levels, but it underestimates hydrogen peroxide mixing ratios at high wind speeds, indicating too-strong dry deposition to the ocean surface. An interesting feature during the cruise is a strong increase of hydrogen peroxide, methylhydroperoxide and ozone shortly after midnight off the west coast of Africa due to an increase in the boundary layer height, leading to downward transport from the free troposphere, which is qualitatively reproduced by the model.

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.

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.

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

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

Critical aspects in the production of periodically ordered mesoporous titania thin films

NASA Astrophysics Data System (ADS)

Soler-Illia, Galo J. A. A.; Angelomé, Paula C.; Fuertes, M. Cecilia; Grosso, David; Boissiere, Cedric

2012-03-01

Periodically ordered mesoporous titania thin films (MTTF) present a high surface area, controlled porosity in the 2-20 nm pore diameter range and an amorphous or crystalline inorganic framework. These materials are nowadays routinely prepared by combining soft chemistry and supramolecular templating. Photocatalytic transparent coatings and titania-based solar cells are the immediate promising applications. However, a wealth of new prospective uses have emerged on the horizon, such as advanced catalysts, perm-selective membranes, optical materials based on plasmonics and photonics, metamaterials, biomaterials or new magnetic nanocomposites. Current and novel applications rely on the ultimate control of the materials features such as pore size and geometry, surface functionality and wall structure. Even if a certain control of these characteristics has been provided by the methods reported so far, the needs for the next generation of MTTF require a deeper insight in the physical and chemical processes taking place in their preparation and processing. This article presents a critical discussion of these aspects. This discussion is essential to evolve from know-how to sound knowledge, aiming at a rational materials design of these fascinating systems.Periodically ordered mesoporous titania thin films (MTTF) present a high surface area, controlled porosity in the 2-20 nm pore diameter range and an amorphous or crystalline inorganic framework. These materials are nowadays routinely prepared by combining soft chemistry and supramolecular templating. Photocatalytic transparent coatings and titania-based solar cells are the immediate promising applications. However, a wealth of new prospective uses have emerged on the horizon, such as advanced catalysts, perm-selective membranes, optical materials based on plasmonics and photonics, metamaterials, biomaterials or new magnetic nanocomposites. Current and novel applications rely on the ultimate control of the materials features such as pore size and geometry, surface functionality and wall structure. Even if a certain control of these characteristics has been provided by the methods reported so far, the needs for the next generation of MTTF require a deeper insight in the physical and chemical processes taking place in their preparation and processing. This article presents a critical discussion of these aspects. This discussion is essential to evolve from know-how to sound knowledge, aiming at a rational materials design of these fascinating systems. Dedicated to Clément Sanchez, on the first anniversary of his appointment to the Hybrid Materials Chair of the Collège de France.

The Apollo Missions and the Chemistry of the Moon

ERIC Educational Resources Information Center

Pacer, Richard A.; Ehmann, William D.

1975-01-01

Presents the principle chemical features of the moon obtained by analyzing lunar samples gathered on the Apollo missions. Outlines the general physical features of the moon and presents theories on its origin. (GS)

A Cognitive Framework for the Analysis of Online Chemistry Courses

ERIC Educational Resources Information Center

Evans, Karen L.; Leinhardt, Gaea

2008-01-01

Many students now are receiving instruction in online environments created by universities, museums, corporations, and even students. What features of a given online course contribute to its effectiveness? This paper addresses that query by proposing and applying an analytic framework to five online introductory chemistry courses. Introductory…

Relativistic Effects and the Chemistry of the Heaviest Main-Group Elements

ERIC Educational Resources Information Center

Thayer, John S.

2005-01-01

The chemical properties of the heaviest main-group elements often show features not found in their lighter counterparts while relativistic effects play an important role in the chemistry of these elements. The unusual properties and their relation to relativistic effects with emphasis on the new research are emphasized.

New ligand platforms featuring boron-rich clusters as organomimetic substituents*,**

PubMed Central

Spokoyny, Alexander M.

2013-01-01

200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the “space race” while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules—a phenomenon best described as “organomimetic”. Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion. PMID:24311823

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

Step Towards Modeling the Atmosphere of Titan: State-Selected Reactions of O+ with Methane.

PubMed

Hrušák, J; Paidarová, I

2016-11-01

Methane conversion and in particular the formation of the C-O bond is one of fundamental entries to organic chemistry and it appears to be essential for understanding parts of atmospheric chemistry of Titan, but, in broader terms it might be also relevant for Earth-like exoplanets. Theoretical study of the reactions of methane with atomic oxygen ion in its excited electronic states requires treating simultaneously at least 19 electronic states. Development of a computational strategy that would allow chemically reasonable and computationally feasible treatment of the CH 4 (X)/O + ( 2 D, 2 P) system is by far not trivial and it requires careful examination of all the complex features of the corresponding 19 potential energy surfaces. Before entering the discussion of the rich (photo) chemistry, inspection of the long range behavior of the system with focus on electric dipole transition moments is required. Our calculations show nonzero probability for the reactants to decay before entering the multiple avoided crossings region of the [CH 4  + O → products] + reaction. For the CH 4 /O + ( 2 P) system non-zero transition moment probabilities occur over the entire range of considered C-O distances (up to 15 Å), while for the CH 4 /O + ( 2 D) system these probabilities are lower by one order of magnitude and were found only at C-O distances smaller than 6 Å.

Mapping bark pH to better understand the cortisphere

NASA Astrophysics Data System (ADS)

Levia, D. F., Jr.; Köhler, S.; Jungkunst, H. F.; Gerold, G.

2016-12-01

The biogeochemistry of the cortisphere is poorly understood, despite the fact that a large variety of microbes, epiphytes, and insects live on, within, and just beneath corticular surfaces. Bark pH is a critical parameter that partially controls the chemodynamics of the cortisphere and its habitability by bark dwelling organisms as well as the chemistry of throughfall and stemflow. This presentation articulates, tests, and validates a method to accurately determine bark pH in situ. We employed agar-agar panels, embedded with a pH marker, to determine the spatiality of bark pH on cacao trees in Indonesia. In contrast to existing ex situ methods, we were able to record spatial differences in bark pH. In particular, bark pH was observed to fluctuate in relation to both morphological features on the bark, possibly corresponding to preferential flowpaths of stemflow, and epiphytic coverage. Due to its simplicity and economical nature, our method may be attractive to a variety of researchers interested in bark pH, its spatial variability, influence on stemflow chemistry, and its effect on organisms dwelling in the cortipshere. Publication note: This presentation is based on the following article: Köhler, S., Levia, D.F., Jungkunst, H.F. and Gerold, G. 2015. An in situ method to measure and map bark pH. Journal of Wood Chemistry and Technology 35(6): 438-449. [DOI: 10.1080/02773813.2015.1025285

The Pursuit of a Scalable Nanofabrication Platform for Use in Material and Life Science Applications

PubMed Central

GRATTON, STEPHANIE E. A.; WILLIAMS, STUART S.; NAPIER, MARY E.; POHLHAUS, PATRICK D.; ZHOU, ZHILIAN; WILES, KENTON B.; MAYNOR, BENJAMIN W.; SHEN, CLIFTON; OLAFSEN, TOVE; SAMULSKI, EDWARD T.; DESIMONE, JOSEPH M.

2008-01-01

CONSPECTUS In this Account, we describe the use of perfluoropolyether (PFPE)-based materials that are able to accurately mold and replicate micro- and nanosized features using traditional techniques such as embossing as well as new techniques that we developed to exploit the exceptional surface characteristics of fluorinated substrates. Because of the unique partial wetting and nonwetting characteristics of PFPEs, we were able to go beyond the usual molding and imprint lithography approaches and have created a technique called PRINT (Particle [or Pattern] Replication In Nonwetting Templates). PRINT is a distinctive “top-down” fabrication technique capable of generating isolated particles, arrays of particles, and arrays of patterned features for a plethora of applications in both nanomedicine and materials science. A particular strength of the PRINT technology is the high-resolution molding of well-defined particles with precise control over size, shape, deformability, and surface chemistry. The level of replication obtained showcases some of the unique characteristics of PFPE molding materials. In particular, these materials arise from very low surface energy precursors with positive spreading coefficients, can be photocured at ambient temperature, and are minimally adhesive, nonswelling, and conformable. These distinctive features enable the molding of materials with unique attributes and nanometer resolution that have unprecedented scientific and technological value. For example, in nanomedicine, the use of PFPE materials with the PRINT technique allows us to design particles in which we can tailor key therapeutic parameters such as bioavailability, biodistribution, target-specific cell penetration, and controlled cargo release. Similarly, in materials science, we can fabricate optical films and lens arrays, replicate complex, naturally occurring objects such as adenovirus particles, and create 2D patterned arrays of inorganic oxides. PMID:18720952

High-Level Spectroscopy, Quantum Chemistry, and Catalysis: Not just a Passing Fad.

PubMed

Neese, Frank

2017-09-04

Quantum chemistry can be used as a powerful link between theory and experiment for studying reactions in all areas of catalysis. The key feature of this approach is the combination of quantum chemistry with a range of high-level spectroscopic methods. This allows for conclusions to be reached that neither theory nor experiment would have been able to obtain in isolation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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.

Physics and Chemistry on Well-Defined Semiconductor and Oxide Surfaces

NASA Astrophysics Data System (ADS)

Chen, Peijun

High resolution electron energy loss spectroscopy (HREELS) and other surface spectroscopic techniques have been employed to investigate the following two classes of surface/interface phenomena on well-defined semiconductor and oxide surfaces: (i) the fundamental physical and chemical processes involved in gas-solid interaction on silicon single crystal surfaces, and (ii) the physical and chemical properties of metal-oxide interfaces. The particular systems reported in this dissertation are: NH_3, PH_3 and B_ {10}H_{14} on Si(111)-(7 x 7); NH_3 on Si(100) -(2 x 1); atomic H on Si(111)-(7 x 7) and boron-modified Si(111); Al on Al_2O_3 and Sn on SiO_2.. On silicon surfaces, the surface dangling bonds function as the primary adsorption sites where surface chemical processes take place. The unambiguous identification of surface species by vibrational spectroscopy allows the elementary steps involved in these surface chemical processes to be followed on a molecular level. For adsorbate molecules such as NH_3 and PH_3, the nature of the initial low temperature (100 -300 K) adsorption is found to be dissociative, while that for B_{10}H_ {14} is non-dissociative. This has been deduced based upon the presence (or absence) of specific characteristic vibrational mode(s) on surface. By following the evolution of surface species as a function of temperature, the elementary steps leading to silicon nitride thin film growth and doping of silicon are elucidated. In the case of NH_3 on Si(111)-(7 x 7) and Si(100)-(2 x 1), a detailed understanding on the role of substrate surface structure in controlling the surface reactivity has been gained on the basis of a Si adatom backbond-strain relief mechanism on the Si(111) -(7 x 7). The electronic modification to Si(111) surface by subsurface boron doping has been shown to quench its surface chemistry, even for the most aggressive atomic H. This discovery is potentially meaningful to the technology of gas-phase silicon etching. The electron energy loss studies on the excitation of surface plasmon in heavily B-doped Si(111) and the investigation of surface optical phonon modes in aluminum oxide thin films provide insights into the sensitive dependence of the physical properties of a solid upon its chemical modification. Successful interpretations of these elementary excitation features are built upon the understanding of the fundamental physics of low-energy electron-solid interaction. Finally, the temperature behavior of the interfacial properties of Sn/SiO_2 are explored.

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...

Design of an activity landscape view taking compound-based feature probabilities into account.

PubMed

Zhang, Bijun; Vogt, Martin; Bajorath, Jürgen

2014-09-01

Activity landscapes (ALs) of compound data sets are rationalized as graphical representations that integrate similarity and potency relationships between active compounds. ALs enable the visualization of structure-activity relationship (SAR) information and are thus computational tools of interest for medicinal chemistry. For AL generation, similarity and potency relationships are typically evaluated in a pairwise manner and major AL features are assessed at the level of compound pairs. In this study, we add a conditional probability formalism to AL design that makes it possible to quantify the probability of individual compounds to contribute to characteristic AL features. Making this information graphically accessible in a molecular network-based AL representation is shown to further increase AL information content and helps to quickly focus on SAR-informative compound subsets. This feature probability-based AL variant extends the current spectrum of AL representations for medicinal chemistry applications.

National hydrography dataset--linear referencing

USGS Publications Warehouse

Simley, Jeffrey; Doumbouya, Ariel

2012-01-01

Geospatial data normally have a certain set of standard attributes, such as an identification number, the type of feature, and name of the feature. These standard attributes are typically embedded into the default attribute table, which is directly linked to the geospatial features. However, it is impractical to embed too much information because it can create a complex, inflexible, and hard to maintain geospatial dataset. Many scientists prefer to create a modular, or relational, data design where the information about the features is stored and maintained separately, then linked to the geospatial data. For example, information about the water chemistry of a lake can be maintained in a separate file and linked to the lake. A Geographic Information System (GIS) can then relate the water chemistry to the lake and analyze it as one piece of information. For example, the GIS can select all lakes more than 50 acres, with turbidity greater than 1.5 milligrams per liter.

Contribution of Surface Chemistry to the Shear Thickening of Silica Nanoparticle Suspensions.

PubMed

Yang, Wufang; Wu, Yang; Pei, Xiaowei; Zhou, Feng; Xue, Qunji

2017-01-31

Shear thickening is a general process crucial for many processed products ranging from food and personal care to pharmaceuticals. Theoretical calculations and mathematical simulations of hydrodynamic interactions and granular-like contacts have proved that contact forces between suspended particles dominate the rheological characteristic of colloidal suspensions. However, relevant experimental studies are very rare. This study was conducted to reveal the influence of nanoparticle (NP) interactions on the rheological behavior of shear-thickening fluids (STFs) by changing the colloidal surface chemistries. Silica NPs with various surface chemical compositions are fabricated and used to prepare dense suspensions. Rheological experiments are conducted to determine the influence of NP interactions on corresponding dense suspension systems. The results suggest that the surface chemistries of silica NPs determine the rheological behavior of dense suspensions, including shear-thickening behavior, onset stress, critical volume fraction, and jamming volume fraction. This study provides useful reference for designing effective STFs and regulating their characteristics.

Clinical Chemistry of Patients With Ebola in Monrovia, Liberia

PubMed Central

de Wit, Emmie; Kramer, Shelby; Prescott, Joseph; Rosenke, Kyle; Falzarano, Darryl; Marzi, Andrea; Fischer, Robert J.; Safronetz, David; Hoenen, Thomas; Groseth, Allison; van Doremalen, Neeltje; Bushmaker, Trenton; McNally, Kristin L.; Feldmann, Friederike; Williamson, Brandi N.; Best, Sonja M.; Ebihara, Hideki; Damiani, Igor A. C.; Adamson, Brett; Zoon, Kathryn C.; Nyenswah, Tolbert G.; Bolay, Fatorma K.; Massaquoi, Moses; Sprecher, Armand; Feldmann, Heinz; Munster, Vincent J.

2016-01-01

The development of point-of-care clinical chemistry analyzers has enabled the implementation of these ancillary tests in field laboratories in resource-limited outbreak areas. The Eternal Love Winning Africa (ELWA) outbreak diagnostic laboratory, established in Monrovia, Liberia, to provide Ebola virus and Plasmodium spp. diagnostics during the Ebola epidemic, implemented clinical chemistry analyzers in December 2014. Clinical chemistry testing was performed for 68 patients in triage, including 12 patients infected with Ebola virus and 18 infected with Plasmodium spp. The main distinguishing feature in clinical chemistry of Ebola virus–infected patients was the elevation in alanine aminotransferase, aspartate aminotransferase, alkaline phosphatase, and γ-glutamyltransferase levels and the decrease in calcium. The implementation of clinical chemistry is probably most helpful when the medical supportive care implemented at the Ebola treatment unit allows for correction of biochemistry derangements and on-site clinical chemistry analyzers can be used to monitor electrolyte balance. PMID:27471319

Magic, science and masculinity: marketing toy chemistry sets.

PubMed

Al-Gailani, Salim

2009-12-01

At least since the late nineteenth century, toy chemistry sets have featured in standard scripts of the achievement of eminence in science, and they remain important in constructions of scientific identity. Using a selection of these toys manufactured in Britain and the United States, and with particular reference to the two dominant American brands, Gilbert and Chemcraft, this paper suggests that early twentieth-century chemistry sets were rooted in overlapping Victorian traditions of entertainment magic and scientific recreations. As chemistry set marketing copy gradually reoriented towards emphasising scientific modernity, citizenship, discipline and educational value, pre-twentieth-century traditions were subsumed within domestic-and specifically masculine-tropes. These developments in branding strategies point to transformations in both users' engagement with their chemistry sets and the role of scientific toys in domestic play. The chemistry set serves here as a useful tool for measuring cultural change and lay engagement with chemistry.

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

Schaeffer, Daniel A.; Polizos, Georgios; Smith, D. Barton

Optical surfaces such as mirrors and windows that are exposed to outdoor environmental conditions are susceptible to dust buildup and water condensation. The application of transparent superhydrophobic coatings on optical surfaces can improve outdoor performance via a self-cleaning effect similar to the Lotus effect. The contact angle (CA) of water droplets on a typical hydrophobic flat surface varies from 100° to 120°. Adding roughness or microtexture to a hydrophobic surface leads to an enhancement of hydrophobicity and the CA can be increased to a value in the range of 16≥0° to 175°. This result is remarkable because such behavior cannotmore » be explained using surface chemistry alone. When surface features are on the order of 100 nm or smaller, surfaces exhibit superhydrophobic behavior and maintain their optical transparency. In this work we discuss our results on transparent superhydrophobic coatings that can be applied across large surface areas. We have used functionalized silica nanoparticles to coat various optical elements and have measured the contact angle and optical transmission between 190 to 1100 nm on these elements. The functionalized silica nanoparticles were dissolved in a solution of the solvents isopropyl alcohol and 4-chlorobenzotrifluoride (PCBTF) and a proprietary ceramic binder (Cerakote ). Finally, this solution was spin-coated onto a variety of test glass substrates, and following a curing period of about 30 minutes, these coatings exhibited superhydrophobic behavior with a static CA ≥160°.« less

First-principles surface interaction studies of aluminum-copper and aluminum-copper-magnesium secondary phases in aluminum alloys

NASA Astrophysics Data System (ADS)

da Silva, Thiago H.; Nelson, Eric B.; Williamson, Izaak; Efaw, Corey M.; Sapper, Erik; Hurley, Michael F.; Li, Lan

2018-05-01

First-principles density functional theory-based calculations were performed to study θ-phase Al2Cu, S-phase Al2CuMg surface stability, as well as their interactions with water molecules and chloride (Cl-) ions. These secondary phases are commonly found in aluminum-based alloys and are initiation points for localized corrosion. Density functional theory (DFT)-based simulations provide insight into the origins of localized (pitting) corrosion processes of aluminum-based alloys. For both phases studied, Cl- ions cause atomic distortions on the surface layers. The nature of the distortions could be a factor to weaken the interlayer bonds in the Al2Cu and Al2CuMg secondary phases, facilitating the corrosion process. Electronic structure calculations revealed not only electron charge transfer from Cl- ions to alloy surface but also electron sharing, suggesting ionic and covalent bonding features, respectively. The S-phase Al2CuMg structure has a more active surface than the θ-phase Al2Cu. We also found a higher tendency of formation of new species, such as Al3+, Al(OH)2+, HCl, AlCl2+, Al(OH)Cl+, and Cl2 on the S-phase Al2CuMg surface. Surface chemical reactions and resultant species present contribute to establishment of local surface chemistry that influences the corrosion behavior of aluminum alloys.

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

Lunar soil and surface processes studies

NASA Technical Reports Server (NTRS)

Glass, B. P.

1975-01-01

Glass particles in lunar soil were characterized and compared to terrestrial analogues. In addition, useful information was obtained concerning the nature of lunar surface processes (e.g. volcanism and impact), maturity of soils and chemistry and heterogeneity of lunar surface material. It is felt, however, that the most important result of the study was that it demonstrated that the investigation of glass particles from the regolith of planetary bodies with little or no atmospheres can be a powerful method for learning about the surface processes and chemistry of planetary surfaces. Thus, the return of samples from other planetary bodies (especially the terrestrial planets and asteroids) using unmanned spacecraft is urged.

The relative effect of surface strontium chemistry and super-hydrophilicity on the early osseointegration of moderately rough titanium surface in the rabbit femur.

PubMed

Park, Jin-Woo; Kwon, Tae-Geon; Suh, Jo-Young

2013-06-01

It is unclear whether surface bioactive chemistry or hydrophilicity plays a more dominant role in the osseointegration of micro-structured titanium implants having the same surface topography at the micrometer and submicrometer scales. To understand their comparative effect on enhancing the early osseointegration of micro-rough-surfaced implants, this study compared the bone healing-promoting effect of surface strontium (Sr) chemistry that has been shown in numerous studies to super-hydrophilicity in the early osseointegration of moderately rough-surfaced clinical oral implants (SLA(®) implant) in rabbit cancellous bone. Hydrothermal treatment was performed to incorporate Sr ions into the surface of clinical SLA implants (SLA/Sr implant). The surface characteristics were evaluated by using field emission-scanning electron microscopy, X-ray photoelectron spectroscopy and optical profilometry. Twenty screw implants (10 control and 10 experimental) were placed in the femoral condyles of 10 New Zealand White rabbits. The early osseointegration of the SLA/Sr implant was compared with a chemically modified super-hydrophilic SLA implant (SLActive(®) implant) by histomorphometric and resonance frequency analysis after 2 weeks of implantation. The SLA/Sr and SLActive implants exhibited an identical surface topography and average R(a) values at the micron and submicron scales. The SLA/Sr implant displayed a high amount of surface Sr content (15.6 at.%). There was no significant difference in the implant stability quotient (ISQ) values between the two groups. However, histomorphometric analysis revealed a significantly higher bone-to-implant contact percentage in the SLA/Sr implants compared with the SLActive implants in rabbit cancellous bone (P < 0.01). The results indicate that the surface Sr chemistry surpasses the effect of super-hydrophilicity in promoting the early bone apposition of moderately rough Ti surface in cancellous bone. © 2012 John Wiley & Sons A/S.

Composition, structure, and chemistry of interstellar dust

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.; Allamandola, L. J.

1987-01-01

Different dust components present in the interstellar medium (IM) such as amorphous carbon, polycyclic aromatic hydrocarbons, and those IM components which are organic refractory grains and icy grain mantles are discussed as well as their relative importance. The physical properties of grain surface chemistry are discussed with attention given to the surface structure of materials, the adsorption energy and residence time of species on a grain surface, and the sticking probability. Consideration is also given to the contribution of grains to the gas-phase composition of molecular clouds.

Using Raman Spectroscopy and Surface-Enhanced Raman Scattering to Identify Colorants in Art: An Experiment for an Upper-Division Chemistry Laboratory

ERIC Educational Resources Information Center

Mayhew, Hannah E.; Frano, Kristen A.; Svoboda, Shelley A.; Wustholz, Kristin L.

2015-01-01

Surface-enhanced Raman scattering (SERS) studies of art represent an attractive way to introduce undergraduate students to concepts in nanoscience, vibrational spectroscopy, and instrumental analysis. Here, we present an undergraduate analytical or physical chemistry laboratory wherein a combination of normal Raman and SERS spectroscopy is used to…

Color and surface chemistry changes of extracted wood flour after heating at 120 °C

Treesearch

Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark

2013-01-01

To investigate the effect of heat on color and surface chemistry of wood flour (WF), unextracted, extracted and delignified samples of commercial WF were heated at 120 °C for 24 h and analyzed by colorimetry, diffuse reflectance visible (DRV), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Fourier transform Raman (FT-Raman) spectroscopies....

Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

ERIC Educational Resources Information Center

Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

2010-01-01

Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

PubMed

Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

2014-12-10

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

The effects of engine operating conditions on CCD chemistry and morphology

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

Yeh, S.W.; Moore, S.M.; Sabourin, E.T.

1996-10-01

The effects of engine driving cycle and engine coolant temperature on combustion chamber deposit (CCD) surface chemistry and morphology were assessed by the use of XPS and scanning electron micrographs. A 3.1L V6 test cell engine was used to generate a six test matrix that compared deposit surface chemistry and morphology under two distinctly different driving cycles, each cycle being evaluated at three separate engine coolant temperatures. Deposit material for each respective test was collected by removable combustion chamber sample probes that were subjected to XPS surface analysis and SEM evaluation. Discernible trends were observed in surface chemistry and depositmore » amounts with respect to changes in both driving cycle and coolant temperature. However, much more pronounced were deposit morphological changes recorded by SEM in different engine coolant temperature regimes for both of the utilized driving cycles. Deposit nodules formed in one temperature regime were seen to be typically much larger in size, highly irregular in shape, and appeared to be porous in structure. At a different operating temperature, the deposit nodules were observed to be extremely uniform and more tightly packed.« less

Quantum Tunneling Affects Engine Performance.

PubMed

Som, Sibendu; Liu, Wei; Zhou, Dingyu D Y; Magnotti, Gina M; Sivaramakrishnan, Raghu; Longman, Douglas E; Skodje, Rex T; Davis, Michael J

2013-06-20

We study the role of individual reaction rates on engine performance, with an emphasis on the contribution of quantum tunneling. It is demonstrated that the effect of quantum tunneling corrections for the reaction HO2 + HO2 = H2O2 + O2 can have a noticeable impact on the performance of a high-fidelity model of a compression-ignition (e.g., diesel) engine, and that an accurate prediction of ignition delay time for the engine model requires an accurate estimation of the tunneling correction for this reaction. The three-dimensional model includes detailed descriptions of the chemistry of a surrogate for a biodiesel fuel, as well as all the features of the engine, such as the liquid fuel spray and turbulence. This study is part of a larger investigation of how the features of the dynamics and potential energy surfaces of key reactions, as well as their reaction rate uncertainties, affect engine performance, and results in these directions are also presented here.

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling in a Green Alcohol Solvent for an Undergraduate Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Hie, Liana; Chang, Jonah J.; Garg, Neil K.

2015-01-01

A modern undergraduate organic chemistry laboratory experiment involving the Suzuki-Miyaura coupling is reported. Although Suzuki-Miyaura couplings typically employ palladium catalysts in environmentally harmful solvents, this experiment features the use of inexpensive nickel catalysis, in addition to a "green" alcohol solvent. The…

Kids and Chemistry: Large Event Guide.

ERIC Educational Resources Information Center

Tinnesand, Michael

This guide is intended to provide Kids and Chemistry (K&C) with a variety of age-appropriate, fun, and safe demonstrations. It features information on planning a large event and includes safety guidelines. Several activities are included under each major topic. Topics include: (1) Acids and Bases; (2) Unsigned; (3) Kool Tie-Dye; (4) Secret…

A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Duff, David B.; Abbe, Tyler G.; Goess, Brian C.

2012-01-01

A multistep synthesis of 5-isopropyl-1,3-cyclohexanedione is carried out from three commodity chemicals. The sequence involves an aldol condensation, Dieckmann-type annulation, ester hydrolysis, and decarboxylation. No purification is required until after the final step, at which point gravity column chromatography provides the desired product in…

Full Field X-Ray Fluorescence Imaging Using Micro Pore Optics for Planetary Surface Exploration

NASA Technical Reports Server (NTRS)

Sarrazin, P.; Blake, D. F.; Gailhanou, M.; Walter, P.; Schyns, E.; Marchis, F.; Thompson, K.; Bristow, T.

2016-01-01

Many planetary surface processes leave evidence as small features in the sub-millimetre scale. Current planetary X-ray fluorescence spectrometers lack the spatial resolution to analyse such small features as they only provide global analyses of areas greater than 100 mm(exp 2). A micro-XRF spectrometer will be deployed on the NASA Mars 2020 rover to analyse spots as small as 120m. When using its line-scanning capacity combined to perpendicular scanning by the rover arm, elemental maps can be generated. We present a new instrument that provides full-field XRF imaging, alleviating the need for precise positioning and scanning mechanisms. The Mapping X-ray Fluorescence Spectrometer - "Map-X" - will allow elemental imaging with approximately 100µm spatial resolution and simultaneously provide elemental chemistry at the scale where many relict physical, chemical and biological features can be imaged in ancient rocks. The arm-mounted Map-X instrument is placed directly on the surface of an object and held in a fixed position during measurements. A 25x25 mm(exp 2) surface area is uniformly illuminated with X-rays or alpha-particles and gamma-rays. A novel Micro Pore Optic focusses a fraction of the emitted X-ray fluorescence onto a CCD operated at a few frames per second. On board processing allows measuring the energy and coordinates of each X-ray photon collected. Large sets of frames are reduced into 2d histograms used to compute higher level data products such as elemental maps and XRF spectra from selected regions of interest. XRF spectra are processed on the ground to further determine quantitative elemental compositions. The instrument development will be presented with an emphasis on the characterization and modelling of the X-ray focussing Micro Pore Optic. An outlook on possible alternative XRF imaging applications will be discussed.

The coupled effects of chemistry and diffusion on the stratospheric ozone reduction

NASA Technical Reports Server (NTRS)

Gupta, R. N.; Grose, W. L.

1980-01-01

The effect of diffusive-mixing on O3-depletion is estimated using the five-step chemistry model. The coupled treatment uses an equilibrium turbulence field and retains the key features of the kinetics while keeping the chemistry simple. Results indicate that those calculations of Hilst and Donaldson (1973) employing the conservation of NO2/NO will yield erroneous results, and it is found that any significant level of turbulence will reduce the severity of the NOx catalytic cycle for O3 destruction.

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.

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage.

PubMed

Guan, Cao; Wang, John

2016-10-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution-based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed.

Interfacial B-site atomic configuration in polar (111) and non-polar (001) SrIrO3/SrTiO3 heterostructures

NASA Astrophysics Data System (ADS)

Anderson, T. J.; Zhou, H.; Xie, L.; Podkaminer, J. P.; Patzner, J. J.; Ryu, S.; Pan, X. Q.; Eom, C. B.

2017-09-01

The precise control of interfacial atomic arrangement in ABO3 perovskite heterostructures is paramount, particularly in cases where the subsequent electronic properties of the material exhibit geometrical preferences along polar crystallographic directions that feature inevitably complex surface reconstructions. Here, we present the B-site interfacial structure in polar (111) and non-polar (001) SrIrO3/SrTiO3 interfaces. The heterostructures were examined using scanning transmission electron microscopy and synchrotron-based coherent Bragg rod analysis. Our results reveal the preference of B-site intermixing across the (111) interface due to the polarity-compensated SrTiO3 substrate surface prior to growth. By comparison, the intermixing at the non-polar (001) interface is negligible. This finding suggests that the intermixing may be necessary to mitigate epitaxy along heavily reconstructed and non-stoichiometric (111) perovskite surfaces. Furthermore, this preferential B-site configuration could allow the geometric design of the interfacial perovskite structure and chemistry to selectively engineer the correlated electronic states of the B-site d-orbital.

Further evidence for a link between Late Pleistocene North Atlantic surface temperatures and North Atlantic deep-water production

NASA Astrophysics Data System (ADS)

Boyle, Edward A.; Rosener, Paula

1990-10-01

Reduced surface temperatures, salinity and North Atlantic Deep-Water (NADW) formation rate may be mechanistically linked. Previous studies have demonstrated the co-occurrence of lowered high-latitude T and NADW during glacial maxima and the brief ( t 1000 yr) Younger Dryas cooling event 10,500 years ago. This behavior also appears as a feature of a recent coupled ocean/atmosphere general circulation model. Here, it is shown that rapid fluctuations in North Atlantic surface temperatures (as indicated by variations from 7 to 22% left-cooling N. pachyderma) during oxygen isotope stage 3 also may be linked to fluctuations in deep-water chemistry (as indicated by benthic Cd/Ca variations from 0.080 to 0.120 μmol. mol. -1). Two complete cycles in both properties are observed in 30 cm of sediment; bioturbation modeling suggests that the true extrema are muted and that the reproducibility of replicate analyses is primarily limited by the sampling statistics of bioturbated mixrure. The current evidence raises the question of whether NADW is regulated by a "switch" or by a "valve".

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage

PubMed Central

2016-01-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution‐based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed. PMID:27840793

Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling in a Green Alcohol Solvent for an Undergraduate Organic Chemistry Laboratory.

PubMed

Hie, Liana; Chang, Jonah J; Garg, Neil K

2015-03-10

A modern undergraduate organic chemistry laboratory experiment involving the Suzuki-Miyaura coupling is reported. Although Suzuki-Miyaura couplings typically employ palladium catalysts in environmentally harmful solvents, this experiment features the use of inexpensive nickel catalysis, in addition to a "green" alcohol solvent. The experiment employs heterocyclic substrates, which are important pharmaceutical building blocks. Thus, this laboratory procedure exposes students to a variety of contemporary topics in organic chemistry, including transition metal-catalyzed cross-couplings, green chemistry, and the importance of heterocycles in drug discovery, none of which are well represented in typical undergraduate organic chemistry curricula. The experimental protocol uses commercially available reagents and is useful in both organic and inorganic instructional laboratories.

Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

PubMed

Williams, David; Viti, Serena

2013-07-13

We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day.

Next Steps Forward in Understanding Martian Surface and Subsurface Chemistry

NASA Astrophysics Data System (ADS)

Carrier, Brandi L.

2017-09-01

The presence of oxidants such as hydrogen peroxide (H2O2) and perchlorate (ClO4-), which have been detected on Mars, has significant implications for chemistry and astrobiology. These oxidants can increase the reactivity of the Martian soil, accelerate the decomposition of organic molecules, and depress the freezing point of water. The study by Crandall et al. "Can Perchlorates be Transformed to Hydrogen Peroxide Products by Cosmic Rays on the Martian Surface" reveals a new formation mechanism by which hydrogen peroxide and other potential oxidants can be generated via irradiation of perchlorate by cosmic rays. This study represents an important next step in developing a full understanding of Martian surface and subsurface chemistry, particularly with respect to degradation of organic molecules and potential biosignatures.

Influence of surface structure and chemistry on water droplet splashing.

PubMed

Koch, Kerstin; Grichnik, Roland

2016-08-06

Water droplet splashing and aerosolization play a role in human hygiene and health systems as well as in crop culturing. Prevention or reduction of splashing can prevent transmission of diseases between animals and plants and keep technical systems such as pipe or bottling systems free of contamination. This study demonstrates to what extent the surface chemistry and structures influence the water droplet splashing behaviour. Smooth surfaces and structured replicas of Calathea zebrina (Sims) Lindl. leaves were produced. Modification of their wettability was done by coating with hydrophobizing and hydrophilizing agents. Their wetting was characterized by contact angle measurement and splashing behaviour was observed with a high-speed video camera. Hydrophobic and superhydrophilic surfaces generally showed fewer tendencies to splash than hydrophobic ones. Structuring amplified the underlying behaviour of the surface chemistries, increasing hydrophobic surfaces' tendency to splash and decreasing splash on hydrophilic surfaces by quickly transporting water off the impact point by capillary forces. The non-porous surface structures found in C. zebrina could easily be applied to technical products such as plastic foils or mats and coated with hydrophilizing agents to suppress splash in areas of increased hygiene requirements or wherever pooling of liquids is not desirable.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'. © 2016 The Author(s).

One-Pot Anchoring of Pd Nanoparticles on Nitrogen-Doped Carbon through Dopamine Self-Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction.

PubMed

Li, Xin; Niu, Xiangheng; Zhang, Wenchi; He, Yanfang; Pan, Jianming; Yan, Yongsheng; Qiu, Fengxian

2017-03-09

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low-cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen-doped carbon support were fabricated using a facile one-pot dopamine self-polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self-polymerization but was also the precursor of the nitrogen-doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal-support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup-shutdown operations) for the MOR in alkaline media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel procedure to enhance PLA surface properties by chitosan irreversible immobilization

NASA Astrophysics Data System (ADS)

Stoleru, Elena; Dumitriu, Raluca Petronela; Munteanu, Bogdanel Silvestru; Zaharescu, Traian; Tănase, Elisabeta Elena; Mitelut, Amalia; Ailiesei, Gabriela-Liliana; Vasile, Cornelia

2016-03-01

A novel two step procedure was applied for poly(lactic acid) (PLA) functionalization consisting in the exposure to cold radiofrequency plasma in nitrogen atmosphere or to gamma irradiation followed by ;grafting to; of a chitosan layer using carbodiimide chemistry. The adhesion and stability of the deposited surface layer was assured by plasma/gamma irradiation treatment while the chitosan layer offers antifungal/antibacterial/antioxidant activities. Chitosan with different viscosities/deacetylation degree was deposited by electrospinning or immersion methods. Correlations between rheological behavior of chitosan solutions and chitosan layer deposition conditions are made. The PLA surface properties were investigated by water contact angle measurements, ATR-FTIR spectroscopy, AFM, chemiluminiscence, etc. It has been established that the surface roughness increases direct proportional with cold plasma duration and gamma irradiation dose and further increases by chitosan coating which at its turn depends on chitosan characteristics (viscosity and deacetylation degree) and method of deposition. Nano-fibers with relatively homogeneous and reproducible features are obtained by electrospinning of highly viscous chitosan while with the other two types of chitosan both microparticles and nano-fibers are formed. The chitosan coating obtained by immersion is more homogenous and compact and has a better antibacterial activity than the electrospun layer as fiber meshes.

Groundwater, springs, and stream flow generation in an alpine meadow of a tropical glacierized catchment

NASA Astrophysics Data System (ADS)

Gordon, R.; Lautz, L. K.; McKenzie, J. M.; Mark, B. G.; Chavez, D.

2013-12-01

Melting tropical glaciers supply approximately half of dry season stream discharge in glacierized valleys of the Cordillera Blanca, Peru. The remainder of streamflow originates as groundwater stored in alpine meadows, moraines and talus slopes. A better understanding of the dynamics of alpine groundwater, including sources and contributions to streamflow, is important for making accurate estimates of glacial inputs to the hydrologic budget, and for our ability to make predictions about future water resources as glaciers retreat. Our field study, conducted during the dry season in the Llanganuco valley, focused on a 0.5-km2 alpine meadow complex at 4400 m elevation, which includes talus slopes, terminal moraines, and a debris fan. Two glacial lakes and springs throughout the complex feed a network of stream channels that flow across the meadow (~2 km total length). We combined tracer measurements of stream and spring discharge and groundwater-surface water exchange with synoptic sampling of water isotopic and geochemical composition, in order to characterize and quantify contributions to streamflow from different geomorphic features. Surface water inputs to the stream channels totaled 58 l/s, while the stream gained an additional 57 l/s from groundwater inputs. Water chemistry is primarily controlled by flowpath type (surface/subsurface) and length, as well as bedrock lithology, while stable water isotopic composition appears to be controlled by water source (glacial lake, meadow or deep groundwater). Stream water chemistry is most similar to meadow groundwater springs, but isotopic composition suggests that the majority of stream water, which issues from springs at the meadow/fan interface, is from the same glacial source as the up-gradient lake. Groundwater sampled from piezometers in confined meadow aquifers is unique in both chemistry and isotopic composition, but does not contribute a large percentage of stream water exiting this small meadow, as quantified by discharge measurements and isotopic mixing. However, we expect that as streams flow down through extensive meadows and wetlands in many Cordillera Blanca valleys, meadow groundwater is a more significant contributor to streamflow. Results from this small, high meadow in Llanganuco will be compared to a larger and lower-elevation meadow system in the Quilcayhuanca valley.

Nuclear Magnetic Resonance (NMR) Spectroscopic Characterization of Nanomaterials and Biopolymers

NASA Astrophysics Data System (ADS)

Guo, Chengchen

Nanomaterials have attracted considerable attention in recent research due to their wide applications in various fields such as material science, physical science, electrical engineering, and biomedical engineering. Researchers have developed many methods for synthesizing different types of nanostructures and have further applied them in various applications. However, in many cases, a molecular level understanding of nanoparticles and their associated surface chemistry is lacking investigation. Understanding the surface chemistry of nanomaterials is of great significance for obtaining a better understanding of the properties and functions of the nanomaterials. Nuclear magnetic resonance (NMR) spectroscopy can provide a familiar means of looking at the molecular structure of molecules bound to surfaces of nanomaterials as well as a method to determine the size of nanoparticles in solution. Here, a combination of NMR spectroscopic techniques including one- and two-dimensional NMR spectroscopies was used to investigate the surface chemistry and physical properties of some common nanomaterials, including for example, thiol-protected gold nanostructures and biomolecule-capped silica nanoparticles. Silk is a natural protein fiber that features unique properties such as excellent mechanical properties, biocompatibility, and non-linear optical properties. These appealing physical properties originate from the silk structure, and therefore, the structural analysis of silk is of great importance for revealing the mystery of these impressive properties and developing novel silk-based biomaterials as well. Here, solid-state NMR spectroscopy was used to elucidate the secondary structure of silk proteins in N. clavipes spider dragline silk and B. mori silkworm silk. It is found that the Gly-Gly-X (X=Leu, Tyr, Gln) motif in spider dragline silk is not in a beta-sheet or alpha-helix structure and is very likely to be present in a disordered structure with evidence for 31-helix confirmation. In addition, the conformations of the Ala, Ser, and Tyr residues in silk fibroin of B. mori were investigated and it indicates that the Ala, Ser, and Tyr residues are all present in disordered structures in silk I (before spinning), while show different conformations in silk II (after spinning). Specifically, in silk II, the Ala and Tyr residues are present in both disordered structures and beta-sheet structures, and the Ser residues are present primarily in beta-sheet structures.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

NASA Astrophysics Data System (ADS)

Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

2018-05-01

The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

Surface topography and chemistry shape cellular behavior on wide band-gap semiconductors.

PubMed

Bain, Lauren E; Collazo, Ramon; Hsu, Shu-Han; Latham, Nicole Pfiester; Manfra, Michael J; Ivanisevic, Albena

2014-06-01

The chemical stability and electrical properties of gallium nitride make it a promising material for the development of biocompatible electronics, a range of devices including biosensors as well as interfaces for probing and controlling cellular growth and signaling. To improve the interface formed between the probe material and the cell or biosystem, surface topography and chemistry can be applied to modify the ways in which the device interacts with its environment. PC12 cells are cultured on as-grown planar, unidirectionally polished, etched nanoporous and nanowire GaN surfaces with and without a physisorbed peptide sequence that promotes cell adhesion. While cells demonstrate preferential adhesion to roughened surfaces over as-grown flat surfaces, the topography of that roughness also influences the morphology of cellular adhesion and differentiation in neurotypic cells. Addition of the peptide sequence generally contributes further to cellular adhesion and promotes development of stereotypic long, thin neurite outgrowths over alternate morphologies. The dependence of cell behavior on both the topographic morphology and surface chemistry is thus demonstrated, providing further evidence for the importance of surface modification for modulating bio-inorganic interfaces. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

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

PubMed

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

2018-03-20

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

Orbital evidence for clay and acidic sulfate assemblages on Mars based on mineralogical analogs from Rio Tinto, Spain

NASA Astrophysics Data System (ADS)

Kaplan, Hannah H.; Milliken, Ralph E.; Fernández-Remolar, David; Amils, Ricardo; Robertson, Kevin; Knoll, Andrew H.

2016-09-01

Outcrops of hydrated minerals are widespread across the surface of Mars, with clay minerals and sulfates being commonly identified phases. Orbitally-based reflectance spectra are often used to classify these hydrated components in terms of a single mineralogy, although most surfaces likely contain multiple minerals that have the potential to record local geochemical conditions and processes. Reflectance spectra for previously identified deposits in Ius and Melas Chasma within the Valles Marineris, Mars, exhibit an enigmatic feature with two distinct absorptions between 2.2 and 2.3 μm. This spectral 'doublet' feature is proposed to result from a mixture of hydrated minerals, although the identity of the minerals has remained ambiguous. Here we demonstrate that similar spectral doublet features are observed in airborne, field, and laboratory reflectance spectra of rock and sediment samples from Rio Tinto, Spain. Combined visible-near infrared reflectance spectra and X-ray diffraction measurements of these samples reveal that the doublet feature arises from a mixture of Al-phyllosilicate (illite or muscovite) and jarosite. Analyses of orbital data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) shows that the martian spectral equivalents are also consistent with mixtures of Al-phyllosilicates and jarosite, where the Al-phyllosilicate may also include kaolinite and/or halloysite. A case study for a region within Ius Chasma demonstrates that the relative proportions of the Al-phyllosilicate(s) and jarosite vary within one stratigraphic unit as well as between stratigraphic units. The former observation suggests that the jarosite may be a diagenetic (authigenic) product and thus indicative of local pH and redox conditions, whereas the latter observation may be consistent with variations in sediment flux and/or fluid chemistry during sediment deposition.

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

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

PubMed

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

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

Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials

PubMed Central

Valentine, M. T.; Perlman, Z. E.; Gardel, M. L.; Shin, J. H.; Matsudaira, P.; Mitchison, T. J.; Weitz, D. A.

2004-01-01

Characterization of the properties of complex biomaterials using microrheological techniques has the promise of providing fundamental insights into their biomechanical functions; however, precise interpretations of such measurements are hindered by inadequate characterization of the interactions between tracers and the networks they probe. We here show that colloid surface chemistry can profoundly affect multiple particle tracking measurements of networks of fibrin, entangled F-actin solutions, and networks of cross-linked F-actin. We present a simple protocol to render the surface of colloidal probe particles protein-resistant by grafting short amine-terminated methoxy-poly(ethylene glycol) to the surface of carboxylated microspheres. We demonstrate that these poly(ethylene glycol)-coated tracers adsorb significantly less protein than particles coated with bovine serum albumin or unmodified probe particles. We establish that varying particle surface chemistry selectively tunes the sensitivity of the particles to different physical properties of their microenvironments. Specifically, particles that are weakly bound to a heterogeneous network are sensitive to changes in network stiffness, whereas protein-resistant tracers measure changes in the viscosity of the fluid and in the network microstructure. We demonstrate experimentally that two-particle microrheology analysis significantly reduces differences arising from tracer surface chemistry, indicating that modifications of network properties near the particle do not introduce large-scale heterogeneities. Our results establish that controlling colloid-protein interactions is crucial to the successful application of multiple particle tracking techniques to reconstituted protein networks, cytoplasm, and cells. PMID:15189896

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

PubMed Central

Syverud, Kristin

2014-01-01

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

Gordon Research Conference on Plasma Chemistry (10th), Held in Tilton, New Hampshire on August 15-19, 1988

DTIC Science & Technology

1989-10-01

The 1988 Gordon Research Conference on Plasma Chemistry was divided into nine sessions. Eight had two or three invited talks and two or three...findings in low pressure, non-equilibrium plasma chemistry , covering the topics of plasmas in device technology, and plasma enhanced processing...applications and surface-plasma interactions. Six joint sessions included sessions on future plasma chemistry , nucleation and growth, plasma modeling, one each

The role of surface chemistry in the cytotoxicity profile of graphene.

PubMed

Majeed, Waqar; Bourdo, Shawn; Petibone, Dayton M; Saini, Viney; Vang, Kieng Bao; Nima, Zeid A; Alghazali, Karrer M; Darrigues, Emilie; Ghosh, Anindya; Watanabe, Fumiya; Casciano, Daniel; Ali, Syed F; Biris, Alexandru S

2017-04-01

Graphene and its derivative, because of their unique physical, electrical and chemical properties, are an important class of nanomaterials being proposed as foundational materials in nanomedicine as well as for a variety of industrial applications. A major limitation for graphene, when used in biomedical applications, is its poor solubility due to its rather hydrophobic nature. Therefore, chemical functionalities are commonly introduced to alter both its surface chemistry and biochemical activity. Here, we show that surface chemistry plays a major role in the toxicological profile of the graphene structures. To demonstrate this, we chemically increased the oxidation level of the pristine graphene and compared the corresponding toxicological effects along with those for the graphene oxide. X-ray photoelectron spectroscopy revealed that pristine graphene had the lowest amount of surface oxygen, while graphene oxide had the highest at 2.5% and 31%, respectively. Low and high oxygen functionalized graphene samples were found to have 6.6% and 24% surface oxygen, respectively. Our results showed a dose-dependent trend in the cytotoxicity profile, where pristine graphene was the most cytotoxic, with decreasing toxicity observed with increasing oxygen content. Increased surface oxygen also played a role in nanomaterial dispersion in water or cell culture medium over longer periods. It is likely that higher dispersity might result in graphene entering into cells as individual flakes ~1 nm thick rather than as more cytotoxic aggregates. In conclusion, changes in graphene's surface chemistry resulted in altered solubility and toxicity, suggesting that a generalized toxicity profile would be rather misleading. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Chemical Gradients on Graphene to Drive Droplet Motion

DTIC Science & Technology

2013-05-09

the flexibility of carbon chemistry, graphene provides many options in designing such gradients. Moreover, to effectively move a liquid droplet, the...surface chemistry gradientmust be both continuous (x and y direction) and uniform in the direc - tion perpendicular to the droplet motion (y direction) to...directing the transport of liquid droplets. This work demonstrates that with careful consideration of the surface chem- istry, electron beam-generated

Knowledge Production at Industrial Research Institutes: Institutional Logics and Struggles for Relevance in the Swedish Institute for Surface Chemistry, 1980-2005

ERIC Educational Resources Information Center

Bruno, Karl; Larsen, Katarina; van Leeuwen, Thed N.

2017-01-01

This article examines dynamics of knowledge production and discourses of basic-applied science and relevance at the Swedish Institute for Surface Chemistry, a semi-public industrially oriented research institute, from 1980 to 2005. We employ a three-pronged method, consisting of (1) an analysis of how the institute articulated its research…

Surface physics of semiconducting nanowires

NASA Astrophysics Data System (ADS)

Amato, Michele; Rurali, Riccardo

2016-02-01

Semiconducting nanowires (NWs) are firm candidates for novel nanoelectronic devices and a fruitful playground for fundamental physics. Ultra-thin nanowires, with diameters below 10 nm, present exotic quantum effects due to the confinement of the wave functions, e.g. widening of the electronic band-gap, deepening of the dopant states. However, although several reports of sub-10 nm wires exist to date, the most common NWs have diameters that range from 20 to 200 nm, where these quantum effects are absent or play a very minor role. Yet, the research activity on this field is very intense and these materials still promise to provide an important paradigm shift for the design of emerging electronic devices and different kinds of applications. A legitimate question is then: what makes a nanowire different from bulk systems? The answer is certainly the large surface-to-volume ratio. In this article we discuss the most salient features of surface physics and chemistry in group-IV semiconducting nanowires, focusing mostly on Si NWs. First we review the state-of-the-art of NW growth to achieve a smooth and controlled surface morphology. Next we discuss the importance of a proper surface passivation and its role on the NW electronic properties. Finally, stressing the importance of a large surface-to-volume ratio and emphasizing the fact that in a NW the surface is where most of the action takes place, we discuss molecular sensing and molecular doping.

Annealing temperature dependent reversible wettability switching of micro/nano structured ZnO superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Velayi, Elmira; Norouzbeigi, Reza

2018-05-01

Superhydrophobic ZnO surfaces with reversibly tunable wettability were fabricated on stainless steel meshes via a facile chemical bath deposition method just by regulating the micro/nano structured ZnO needles without using chemical post modifications. The obtained surfaces can be easily and reversibly switched between superhydrophobic and superhydrophilic/underwater superoleophobic characteristics by altering the annealing temperatures. As-prepared sample exhibited long-term superhydrophobic properties with a water contact angle (WCA) of 163.8° ± 1.8° and contact angle hysteresis (CAH) of 1.1° ± 0.8°. The SEM, XRD, XPS and Raman analyses were employed to characterize the morphological features and surface chemistry of the prepared samples. SEM images showed the formation of ZnO micro/nanoneedles with a diameter of ∼90 nm on the substrate. The superhydrophobic ZnO surface was switched to highly hydrophilic and underwater superoleophobic properties with an oil contact angle (OCA) of about 172.5° after being annealed at 400 °C in air for 30 min and restored to superhydrophobic state again by altering the annealing temperature to 150 °C. Mechanical durability of the ZnO superhydrophobic surface was tested by an abrasion test. Results confirmed that the prepared surface exhibited an excellent robustness after 20 abrasion cycles under the pressure of 4.7 kPa.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Saturn's satellites: Potential for organic chemistry

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Lane, A. L.; Henry-Riyad, H.; Tidwell, T. T.

2003-05-01

The surfaces of the Saturnian satellites are subjected to irradiation from solar wind ions, photons, and magnetospheric ions and electrons. This bombardment will transform the chemical nature of the surfaces. At present, only water ice has been detected on their surfaces. Further studies by the Cassini spacecraft may reveal other molecules. If CO2 ice is found there, a whole panoply of new species may be detected. As nitrogen ions in the magnetosphere are thought to be an important species bombarding the satellites, Delitsky and Lane (2002) outlined the nitrogen oxides chemistry that may result from implantation of N+ into the water ice surfaces. Sittler et al (2002) showed that N+ ions originating from Titan will be enriched in the magnetospheric ion population as they move inwards towards Saturn, making the nitrogen oxides chemistry more likely. If CO2 is present, a complicated C-H-N-O chemistry may result from deposition of the N+ into a H2O/CO2 mixed ice, including nitriles, isocyanates, polymers, and amino acids. The combination of H2O/CO2 upon irradiation may also yield a complex mixture of hydrocarbons, esters, alcohols, organic acids and ketones. Possible chemical pathways and computations of their energetics will be presented. -Ref:- 1. Delitsky and Lane, Saturn's inner satellites: Ice chemistry and magnetosphere effects, JGR (Planets), Nov 2002, 3-1;; 2. Sittler et al., Energetic nitrogen ions within the inner magnetosphere of Saturn, Fall AGU meeting, Dec 2002, abstracts, pg F858, P21B-0379

Influence of a magnetic field during directional solidification of MAR-M 246 + Hf superalloy

NASA Technical Reports Server (NTRS)

Andrews, J. Barry; Alter, Wendy; Schmidt, Dianne

1991-01-01

An area that has been almost totally overlooked in the optimization of properties in directionally solidified superalloys is the control of microstructural features through the application of a magnetic field during solidification. The influence of a magnetic field on the microstructural features of a nickel-base superalloys is investigated. Studies were performed on the dendritic MAR-M 246+Hf alloy, which was solidified under both a 5 K gauss magnetic field and under no-applied-field conditions. The possible influences of the magnetic field on the solidification process were observed by studying variations in microstructural features including volume fraction, surface area, number, and shape of the carbide particles. Stereological factors analyzed also included primary and secondary dendrite arm spacing and the volume fraction of the interdendritic eutectic constituent. Microprobe analysis was performed to determine the chemistry of the carbides, dendrites, and interdendritic constituents, and how it varied between field and no-field solidification samples. Experiments involving periodic application and removal of the magnetic field were also performed in order to permit a comparison with structural variations observed in a MAR-M 246+Hf alloy solidified during KC-135 high-g, low-g maneuvers.

Atomic-scale simulation of dust grain collisions: Surface chemistry and dissipation beyond existing theory

NASA Astrophysics Data System (ADS)

Quadery, Abrar H.; Doan, Baochi D.; Tucker, William C.; Dove, Adrienne R.; Schelling, Patrick K.

2017-10-01

The early stages of planet formation involve steps where submicron-sized dust particles collide to form aggregates. However, the mechanism through which millimeter-sized particles aggregate to kilometer-sized planetesimals is still not understood. Dust grain collision experiments carried out in the environment of the Earth lead to the prediction of a 'bouncing barrier' at millimeter-sizes. Theoretical models, e.g., Johnson-Kendall-Roberts and Derjaguin-Muller-Toporov theories, lack two key features, namely the chemistry of dust grain surfaces, and a mechanism for atomic-scale dissipation of energy. Moreover, interaction strengths in these models are parameterized based on experiments done in the Earth's environment. To address these issues, we performed atomic-scale simulations of collisions between nonhydroxylated and hydroxylated amorphous silica nanoparticles. We used the ReaxFF approach which enables modeling chemical reactions using an empirical potential. We found that nonhydroxylated nanograins tend to adhere with much higher probability than suggested by existing theories. By contrast, hydroxylated nanograins exhibit a strong tendency to bounce. Also, the interaction between dust grains has the characteristics of a strong chemical force instead of weak van der Waals forces. This suggests that the formation of strong chemical bonds and dissipation via internal atomic vibration may result in aggregation beyond what is expected based on our current understanding. Our results also indicate that experiments should more carefully consider surface conditions to mimic the space environment. We also report results of simulations with molten silica nanoparticles. It is found that molten particles are more likely to adhere due to viscous dissipation, which supports theories that suggest aggregation to kilometer scales might require grains to be in a molten state.

Stratospheric ozone loss and Antarctic climate change: an update from a stratosphere resolving Chemistry Climate Model simulation

NASA Astrophysics Data System (ADS)

Abalichin, Janna; Kubin, Anne; Grieger, Jens; Langematz, Ulrike; Leckebusch, Gregor C.; Joeckel, Patrick; Brühl, Christoph

2010-05-01

The evolution of Antarctic climate during the past four decades was characterized by enhanced tropospheric westerlies and a negative trend in near-surface temperature over the Antarctic plateau during the austral summer, while the Antarctic Peninsula showed a warming (Thompson and Solomon, 2002). Model simulations suggested that these trends are most certainly attributable to the Antarctic ozone depletion since the early 1980s (Gillett and Thompson, 2003). However, the more recent publication of Steig et al. (2009) finds a warming of the whole Antarctic continent since 1957 in data from satellites and automatic weather stations. Motivated by this discussion we have analysed changes in stratospheric ozone, temperature and dynamics, and the corresponding signal in Antarctic climate in a transient simulation of the period 1960 to 2000, performed with the stratosphere-troposphere Chemistry-Climate Model (CCM) EMAC. The model has been integrated following the SCN2d scenario recommendations of the SPARC CCMVal initiative for the temporal evolution of greenhouse gases, ozone depleting substances and sea surface temperatures/sea ice. The model reproduces the main observed features of the Antarctic stratosphere since the 1960s, e.g. the establishment of the ozone hole in the 1980s, a negative stratospheric temperature trend, and a longer lived and deeper polar vortex and its more intense breakdown. The enhancement of the tropospheric jet is well reproduced as well. With respect to the near surface trends the model seems to support the recently published results of a weak positive temperature trend all over Antarctica. Analyses of heat and humidity fluxes will be used to support the interpretation of the model results.

Surface charge fine tuning of reversed-phase/weak anion-exchange type mixed-mode stationary phases for milder elution conditions.

PubMed

Zimmermann, Aleksandra; Horak, Jeannie; Sánchez-Muñoz, Orlando L; Lämmerhofer, Michael

2015-08-28

A series of new mixed-mode reversed-phase/weak anion-exchange (RP/WAX) phases have been synthesized by immobilization of N-undecenyl-3-α-aminotropane onto thiol-modified silica gel by thiol-ene click chemistry and subsequent introduction of acidic thiol-endcapping functionalities of different type and surface densities. Click chemistry allowed to adjust a controlled surface concentration of the RP/WAX ligand in such a way that a sufficient quantity of residual thiols remained unmodified which have been capped by thiol click with either 3-butenoic acid or allylsulfonic acid as co-ligands. In another embodiment, performic acid oxidation of N-undecenyl-3-α-aminotropane-derivatized thiol-modified silica gave a RP/WAX phase with high density of sulfonic acid end-capping groups. ζ-Potential determinations confirmed the fine-tuned pI of these mixed-mode stationary phases which was shifted from 9.5 to 8.2, 7.8, and 6.5 with 3-butenoic acid and allylsulfonic acid end-capping as well as performic acid oxidation. For acidic solutes, the co-ionic endcapping leads to strongly reduced retention times and clearly allowed elution of these analytes under lower ionic strength thus milder elution conditions. In spite of the acidic endcapping, the new mixed-mode phases maintained their hydrophobic and anion-exchange selectivity as well as their multimodal nature featuring RP and HILIC elution domains at acetonitrile percentages below and above 50%, respectively. Column classification by principal component analysis of an extended retention map in comparison to a set of polar commercial and in-house synthesized stationary phases confirmed complementarity of the new mixed-mode phases with respect to HILIC, polar RP, amino and commercial mixed-mode phases. Copyright © 2015 Elsevier B.V. All rights reserved.

Computational Modeling as a Design Tool in Microelectronics Manufacturing

NASA Technical Reports Server (NTRS)

Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

1997-01-01

Plans to introduce pilot lines or fabs for 300 mm processing are in progress. The IC technology is simultaneously moving towards 0.25/0.18 micron. The convergence of these two trends places unprecedented stringent demands on processes and equipments. More than ever, computational modeling is called upon to play a complementary role in equipment and process design. The pace in hardware/process development needs a matching pace in software development: an aggressive move towards developing "virtual reactors" is desirable and essential to reduce design cycle and costs. This goal has three elements: reactor scale model, feature level model, and database of physical/chemical properties. With these elements coupled, the complete model should function as a design aid in a CAD environment. This talk would aim at the description of various elements. At the reactor level, continuum, DSMC(or particle) and hybrid models will be discussed and compared using examples of plasma and thermal process simulations. In microtopography evolution, approaches such as level set methods compete with conventional geometric models. Regardless of the approach, the reliance on empricism is to be eliminated through coupling to reactor model and computational surface science. This coupling poses challenging issues of orders of magnitude variation in length and time scales. Finally, database development has fallen behind; current situation is rapidly aggravated by the ever newer chemistries emerging to meet process metrics. The virtual reactor would be a useless concept without an accompanying reliable database that consists of: thermal reaction pathways and rate constants, electron-molecule cross sections, thermochemical properties, transport properties, and finally, surface data on the interaction of radicals, atoms and ions with various surfaces. Large scale computational chemistry efforts are critical as experiments alone cannot meet database needs due to the difficulties associated with such controlled experiments and costs.

A quantified dosing ALD reactor with in-situ diagnostics for surface chemistry studies

NASA Astrophysics Data System (ADS)

Larrabee, Thomas J.

A specialized atomic layer deposition (ALD) reactor has been constructed to serve as an instrument to simultaneously study the surface chemistry of the ALD process, and perform ALD as is conventionally done in continuum flow of inert gas. This reactor is uniquely useful to gain insight into the ALD process because of the combination of its precise, controllable, and quantified dosing/microdosing capability; its in-situ quadrupole mass spectrometer for gas composition analysis; its pair of highly-sensitive in-situ quartz crystal microbalances (QCMs); and its complete spectrum of pressures and operating conditions --- from viscous to molecular flow regimes. Control of the dose is achieved independently of the conditions by allowing a reactant gas to fill a fixed volume and measured pressure, which is held at a controlled temperature, and subsequently dosed into the system by computer controlled pneumatic valves. Absolute reactant exposure to the substrate and QCMs is unambiguously calculated from the molecular impingement flux, and its relationship to dose size is established, allowing means for easily intentionally reproducing specific exposures. Methods for understanding atomic layer growth and adsorption phenomena, including the precursor sticking probability, dynamics of molecular impingement, size of dose, and other operating variables are for the first time quantitatively related to surface reaction rates by mass balance. Extensive characterization of the QCM as a measurement tool for adsorption under realistic ALD conditions has been examined, emphasizing the state-of-the-art and importance of QCM system features required. Finally, the importance of dose-quantification and microdosing has been contextualized in view of the ALD literature, underscoring the significance of more precise condition specification in establishing a better basis for reactor and reactant comparison.

Perspective of Fe3O4 Nanoparticles Role in Biomedical Applications

PubMed Central

Kashefi, Mehrdad; Shams, Seyyedeh Fatemeh; Jaafari, Mahmoud Reza

2016-01-01

In recent years, although many review articles have been presented about bioapplications of magnetic nanoparticles by some research groups with different expertise such as chemistry, biology, medicine, pharmacology, and materials science and engineering, the majority of these reviews are insufficiently comprehensive in all related topics like magnetic aspects of process. In the current review, it is attempted to carry out the inclusive surveys on importance of magnetic nanoparticles and especially magnetite ones and their required conditions for appropriate performance in bioapplications. The main attentions of this paper are focused on magnetic features which are less considered. Accordingly, the review contains essential magnetic properties and their measurement methods, synthesis techniques, surface modification processes, and applications of magnetic nanoparticles. PMID:27293893

Multidimensional nanomaterials for the control of stem cell fate

NASA Astrophysics Data System (ADS)

Chueng, Sy-Tsong Dean; Yang, Letao; Zhang, Yixiao; Lee, Ki-Bum

2016-09-01

Current stem cell therapy suffers low efficiency in giving rise to differentiated cell lineages, which can replace the original damaged cells. Nanomaterials, on the other hand, provide unique physical size, surface chemistry, conductivity, and topographical microenvironment to regulate stem cell differentiation through multidimensional approaches to facilitate gene delivery, cell-cell, and cell-ECM interactions. In this review, nanomaterials are demonstrated to work both alone and synergistically to guide selective stem cell differentiation. From three different nanotechnology families, three approaches are shown: (1) soluble microenvironmental factors; (2) insoluble physical microenvironment; and (3) nano-topographical features. As regenerative medicine is heavily invested in effective stem cell therapy, this review is inspired to generate discussions in the potential clinical applications of multi-dimensional nanomaterials.

Solid-State Photochemistry as a Formation Mechanism for Titan's Stratospheric C4N2 Ice Clouds

NASA Technical Reports Server (NTRS)

Anderson, C. M.; Samuelson, R. E.; Yung, Y. L.; McLain, J. L.

2016-01-01

We propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid-state photochemistry occurring within extant ice cloud particles of HCN-HC3N mixtures. This formation process resembles the halogen-induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 per centimeter ice emission feature demonstrates, this solid-state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

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.

Constraints on iron sulfate and iron oxide mineralogy from ChemCam visible/near-infrared reflectance spectroscopy of Mt. Sharp basal units, Gale Crater, Mars

DOE PAGES

Johnson, Jeffrey R.; Bell, James F.; Bender, Steve; ...

2016-07-01

Relative reflectace point spectra (400–840 nm) were acquired by the Chemistry and Camera (ChemCam) instrument on the Mars Science Laboratory (MSL) rover Curiosity in passive mode (no laser) of drill tailings and broken rock fragments near the rover as it entered the lower reaches of Mt. Sharp and of landforms at distances of 2–8 km. Freshly disturbed surfaces are less subject to the spectral masking effects of dust, and revealed spectral features consistent with the presence of iron oxides and ferric sulfates. Here, we present the first detection on Mars of a ~433 nm absorption band consistent with small abundancesmore » of ferric sulfates, corroborated by jarosite detections by the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument in the Mojave, Telegraph Peak, and Confidence Hills drilled samples. The disturbed materials near the Bonanza King region also exhibited strong 433 nm bands and negative near-infrared spectral slopes consistent with jarosite. ChemCam passive spectra of the Confidence Hills and Mojave drill tailings showed features suggestive of the crystalline hematite identified by CheMin analyses. The Windjana drill sample tailings exhibited flat, low relative reflectance spectra, explained by the occurrence of magnetite detected by CheMin. Passive spectra of Bonanza King were similar, suggesting the presence of spectrally dark and neutral minerals such as magnetite. Long-distance spectra of the “Hematite Ridge” feature (3–5 km from the rover) exhibited features consistent with crystalline hematite. The Bagnold dune field north of the Hematite Ridge area exhibited low relative reflectance and near-infrared features indicative of basaltic materials (olivine, pyroxene). Light-toned layers south of Hematite Ridge lacked distinct spectral features in the 400–840 nm region, and may represent portions of nearby clay minerals and sulfates mapped with orbital near-infrared observations. The presence of ferric sulfates such as jarosite in the drill tailings suggests a relatively acidic environment, likely associated with flow of iron-bearing fluids, associated oxidation, and/or hydrothermal leaching of sedimentary rocks. Combined with other remote sensing data sets, mineralogical constraints from ChemCam passive spectra will continue to play an important role in interpreting the mineralogy and composition of materials encountered as Curiosity traverses further south within the basal layers of the Mt. Sharp complex.« less

Constraints on iron sulfate and iron oxide mineralogy from ChemCam visible/near-infrared reflectance spectroscopy of Mt. Sharp basal units, Gale Crater, Mars

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

Johnson, Jeffrey R.; Bell, James F.; Bender, Steve

Relative reflectace point spectra (400–840 nm) were acquired by the Chemistry and Camera (ChemCam) instrument on the Mars Science Laboratory (MSL) rover Curiosity in passive mode (no laser) of drill tailings and broken rock fragments near the rover as it entered the lower reaches of Mt. Sharp and of landforms at distances of 2–8 km. Freshly disturbed surfaces are less subject to the spectral masking effects of dust, and revealed spectral features consistent with the presence of iron oxides and ferric sulfates. Here, we present the first detection on Mars of a ~433 nm absorption band consistent with small abundancesmore » of ferric sulfates, corroborated by jarosite detections by the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument in the Mojave, Telegraph Peak, and Confidence Hills drilled samples. The disturbed materials near the Bonanza King region also exhibited strong 433 nm bands and negative near-infrared spectral slopes consistent with jarosite. ChemCam passive spectra of the Confidence Hills and Mojave drill tailings showed features suggestive of the crystalline hematite identified by CheMin analyses. The Windjana drill sample tailings exhibited flat, low relative reflectance spectra, explained by the occurrence of magnetite detected by CheMin. Passive spectra of Bonanza King were similar, suggesting the presence of spectrally dark and neutral minerals such as magnetite. Long-distance spectra of the “Hematite Ridge” feature (3–5 km from the rover) exhibited features consistent with crystalline hematite. The Bagnold dune field north of the Hematite Ridge area exhibited low relative reflectance and near-infrared features indicative of basaltic materials (olivine, pyroxene). Light-toned layers south of Hematite Ridge lacked distinct spectral features in the 400–840 nm region, and may represent portions of nearby clay minerals and sulfates mapped with orbital near-infrared observations. The presence of ferric sulfates such as jarosite in the drill tailings suggests a relatively acidic environment, likely associated with flow of iron-bearing fluids, associated oxidation, and/or hydrothermal leaching of sedimentary rocks. Combined with other remote sensing data sets, mineralogical constraints from ChemCam passive spectra will continue to play an important role in interpreting the mineralogy and composition of materials encountered as Curiosity traverses further south within the basal layers of the Mt. Sharp complex.« less

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

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa

1989-01-01

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

Solder flow over fine line PWB surface finishes

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

Hosking, F.M.; Hernandez, C.L.

1998-08-01

The rapid advancement of interconnect technology has stimulated the development of alternative printed wiring board (PWB) surface finishes to enhance the solderability of standard copper and solder-coated surfaces. These new finishes are based on either metallic or organic chemistries. As part of an ongoing solderability study, Sandia National Laboratories has investigated the solder flow behavior of two azole-based organic solderability preservations, immersion Au, immersion Ag, electroless Pd, and electroless Pd/Ni on fine line copper features. The coated substrates were solder tested in the as-fabricated and environmentally-stressed conditions. Samples were processed through an inerted reflow machine. The azole-based coatings generally providedmore » the most effective protection after aging. Thin Pd over Cu yielded the best wetting results of the metallic coatings, with complete dissolution of the Pd overcoat and wetting of the underlying Cu by the flowing solder. Limited wetting was measured on the thicker Pd and Pd over Ni finishes, which were not completely dissolved by the molten solder. The immersion Au and Ag finishes yielded the lowest wetted lengths, respectively. These general differences in solderability were directly attributed to the type of surface finish which the solder came in contact with. The effects of circuit geometry, surface finish, stressing, and solder processing conditions are discussed.« less

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

Tao, Franklin

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less

The role of "inert" surface chemistry in marine biofouling prevention.

PubMed

Rosenhahn, Axel; Schilp, Sören; Kreuzer, Hans Jürgen; Grunze, Michael

2010-05-07

The settlement and colonization of marine organisms on submerged man-made surfaces is a major economic problem for many marine industries. The most apparent detrimental effects of biofouling are increased fuel consumption of ships, clogging of membranes and heat exchangers, disabled underwater sensors, and growth of biofoulers in aquaculture systems. The presently common-but environmentally very problematic-way to deal with marine biofouling is to incorporate biocides, which use biocidal products in the surface coatings to kill the colonizing organisms, into the surface coatings. Since the implementation of the International Maritime Organization Treaty on biocides in 2008, the use of tributyltin (TBT) is restricted and thus environmentally benign but effective surface coatings are required. In this short review, we summarize the different strategies which are pursued in academia and industry to better understand the mechanisms of biofouling and to develop strategies which can be used for industrial products. Our focus will be on chemically "inert" model surface coatings, in particular oligo- and poly(ethylene glycol) (OEG and PEG) functionalized surface films. The reasons for choosing this class of chemistry as an example are three-fold: Firstly, experiments on spore settlement on OEG and PEG coatings help to understand the mechanism of non-fouling of highly hydrated interfaces; secondly, these studies defy the common assumption that surface hydrophilicity-as measured by water contact angles-is an unambiguous and predictive tool to determine the fouling behavior on the surface; and thirdly, choosing this system is a good example for "interfacial systems chemistry": it connects the behavior of unicellular marine organisms with the antifouling properties of a hydrated surface coating with structural and electronic properties as derived from ab initio quantum mechanical calculations using the electronic wave functions of oxygen, hydrogen, and carbon. This short review is written to outline for non-experts the hierarchical structure in length- and timescale of marine biofouling and the role of surface chemistry in fouling prevention. Experts in the field are referred to more specialized recent reviews.

Resist surface crosslinking using amine-based reactive rinses to mitagate pattern collapse in thin film lithography

NASA Astrophysics Data System (ADS)

Yeh, Wei-Ming; Lawson, Richard A.; Tolbert, Laren M.; Henderson, Clifford L.

2012-03-01

As the semiconductor industry continues to push to smaller critical dimensions, pattern collapse during lithographic processing caused by unbalanced capillary forces during the final rinse and drying process has become an important problem that can limit the practical resolution of a resist material to feature sizes larger than its intrinsic resolution limit. One of the primary modes of pattern collapse is via elastoplastic pattern deformation which is strongly related to the mechanical properties of the resist. One approach to mitigating such collapse problems is to enhance the mechanical properties of the resist features. Since such modification of resist physical properties for pattern collapse purposes is difficult to achieve through modified formulation of the resist itself (i.e. due to the complex set of requirements that a resist must satisfy and the complex set of physical and chemical phenomena that underlie the imaging processing itself), we have pursued an alternative strategy for improving the resist mechanical properties after features are developed in the film but before they are rinsed and dried. The family of techniques being developed in this work function through the use of aqueous compatible reactive rinse solutions that can be applied to developed resist features while they are wet during normal rinse processing on a track system. By applying these techniques during the rinse process, the resist features can be strengthened before they are subjected to significant capillary forces during the final drying step. In this work, the use of diamine compounds to reactively crosslink the surface of resists containing carboxylic acid groups through formation of amide bonds using carbodiimide chemistry has been explored. One advantage of this approach is that it is an aqueous process that should be easily compatible with high volume, track-based lithographic processes. Contact angle studies and x-ray photoelectron spectroscopy (XPS) were used to characterize the surface crosslinking reaction using such diamine surface rinse treatments. Pattern collapse test structures were fabricated and analyzed to measure the amount of mechanical property improvement imparted by such treatments. Application of such amine reactive rinses was found to clearly result in an improvement in the resistance of resists to pattern collapse as observed by SEM. A comparison of the critical stress at the point of pattern collapse as a function of resist feature size also clearly shows a significant improvement in mechanical resilience of resist samples processed with the reactive rinse treatment.

The development and advantages of helium ion microscopy for the study of block copolymer nanopatterns

NASA Astrophysics Data System (ADS)

Bell, Alan P.; Senthamaraikannan, Ramsankar; Ghoshal, Tandra; Chaudhari, Atul; Leeson, Michael; Morris, Mick A.

2015-03-01

Helium ion microscopy (HIM) has been used to study nanopatterns formed in block copolymer (BCP) thin films. Owing to its' small spot size, minimal forward scattering of the incident ion and reduced velocity compared to electrons of comparable energy, HIM has considerable advantages and provides pattern information and resolution not attainable with other commercial microscopic techniques. In order to realize the full potential of BCP nanolithography in producing high density ultra-small features, the dimensions and geometry of these BCP materials will need to be accurately characterized through pattern formation, development and pattern transfer processes. The preferred BCP pattern inspection techniques (to date) are principally atomic force microscopy (AFM) and secondary electron microscopy (SEM) but suffer disadvantages in poor lateral resolution (AFM) and the ability to discriminate individual polymer domains (SEM). SEM suffers from reduced resolution when a more surface sensitive low accelerating voltage is used and low surface signal when a high accelerating voltage is used. In addition to these drawbacks, SEM can require the use of a conductive coating on these insulating materials and this reduces surface detail as well as increasing the dimensions of coated features. AFM is limited by the dimensions of the probe tip and a skewing of lateral dimension results. This can be eliminated through basic geometry for large sparse features, but when dense small features need to be characterized AFM lacks reliability. With this in mind, BCP inspection by HIM can offer greater insight into block ordering, critical dimensions and, critically, line edge roughness (LER) a critical parameter whose measurement is well suited to HIM because of its' enhanced edge contrast. In this work we demonstrate the resolution capabilities of HIM using various BCP systems (lamellar and cylinder structures). Imaging of BCP patterns of low molecular weight (MW)/low feature size which challenges the resolution of HIM technique. Further, studies of BCP patterns with domains of similar chemistry will be presented demonstrating the superior chemical contrast compared to SEM. From the data, HIM excels as a BCP inspection tool in four distinct areas. Firstly, HIM offers higher resolution at standard imaging conditions than SEM. Secondly, the signal generated from He+ is more surface sensitive and enables visualization of features that cannot be resolved using SEM. Thirdly; superior chemical contrast enables the imaging of un etched samples with almost identical chemical composition. Finally, dimensional measurement accuracy is high and consistent with requirements for advanced lithographic masks.

Curriculum and Testing Strategies to Maximize Special Education STAAR Achievement

ERIC Educational Resources Information Center

Johnson, William L.; Johnson, Annabel M.; Johnson, Jared W.

2015-01-01

This document is from a presentation at the 2015 annual conference of the Science Teachers Association of Texas (STAT). The two sessions (each listed as feature sessions at the state conference) examined classroom strategies the presenter used in his chemistry classes to maximize Texas end-of-course chemistry test scores for his special population…

Enhancing Pre-Service Elementary Teachers' Conceptual Understanding of Solution Chemistry with Conceptual Change Text

ERIC Educational Resources Information Center

Calik, Muammer; Ayas, Alipasa; Coll, Richard Kevin

2007-01-01

This paper reports on the use of a constructivist-based pedagogy to enhance understanding of some features of solution chemistry. Pre-service science teacher trainees' prior knowledge about the dissolution of salts and sugar in water were elicited by the use of a simple diagnostic tool. The test revealed widespread alternative conceptions. These…

Plasma chemistry and organic synthesis

NASA Technical Reports Server (NTRS)

Tezuka, M.

1980-01-01

The characteristic features of chemical reactions using low temperature plasmas are described and differentiated from those seen in other reaction systems. A number of examples of applications of plasma chemistry to synthetic reactions are mentioned. The production of amino acids by discharge reactions in hydrocarbon-ammonia-water systems is discussed, and its implications for the origins of life are mentioned.

Characteristics and Levels of Sophistication: An Analysis of Chemistry Students' Ability to Think with Mental Models

ERIC Educational Resources Information Center

Wang, Chia-Yu; Barrow, Lloyd H.

2011-01-01

This study employed a case-study approach to reveal how an ability to think with mental models contributes to differences in students' understanding of molecular geometry and polarity. We were interested in characterizing features and levels of sophistication regarding first-year university chemistry learners' mental modeling behaviors while the…

Ab Initio Determinations of Photoelectron Spectra Including Vibronic Features: An Upper-Level Undergraduate Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Lord, Richard L.; Davis, Lisa; Millam, Evan L.; Brown, Eric; Offerman, Chad; Wray, Paul; Green, Susan M. E.

2008-01-01

We present a first-principles determination of the photoelectron spectra of water and hypochlorous acid as a laboratory exercise accessible to students in an undergraduate physical chemistry course. This paper demonstrates the robustness and user-friendliness of software developed for the Franck-Condon factor calculation. While the calculator is…

Student Perceptions of Learning Data-Creation and Data-Analysis Skills in an Introductory College-Level Chemistry Course

ERIC Educational Resources Information Center

Glazer, Nirit

2015-01-01

This study examines how students perceive their learning of creating and analyzing data in an introductory inquiry chemistry course at a college level that features oral presentations in student-centered discussions. A student Participant Perception Indicator (PPI) survey was administered in order to obtain data on student perceptions with respect…

Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Kessler, Vadim G.

2014-05-01

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

Photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Lee, J.-S.; Stanford, J. A.; Grant, W. K.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Swanberg, E. L.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L. J.; Shah, K.

2013-09-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. Samples of as polished TlBr were treated separately with 2%Br:MeOH, 10%HF, 10%HCl and 96%SOCl2 solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry. Results suggest anion substitution at the surface with subsequent shallow heterojunction formation. Surface chemistry and valence band electronic structure were further correlated with the goal of optimizing the long-term stability and radiation response.

Particle self-assembly at ionic liquid-based interfaces.

PubMed

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

2014-04-01

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

Surface chemistry of gold nanoparticles determines the biocorona composition impacting cellular uptake, toxicity and gene expression profiles in human endothelial cells.

PubMed

Chandran, Parwathy; Riviere, Jim E; Monteiro-Riviere, Nancy A

2017-05-01

This study investigated the role of nanoparticle size and surface chemistry on biocorona composition and its effect on uptake, toxicity and cellular responses in human umbilical vein endothelial cells (HUVEC), employing 40 and 80 nm gold nanoparticles (AuNP) with branched polyethyleneimine (BPEI), lipoic acid (LA) and polyethylene glycol (PEG) coatings. Proteomic analysis identified 59 hard corona proteins among the various AuNP, revealing largely surface chemistry-dependent signature adsorbomes exhibiting human serum albumin (HSA) abundance. Size distribution analysis revealed the relative instability and aggregation inducing potential of bare and corona-bound BPEI-AuNP, over LA- and PEG-AuNP. Circular dichroism analysis showed surface chemistry-dependent conformational changes of proteins binding to AuNP. Time-dependent uptake of bare, plasma corona (PC) and HSA corona-bound AuNP (HSA-AuNP) showed significant reduction in uptake with PC formation. Cell viability studies demonstrated dose-dependent toxicity of BPEI-AuNP. Transcriptional profiling studies revealed 126 genes, from 13 biological pathways, to be differentially regulated by 40 nm bare and PC-bound BPEI-AuNP (PC-BPEI-AuNP). Furthermore, PC formation relieved the toxicity of cationic BPEI-AuNP by modulating expression of genes involved in DNA damage and repair, heat shock response, mitochondrial energy metabolism, oxidative stress and antioxidant response, and ER stress and unfolded protein response cascades, which were aberrantly expressed in bare BPEI-AuNP-treated cells. NP surface chemistry is shown to play the dominant role over size in determining the biocorona composition, which in turn modulates cell uptake, and biological responses, consequently defining the potential safety and efficacy of nanoformulations.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Aqueous aerosol SOA formation: impact on aerosol physical properties.

PubMed

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

2013-01-01

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

Hydrologic and geochemical monitoring in Long Valley Caldera, Mono County, California, 1982-1984

USGS Publications Warehouse

Farrar, C.D.; Sorey, M.L.; Rojstaczer, S.; Janik, C.J.; Mariner, R.H.; Winnett, T.L.; Clark, M.D.

1985-01-01

The Long Valley caldera is a potentially active volcanic area on the eastern side of the Sierra Nevada in east-central California. Hydrologic and geochemical monitoring of surface and subsurface features began in July 1982 to determine if changes were occurring in response to processes causing earthquakes and crustal deformation. Differences since 1982 in fluid chemistry of springs has been minor except at Casa Diablo, where rapid fluctuations in chemistry result from near surface boiling and mixing. Ratios of 3-He/4-He and 13-C/12-C in hot springs and fumaroles are consistent with a magnetic source for some of the carbon and helium discharged in thermal areas, and observed changes in 3-He/4-He between 1978 and 1984 suggest changes in the magmatic component. Significant fluctuations in hot spring discharge recorded at several sites since 1982 closely followed earthquake activity. Water levels in wells have been used as strain meters to detect rock deformation associated with magmatic and tectonic activity and to construct a water table contour map. Coseismic water level fluctuations of as much as 0.6 ft have been observed but no clear evidence of deformation caused by magmatic intrusions can be seen in the well records through 1984. Temperature profiles in wells, which can be used to delineate regionally continuous zones of lateral flow of hot water across parts of the caldera, have remained constant at all but two sites. (Author 's abstract)

Dust evolution, a global view I. Nanoparticles, nascence, nitrogen and natural selection … joining the dots

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

The role and importance of nanoparticles for interstellar chemistry and beyond is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), focusing on their active surface chemistry, the effects of nitrogen doping and the natural selection of interesting nanoparticle sub-structures. Nanoparticle-driven chemistry, and in particular the role of intrinsic epoxide-type structures, could provide a viable route to the observed gas phase OH in tenuous interstellar clouds en route to becoming molecular clouds. The aromatic-rich moieties present in asphaltenes probably provide a viable model for the structures present within aromatic-rich interstellar carbonaceous grains. The observed doping of such nanoparticle structures with nitrogen, if also prevalent in interstellar dust, could perhaps have important and observable consequences for surface chemistry and the formation of precursor pre-biotic species.

Automated Spectral System for Terrain Classification, Mineralogy of Vesta from the Dawn Framing Cameras

NASA Astrophysics Data System (ADS)

Reddy, V.; Le Corre, L.; Nathues, A.; Hall, I.; Gutierrez-Marques, P.; Hoffmann, M.

2011-10-01

The Dawn mission will rendezvous with asteroid (4) Vesta in July 2011. We have developed a set of equations for extracting mean pyroxene chemistry (Ferrosilite and Wollastonite) for classifying terrains on Vesta by using the Dawn Framing Camera (FC) multi-color bands. The Automated Spectral System (ASS) utilizes pseudo-Band I minima to estimate the mean pyroxene chemistry of diogenites, and basaltic eucrites. The mean pyroxene chemistries of cumulate eucrites, and howardites overlap each other on the pyroxene quadrilateral and hence are harder to distinguish. We expect our ASS to carry a bulk of the terrain classification and mineralogy workload utilizing these equations and complement the work of DawnKey (Le Corre et al., 2011, DPS/EPSC 2011). The system will also provide surface mineral chemistry layers that can be used for mapping Vesta's surface.

Correlation between surface chemistry and ion energy dependence of the etch yield in multicomponent oxides etching

NASA Astrophysics Data System (ADS)

Bérubé, P.-M.; Poirier, J.-S.; Margot, J.; Stafford, L.; Ndione, P. F.; Chaker, M.; Morandotti, R.

2009-09-01

The influence of surface chemistry in plasma etching of multicomponent oxides was investigated through measurements of the ion energy dependence of the etch yield. Using pulsed-laser-deposited CaxBa(1-x)Nb2O6 (CBN) and SrTiO3 thin films as examples, it was found that the etching energy threshold shifts toward values larger or smaller than the sputtering threshold depending on whether or not ion-assisted chemical etching is the dominant etching pathway and whether surface chemistry is enhancing or inhibiting desorption of the film atoms. In the case of CBN films etched in an inductively coupled Cl2 plasma, it is found that the chlorine uptake is inhibiting the etching reaction, with the desorption of nonvolatile NbCl2 and BaCl2 compounds being the rate-limiting step.

Effects of Chemistry on Blunt-Body Wake Structure

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

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

Nelson, A. J.; Voss, L. F.; Beck, P. R.

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Solid-State Chemistry as a Formation Mechanism for C 4N 2 Ice and Possibly the Haystack (220 cm -1 ice emission feature) in Titan's Stratosphere as Observed by Cassini CIRS

NASA Astrophysics Data System (ADS)

Anderson, Carrie; Samuelson, Robert E.; McLain, Jason L.; Nna Mvondo, Delphine; Romani, Paul; Flasar, F. Michael

2016-10-01

A profusion of organic ices containing hydrocarbons, nitriles, and combinations of their mixtures comprise Titan's complex stratospheric cloud systems, and are typically formed via vapor condensation. These ice particles are then distributed throughout the mid-to-lower stratosphere, with an increased abundance near the winter poles (see Anderson et al., 2016). The cold temperatures and the associated strong circumpolar winds that isolate polar air act in much the same way as on Earth, giving rise to compositional anomalies and stratospheric clouds that provide heterogeneous chemistry sites.Titan's C4N2 ice emission feature at 478 cm-1 and "the Haystack," a strong unidentified stratospheric ice emission feature centered at 220 cm-1, share a common characteristic. Even though both are distinctive ice emission features evident in Cassini Composite InfraRed (CIRS) far-IR spectra, no associated vapor emission features can be found in Titan's atmosphere. Without a vapor phase, solid-state chemistry provides an alternate mechanism beside vapor condensation for producing these observed stratospheric ices.Anderson et al., (2016) postulated that C4N2 ice formed in Titan's stratosphere via the solid-state photochemical reaction HCN + HC3N → C4N2 + H2 can occur within extant HCN-HC3N composite ice particles. Such a reaction, and potentially similar reactions that may produce the Haystack ice, are specific examples of solid-state chemistry in solar system atmospheres. This is in addition to the reaction HCl + ClONO2 → HNO3 + Cl2, which is known to produce HNO3 coatings on terrestrial water ice particles, a byproduct of the catalytic chlorine chemistry that produces ozone holes in Earth's polar stratosphere (see for example, Molina et al., 1987 Soloman, 1999).A combination of radiative transfer modeling of CIRS far-IR spectra, coupled with optical constants derived from thin film transmittance spectra of organic ice mixtures obtained in our Spectroscopy for Planetary ICes Environments (SPICE) laboratory, will be used to: 1) derive the vertical column abundance of C4N2 ice in Titan's early spring polar stratosphere, and 2) narrow the range of possible chemical compositions for the material comprising the Haystack.

Europa Surface Radiation Environment for Lander Assessment

NASA Technical Reports Server (NTRS)

Cooper, John F.; Sturner, Steven J.

2006-01-01

The Jovian magnetospheric particle environment at Europa's surface is critical to assessment of landed astrobiological experiments in three respects: (1) the landing site must be chosen for the best prospects for detectable organic or inorganic signs of Life, e.g. regions of freshly emergent flows from the subsurface; (2) lander systems must reach the surface through the Jovian magnetospheric environment and operate long enough on the surface to return useful data; (3) lander instrumentation must be capable of detecting signs of life in the context of the local environmental radiation and associated chemistry. The Galileo, Voyager, and Pioneer missions have provided a wealth of data on energetic particle intensities throughout the Jovian magnetosphere including from many flybys of Europa. cumulative radiation dosages for spacecraft enroute to Europa can be well characterized, but knowledge of the surface radiation environment is very limited. Energetic electrons should primarily impact the trailing hemisphere with decreasing intensity towards the center of the leading hemisphere and are the most significant radiation component down to meter depths in the surface regolith due to secondary interactions. Observed surface distribution for sulfates is suggestive of electron irradiation but may have alternative interpretations. Having much-larger magnetic gyroradii than electrons, energetic protons and heavier ions irradiate more of the global surface. The particular orientations of electron, proton, and ion gyromotion would project into corresponding directional (e.g., east-west) anisotropies of particle flu into the surface. Particular topographic features at the landing site may therefore offer shielding from part of the incident radiation.

The study of non-fouling and non-specific cellular binding on functionalized surface for mammalian cell identification and manipulation

NASA Astrophysics Data System (ADS)

Zainudin, Nor Syuhada; Hambali, Nor Azura Malini Ahmad; Wahid, Mohamad Halim Abd; Retnasamy, Vithyacharan; Shahimin, Mukhzeer Mohamad

2017-04-01

Surface functionalization has emerged as a powerful tool for mapping limitless surface-cell membrane interaction in diverse biomolecular applications. Inhibition of non-specific biomolecular and cellular adhesion to solid surfaces is critical in improving the performance of some biomedical devices, particularly for in vitro bioassays. Some factors have to be paid particular attention in determining the right surface modification which are the types of surface, the methods and chemical solution that being used during the experimentation and also tools for analyzing the results. Improved surface functionalization technologies that provide better non-fouling performance in conjunction with specific attachment chemistries are sought for these applications. Hence, this paper serves as a review for multiple surface treatment methods including PEG grafting, adsorptive chemistries, self-assembled monolayers (SAMs) and plasma treatments.

Chemistry of the surface and lower atmosphere of Venus

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

A Monte Carlo Sensitivity Analysis of CF2 and CF Radical Densities in a c-C4F8 Plasma

NASA Technical Reports Server (NTRS)

Bose, Deepak; Rauf, Shahid; Hash, D. B.; Govindan, T. R.; Meyyappan, M.

2004-01-01

A Monte Carlo sensitivity analysis is used to build a plasma chemistry model for octacyclofluorobutane (c-C4F8) which is commonly used in dielectric etch. Experimental data are used both quantitatively and quantitatively to analyze the gas phase and gas surface reactions for neutral radical chemistry. The sensitivity data of the resulting model identifies a few critical gas phase and surface aided reactions that account for most of the uncertainty in the CF2 and CF radical densities. Electron impact dissociation of small radicals (CF2 and CF) and their surface recombination reactions are found to be the rate-limiting steps in the neutral radical chemistry. The relative rates for these electron impact dissociation and surface recombination reactions are also suggested. The resulting mechanism is able to explain the measurements of CF2 and CF densities available in the literature and also their hollow spatial density profiles.

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.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-04-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl2, Br:MeOH, and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p, and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Does Translational Symmetry Matter on the Micro Scale? Fibroblastic and Osteoblastic Interactions with the Topographically Distinct Poly(ε-caprolactone)/Hydroxyapatite Thin Films

PubMed Central

2015-01-01

Material composition and topography of the cell-contacting material interface are important considerations in the design of biomaterials at the nano and micro scales. This study is one of the first to have assessed the osteoblastic response to micropatterned polymer–ceramic composite surfaces. In particular, the effect of topographic variations of composite poly(ε-caprolactone)/hydroxyapatite (PCL/HAp) films on viability, proliferation, migration and osteogenesis of fibroblastic and osteoblastic MC3T3-E1 cells was evaluated. To that end, three different micropatterned PCL/HAp films were compared: flat and textured, the latter of which included films comprising periodically arranged and randomly distributed oval topographic features 10 μm in diameter, 20 μm in separation and 10 μm in height, comparable to the dimensions of MC3T3-E1 cells. PCL/HAp films were fabricated by the combination of a bottom-up, soft chemical synthesis of the ceramic, nanoparticulate phase and a top-down, photolithographic technique for imprinting fine, microscale features on them. X-ray diffraction analysis indicated an isotropic orientation of both the polymeric chains and HAp crystallites in the composite samples. Biocompatibility tests indicated no significant decrease in their viability when grown on PCL/HAp films. Fibroblast proliferation and migration onto PCL/HAp films proceeded slower than on the control borosilicate glass, with the flat composite film fostering more cell migration activity than the films containing topographic features. The gene expression of seven analyzed osteogenic markers, including procollagen type I, osteocalcin, osteopontin, alkaline phosphatase, and the transcription factors Runx2 and TGFβ-1, was, however, consistently upregulated in cells grown on PCL/HAp films comprising periodically ordered topographic features, suggesting that the higher levels of symmetry of the topographic ordering impose a moderate mechanochemical stress on the adherent cells and thus promote a more favorable osteogenic response. The obtained results suggest that topography can be a more important determinant of the cell/surface interaction than the surface chemistry and/or stiffness as well as that the regularity of the distribution of topographic features can be a more important variable than the topographic features per se. PMID:25014232

Effect of Gold Nanorod Surface Chemistry on Cellular Interactions In Vitro

DTIC Science & Technology

2010-09-01

properties of GNRs on cells. Previous studies on the cytotoxicity of various nanoparticles indicated that surface chemistry has a strong influence on cell...supplemented with 10% fetal bovine serum (FBS, ATCC) and 1% penicillin/streptomycin (pen/strep, Sigma). For nanoparticle exposure, media was supplemented...reagent ( phenazine ethosulfate; PES). Metabolically active cells reduce the MTS compound into a colored formazan product that is soluble in tissue

Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

ERIC Educational Resources Information Center

Martins, Angela; Nunes, Nelson

2015-01-01

In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

PubMed

Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

2015-08-04

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Design of Ultrathin Pt-Based Multimetallic Nanostructures for Efficient Oxygen Reduction Electrocatalysis.

PubMed

Lai, Jianping; Guo, Shaojun

2017-12-01

Nanocatalysts with high platinum (Pt) utilization efficiency are attracting extensive attention for oxygen reduction reactions (ORR) conducted at the cathode of fuel cells. Ultrathin Pt-based multimetallic nanostructures show obvious advantages in accelerating the sluggish cathodic ORR due to their ultrahigh Pt utilization efficiency. A focus on recent important developments is provided in using wet chemistry techniques for making/tuning the multimetallic nanostructures with high Pt utilization efficiency for boosting ORR activity and durability. First, new synthetic methods for multimetallic core/shell nanoparticles with ultrathin shell sizes for achieving highly efficient ORR catalysts are reviewed. To obtain better ORR activity and stability, multimetallic nanowires or nanosheets with well-defined structure and surface are further highlighted. Furthermore, ultrathin Pt-based multimetallic nanoframes that feature 3D molecularly accessible surfaces for achieving more efficient ORR catalysis are discussed. Finally, the remaining challenges and outlooks for the future will be provided for this promising research field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition boiling heat transfer and the film transition regime

NASA Technical Reports Server (NTRS)

Ramilison, J. M.; Lienhard, J. H.

1987-01-01

The Berenson (1960) flat-plate transition-boiling experiment has been recreated with a reduced thermal resistance in the heater, and an improved access to those portions of the transition boiling regime that have a steep negative slope. Tests have been made in Freon-113, acetone, benzene, and n-pentane boiling on horizontal flat copper heaters that have been mirror-polished, 'roughened', or teflon-coated. The resulting data reproduce and clarify certain features observed by Berenson: the modest surface finish dependence of boiling burnout, and the influence of surface chemistry on both the minimum heat flux and the mode of transition boiling, for example. A rational scheme of correlation yields a prediction of the heat flux in what Witte and Lienhard (1982) previously identified as the 'film-transition boiling' region. It is also shown how to calculate the heat flux at the boundary between the pure-film, and the film-transition, boiling regimes, as a function of the advancing contact angle.

Recognition-mediated activation of therapeutic gold nanoparticles inside living cells

NASA Astrophysics Data System (ADS)

Kim, Chaekyu; Agasti, Sarit S.; Zhu, Zhengjiang; Isaacs, Lyle; Rotello, Vincent M.

2010-11-01

Supramolecular chemistry provides a versatile tool for the organization of molecular systems into functional structures and the actuation of these assemblies for applications through the reversible association between complementary components. Use of this methodology in living systems, however, represents a significant challenge owing to the chemical complexity of cellular environments and lack of selectivity of conventional supramolecular interactions. Herein, we present a host-guest system featuring diaminohexane-terminated gold nanoparticles (AuNP-NH2) and complementary cucurbit[7]uril (CB[7]). In this system, threading of CB[7] on the particle surface reduces the cytotoxicity of AuNP-NH2 through sequestration of the particle in endosomes. Intracellular triggering of the therapeutic effect of AuNP-NH2 was then achieved through the administration of 1-adamantylamine (ADA), removing CB[7] from the nanoparticle surface, causing the endosomal release and concomitant in situ cytotoxicity of AuNP-NH2. This supramolecular strategy for intracellular activation provides a new tool for potential therapeutic applications.

Creating a Context for Chemistry

NASA Astrophysics Data System (ADS)

Truman Schwartz, A.

Until relatively recently, the teaching of chemistry at the college and university level in the United States has been quite traditional and oriented primarily toward the preparation of chemists. Students not concentrating in the sciences have often been poorly served by existing courses. Chemistry in Context: Applying Chemistry to Society, a textbook for nonscience majors developed under the sponsorship of the American Chemical Society, is an effort to address the needs and interests of this audience. The book introduces the phenomena and principles of chemistry within the context of socially significant issues such as global warming, ozone depletion, alternate energy sources, nutrition, and genetic engineering. The chemistry is presented as needed to inform an understanding of the central topics, and the text features student-centered activities designed to promote critical thinking and risk-benefit analysis as well as an understanding of chemical principles. This paper summarizes the origin, development, content, pedagogy, evaluation, and influence of Chemistry in Context and considers its potential implications for other disciplines and the instruction of science majors.

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.

Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

PubMed

Thiemens, Mark H

2013-10-29

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

Simulating Local and Intercontinental Pollutant Effects of Biomass Burning: Integration of Several Remotely Sensed Datasets

NASA Technical Reports Server (NTRS)

Chatfield, Robert B.; Vastano, John A.; Guild, Liane; Hlavka, Christine; Brass, James A.; Russell, Philip B. (Technical Monitor)

1994-01-01

Burning to clear land for crops and to destroy pests is an integral and largely unavoidable part of tropical agriculture. It is easy to note but difficult to quantify using remote sensing. This report describes our efforts to integrate remotely sensed data into our computer model of tropical chemical trace-gas emissions, weather, and reaction chemistry (using the MM5 mesoscale model and our own Global-Regional Atmospheric Chemistry Simulator). The effects of burning over the continents of Africa and South America have been noticed in observations from several satellites. Smoke plumes hundreds of kilometers long may be seen individually, or may merge into a large smoke pall over thousands of kilometers of these continents. These features are related to intense pollution in the much more confined regions with heavy burning. These emissions also translocate nitrogen thousands of kilometers in the tropical ecosystems, with large fixed-nitrogen losses balanced partially by locally intense fertilization downwind, where nitric acid is rained out. At a much larger scale, various satellite measurements have indicated the escape of carbon monoxide and ozone into large filaments which extend across the Tropical and Southern Atlantic Ocean. Our work relates the source emissions, estimated in part from remote sensing, in part from conventional surface reports, to the concentrations of these gases over these intercontinental regions. We will mention work in progress to use meteorological satellite data (AVHRR, GOES, and Meteosat) to estimate the surface temperature and extent and height of clouds, and explain why these uses are so important in our computer simulations of global biogeochemistry. We will compare our simulations and interpretation of remote observations to the international cooperation involving Brazil, South Africa, and the USA in the TRACE-A (Transport and Atmospheric Chemistry near the Equator - Atlantic) and SAFARI (Southern Africa Fire Atmosphere Research Initiative) and remote-sensing /aircraft/ecosystem observational campaigns.

USArray Imaging of North American Continental Crust

NASA Astrophysics Data System (ADS)

Ma, Xiaofei

The layered structure and bulk composition of continental crust contains important clues about its history of mountain-building, about its magmatic evolution, and about dynamical processes that continue to happen now. Geophysical and geological features such as gravity anomalies, surface topography, lithospheric strength and the deformation that drives the earthquake cycle are all directly related to deep crustal chemistry and the movement of materials through the crust that alter that chemistry. The North American continental crust records billions of years of history of tectonic and dynamical changes. The western U.S. is currently experiencing a diverse array of dynamical processes including modification by the Yellowstone hotspot, shortening and extension related to Pacific coast subduction and transform boundary shear, and plate interior seismicity driven by flow of the lower crust and upper mantle. The midcontinent and eastern U.S. is mostly stable but records a history of ancient continental collision and rifting. EarthScope's USArray seismic deployment has collected massive amounts of data across the entire United States that illuminates the deep continental crust, lithosphere and deeper mantle. This study uses EarthScope data to investigate the thickness and composition of the continental crust, including properties of its upper and lower layers. One-layer and two-layer models of crustal properties exhibit interesting relationships to the history of North American continental formation and recent tectonic activities that promise to significantly improve our understanding of the deep processes that shape the Earth's surface. Model results show that seismic velocity ratios are unusually low in the lower crust under the western U.S. Cordillera. Further modeling of how chemistry affects the seismic velocity ratio at temperatures and pressures found in the lower crust suggests that low seismic velocity ratios occur when water is mixed into the mineral matrix, and the combination of high temperature and water may point to small amounts of melt in the lower crust of Cordillera.

Host-Guest Chemistry in Integrated Porous Space Formed by Molecular Self-Assembly at Liquid-Solid Interfaces.

PubMed

Iritani, Kohei; Tahara, Kazukuni; De Feyter, Steven; Tobe, Yoshito

2017-05-16

Host-guest chemistry in two-dimensional (2D) space, that is, physisorbed monolayers of a single atom or a single molecular thickness on surfaces, has become a subject of intense current interest because of perspectives for various applications in molecular-scale electronics, selective sensors, and tailored catalysis. Scanning tunneling microscopy has been used as a powerful tool for the visualization of molecules in real space on a conducting substrate surface. For more than a decade, we have been investigating the self-assembly of a series of triangle-shaped phenylene-ethynylene macrocycles called dehydrobenzo[12]annulenes (DBAs). These molecules are substituted with six alkyl chains and are capable of forming hexagonal porous 2D molecular networks via van der Waals interactions between interdigitated alkyl chains at the interface of organic solvents and graphite. The dimension of the nanoporous space or nanowell formed by the self-assembly of DBAs can be controlled from 1.6 to 4.7 nm by simply changing the alkyl chain length from C 6 to C 20 . Single molecules as well as homoclusters and heteroclusters are capable of coadsorbing within the host matrix using shape- and size-complementarity principles. Moreover, on the basis of the versatility of the DBA molecules that allows chemical modification of the alkyl chain terminals, we were able to decorate the interior space of the nanoporous networks with functional groups such as azobenzenedicarboxylic acid for photoresponsive guest adsorption/desorption or fluoroalkanes and tetraethylene glycol groups for selective guest binding by electrostatic interactions and zinc-porphyrin units for complexation with a guest by charge-transfer interactions. In this Feature Article, we describe the general aspects of molecular self-assembly at liquid/solid interfaces, followed by the formation of programmed porous molecular networks using rationally designed molecular building blocks. We focus on our own work involving host-guest chemistry in integrated nanoporous space that is modified for specific purposes.

Titan: a laboratory for prebiological organic chemistry

NASA Technical Reports Server (NTRS)

Sagan, C.; Thompson, W. R.; Khare, B. N.

1992-01-01

When we examine the atmospheres of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune), the satellites in the outer solar system, comets, and even--through microwave and infrared spectroscopy--the cold dilute gas and grains between the stars, we find a rich organic chemistry, presumably abiological, not only in most of the solar system but throughout the Milky Way galaxy. In part because the composition and surface pressure of the Earth's atmosphere 4 x 10(9) years ago are unknown, laboratory experiments on prebiological organic chemistry are at best suggestive; but we can test our understanding by looking more closely at the observed extraterrestrial organic chemistry. The present Account is restricted to atmospheric organic chemistry, primarily on the large moon of Saturn. Titan is a test of our understanding of the organic chemistry of planetary atmospheres. Its atmospheric bulk composition (N2/CH4) is intermediate between the highly reducing (H2/He/CH4/NH3/H2O) atmospheres of the Jovian planets and the more oxidized (N2/CO2/H2O) atmospheres of the terrestrial planets Mars and Venus. It has long been recognized that Titan's organic chemistry may have some relevance to the events that led to the origin of life on Earth. But with Titan surface temperatures approximately equal to 94 K and pressures approximately equal to 1.6 bar, the oceans of the early Earth have no ready analogue on Titan. Nevertheless, tectonic events in the water ice-rich interior or impact melting and slow re-freezing may lead to an episodic availability of liquid water. Indeed, the latter process is the equivalent of a approximately 10(3)-year-duration shallow aqueous sea over the entire surface of Titan.