Coupled effects of solution chemistry and hydrodynamics on the mobility and transport of quantum dot nanomaterials in the Vadose Zone

USDA-ARS?s Scientific Manuscript database

To investigate the coupled effects of solution chemistry and vadose zone processes on the mobility of quantum dot (QD) nanoparticles, laboratory scale transport experiments were performed. The complex coupled effects of ionic strength, size of QD aggregates, surface tension, contact angle, infiltrat...

Playing with Liquid Foams: Learning Physical Chemistry

ERIC Educational Resources Information Center

Ritacco, Hernan

2008-01-01

Who has never played with soap bubbles? They are so beautiful and amazing, they have a perfect spherical shape and surprising tints. Foams are structures of bubbles of an incredible complexity and they are a perfect system to stimulate students' interest in the chemistry and physics of surface phenomena. In this article I propose a simple…

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

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

2015-04-01

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

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.

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.

Grain Surface Chemistry and the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.

2006-01-01

Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

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

PubMed

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

2018-06-14

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

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.

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.

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.

Chemistry in protoplanetary disks

NASA Astrophysics Data System (ADS)

Semenov, D. A.

2012-01-01

In this lecture I discuss recent progress in the understanding of the chemical evolution of protoplanetary disks that resemble our Solar system during the first ten million years. At the verge of planet formation, strong variations of temperature, density, and radiation intensities in these disks lead to a layered chemical structure. In hot, dilute and heavily irradiated atmosphere only simple radicals, atoms, and atomic ions can survive, formed and destroyed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex (organic) species are synthesized.

Prebiotic-like chemistry on Titan.

PubMed

Raulin, François; Brassé, Coralie; Poch, Olivier; Coll, Patrice

2012-08-21

Titan, the largest satellite of Saturn, is the only one in the solar system with a dense atmosphere. Mainly composed of dinitrogen with several % of methane, this atmosphere experiences complex organic processes, both in the gas and aerosol phases, which are of prebiotic interest and within an environment of astrobiological interest. This tutorial review presents the different approaches which can be followed to study such an exotic place and its chemistry: observation, theoretical modeling and experimental simulation. It describes the Cassini-Huygens mission, as an example of observational tools, and gives the new astrobiologically oriented vision of Titan which is now available by coupling the three approaches. This includes the many analogies between Titan and the Earth, in spite of the much lower temperature in the Saturn system, the complex organic chemistry in the atmosphere, from the gas to the aerosol phases, but also the potential organic chemistry on Titan's surface, and in its possible internal water ocean.

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

Complex amine-based reagents

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

SmallSat Spinning Lander with a Raman Spectrometer Payload for Future Ocean Worlds Exploration Missions

NASA Technical Reports Server (NTRS)

Ridenoure, R.; Angel, S. M.; Aslam, S.; Gorius, N.; Hewagama, T.; Nixon, C. A.; Sharma, S.

2017-01-01

We describe an Evolved Expendable Launch Vehicle Secondary Payload Adapter (ESPA)-class SmallSat spinning lander concept for the exploration of Europa or other Ocean World surfaces to ascertain the potential for life. The spinning lander will be ejected from an ESPA ring from an orbiting or flyby spacecraft and will carry on-board a standoff remote Spatial Heterodyne Raman spectrometer (SHRS) and a time resolved laser induced fluorescence spectrograph (TR-LIFS), and once landed and stationary the instruments will make surface chemical measurements. The SHRS and TR-LIFS have no moving parts have minimal mass and power requirements and will be able to characterize the surface and near-surface chemistry, including complex organic chemistry to constrain the ocean composition.

SmallSat Spinning Lander with a Raman Spectrometer Payload for Future Ocean Worlds Exploration Missions

NASA Astrophysics Data System (ADS)

Ridenoure, R.; Angel, S. M.; Aslam, S.; Gorius, N.; Hewagama, T.; Nixon, C. A.; Sharma, S.

2017-09-01

We describe an Evolved Expendable Launch Vehicle Secondary Payload Adapter (ESPA)-class SmallSat spinning lander concept for the exploration of Europa or other Ocean World surfaces to ascertain the potential for life. The spinning lander will be ejected from an ESPA ring from an orbiting or flyby spacecraft and will carry on-board a standoff remote Spatial Heterodyne Raman spectrometer (SHRS) and a time resolved laser induced fluorescence spectrograph (TR-LIFS), and once landed and stationary the instruments will make surface chemical measurements. The SHRS and TR-LIFS have no moving parts have minimal mass and power requirements and will be able to characterize the surface and near-surface chemistry, including complex organic chemistry to constrain the ocean composition.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

Functionalization of multilayer fullerenes (carbon nano-onions) using diazonium compounds and "click" chemistry.

PubMed

Flavin, Kevin; Chaur, Manuel N; Echegoyen, Luis; Giordani, Silvia

2010-02-19

A novel versatile approach for the functionalization of multilayer fullerenes (carbon nano-onions) has been developed, which involves the facile introduction of a variety of simple functionalities onto their surface by treatment with in situ generated diazonium compounds. This approach is complemented by use of "click" chemistry which was used for the covalent introduction of more complex porphyrin molecules.

Colloidal characterization of silicon nitride and silicon carbide

NASA Technical Reports Server (NTRS)

Feke, Donald L.

1986-01-01

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

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

NASA Astrophysics Data System (ADS)

Hudson, R.; Loeffler, M. J.; Gerakines, P.

2017-12-01

The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

Titan's atmosphere and climate

NASA Astrophysics Data System (ADS)

Hörst, S. M.

2017-03-01

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

Interstellar Antifreeze: Ethylene Glycol

NASA Technical Reports Server (NTRS)

Hollis, J. M.; Lovas, F. J.; Jewell, P. R.; Coudert, L. H.

2002-01-01

Interstellar ethylene glycol (HOCH2CH2,OH) has been detected in emission toward the Galactic center source Sagittarius B2(N-LMH) by means of several millimeter-wave rotational torsional transitions of its lowest energy conformer. The types and kinds of molecules found to date in interstellar clouds suggest a chemistry that favors aldehydes and their corresponding reduced alcohols-e.g., formaldehyde (H2CO)/methanol (CH3OH), acetaldehyde (CH3CHO)/ethanol (CH3CH2OH). Similarly, ethylene glycol is the reduced alcohol of glycolaldehyde (CH2OHCHO), which has also been detected toward Sgr B2(N-LMH). While there is no consensus as to how any such large complex molecules are formed in the interstellar clouds, atomic hydrogen (H) and carbon monoxide (CO) could form formaldehyde on grain surfaces, but such surface chemistry beyond that point is uncertain. However, laboratory experiments have shown that the gas-phase reaction of atomic hydrogen (H) and solid-phase CO at 10-20 K can produce formaldehyde and methanol and that alcohols and other complex molecules can be synthesized from cometary ice analogs when subject to ionizing radiation at 15 K. Thus, the presence of aldehyde/ reduced alcohol pairs in interstellar clouds implies that such molecules are a product of a low-temperature chemistry on grain surfaces or in grain ice mantles. This work suggests that aldehydes and their corresponding reduced alcohols provide unique observational constraints on the formation of complex interstellar molecules.

Chemical Evolution of a Protoplanetary Disk

NASA Astrophysics Data System (ADS)

Semenov, Dmitry A.

2011-12-01

In this paper we review recent progress in our understanding of the chemical evolution of protoplanetary disks. Current observational constraints and theoretical modeling on the chemical composition of gas and dust in these systems are presented. Strong variations of temperature, density, high-energy radiation intensities in these disks, both radially and vertically, result in a peculiar disk chemical structure, where a variety of processes are active. In hot, dilute and heavily irradiated atmosphere only the most photostable simple radicals and atoms and atomic ions exist, formed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich ion-molecule and radical-radical chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex polyatomic (organic) species are synthesized. Dynamical processes affect disk chemical composition by enriching it in abundances of complex species produced via slow surface processes, which will become detectable with ALMA.

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.

Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

NASA Astrophysics Data System (ADS)

Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

NASA Technical Reports Server (NTRS)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Titan's Lakes in a Beaker

NASA Astrophysics Data System (ADS)

Hodyss, R. P.

2017-12-01

The surface of Titan presents a complex, varied surfaced, with mountains, plains, dunes, rivers, lakes and seas, composed of a layer of organics over a water ice bedrock. Over the past 10 years, our group at JPL has developed a variety of techniques to study the chemistry of Titan's organic surface under relevant temperature and pressure conditions (90-100 K, 1.5 bar). Dissolution, precipitation, and both covalent and non-covalent chemical processes are examined using Raman and infrared spectroscopy, mass spectrometry, optical microscopy, and synchrotron X-ray powder diffraction. Despite the low temperatures, our experiments are revealing that a rich and active organic chemistry is possible on Titan's surface. Laboratory experiments like these can provide crucial insights into the geological processes occurring Titan's surface, and help explain the wealth of observational data returned by the Cassini/Huygens mission. This type of data is also critical for the development of future missions to Titan.

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

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

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

Host-guest chemistry of dendrimer-drug complexes. 4. An in-depth look into the binding/encapsulation of guanosine monophosphate by dendrimers.

PubMed

Hu, Jingjing; Fang, Min; Cheng, Yiyun; Zhang, Jiahai; Wu, Qinglin; Xu, Tongwen

2010-06-03

In the present study, we investigated the host-guest chemistry of dendrimer/guanosine monophosphate (GMP) and present an in-depth look into the binding/encapsulation of GMP by dendrimers using NMR studies. (1)H NMR spectra showed a significant downfield shift of methylene protons in the outmost layer of the G5 dendrimer, indicating the formation of ion pairs between cationic amine groups of dendrimer and anionic phosphate groups of GMP. Chemical shift titration results showed that the binding constant between G5 dendrimer and GMP is 17,400 M(-1) and each G5 dendrimer has 107 binding sites. The binding of GMP to dendrimers prevents its aggregation in aqueous solutions and thereby enhances its stability. Nuclear Overhauser effect measurements indicated that a GMP binding and encapsulation balance occurs on the surface and in the interior of dendrimer. The binding/encapsulation transitions can be easily tailored by altering the surface and interior charge densities of the dendrimer. All these findings provide a new insight into the host-guest chemistry of dendrimer/guest complexes and may play important roles in the study of dendrimer/DNA aggregates by a "bottom-up" strategy.

Peptide interfaces with graphene: an emerging intersection of analytical chemistry, theory, and materials.

PubMed

Russell, Shane R; Claridge, Shelley A

2016-04-01

Because noncovalent interface functionalization is frequently required in graphene-based devices, biomolecular self-assembly has begun to emerge as a route for controlling substrate electronic structure or binding specificity for soluble analytes. The remarkable diversity of structures that arise in biological self-assembly hints at the possibility of equally diverse and well-controlled surface chemistry at graphene interfaces. However, predicting and analyzing adsorbed monolayer structures at such interfaces raises substantial experimental and theoretical challenges. In contrast with the relatively well-developed monolayer chemistry and characterization methods applied at coinage metal surfaces, monolayers on graphene are both less robust and more structurally complex, levying more stringent requirements on characterization techniques. Theory presents opportunities to understand early binding events that lay the groundwork for full monolayer structure. However, predicting interactions between complex biomolecules, solvent, and substrate is necessitating a suite of new force fields and algorithms to assess likely binding configurations, solvent effects, and modulations to substrate electronic properties. This article briefly discusses emerging analytical and theoretical methods used to develop a rigorous chemical understanding of the self-assembly of peptide-graphene interfaces and prospects for future advances in the field.

Predictive Surface Complexation Modeling

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

Sverjensky, Dimitri A.

Surface complexation plays an important role in the equilibria and kinetics of processes controlling the compositions of soilwaters and groundwaters, the fate of contaminants in groundwaters, and the subsurface storage of CO 2 and nuclear waste. Over the last several decades, many dozens of individual experimental studies have addressed aspects of surface complexation that have contributed to an increased understanding of its role in natural systems. However, there has been no previous attempt to develop a model of surface complexation that can be used to link all the experimental studies in order to place them on a predictive basis. Overall,more » my research has successfully integrated the results of the work of many experimentalists published over several decades. For the first time in studies of the geochemistry of the mineral-water interface, a practical predictive capability for modeling has become available. The predictive correlations developed in my research now enable extrapolations of experimental studies to provide estimates of surface chemistry for systems not yet studied experimentally and for natural and anthropogenically perturbed systems.« less

Microbiologically Influenced Corrosion: Causative Organisms and Mechanisms

DTIC Science & Technology

2012-01-31

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

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

PubMed

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

2015-08-11

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

How micron-sized dust particles determine the chemistry of our Universe

PubMed Central

Dulieu, François; Congiu, Emanuele; Noble, Jennifer; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Minissale, Marco; Cazaux, Stéphanie

2013-01-01

In the environments where stars and planets form, about one percent of the mass is in the form of micro-meter sized particles known as dust. However small and insignificant these dust grains may seem, they are responsible for the production of the simplest (H2) to the most complex (amino-acids) molecules observed in our Universe. Dust particles are recognized as powerful nano-factories that produce chemical species. However, the mechanism that converts species on dust to gas species remains elusive. Here we report experimental evidence that species forming on interstellar dust analogs can be directly released into the gas. This process, entitled chemical desorption (fig. 1), can dominate over the chemistry due to the gas phase by more than ten orders of magnitude. It also determines which species remain on the surface and are available to participate in the subsequent complex chemistry that forms the molecules necessary for the emergence of life. PMID:23439221

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

PubMed Central

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

2016-01-01

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

Monte Carlo simulation of a near-continuum shock-shock interaction problem

NASA Technical Reports Server (NTRS)

Carlson, Ann B.; Wilmoth, Richard G.

1992-01-01

A complex shock interaction is calculated with direct simulation Monte Carlo (DSMC). The calculation is performed for the near-continuum flow produced when an incident shock impinges on the bow shock of a 0.1 in. radius cowl lip for freestream conditions of approximately Mach 15 and 35 km altitude. Solutions are presented both for a full finite-rate chemistry calculation and for a case with chemical reactions suppressed. In each case, both the undisturbed flow about the cowl lip and the full shock interaction flowfields are calculated. Good agreement has been obtained between the no-chemistry simulation of the undisturbed flow and a perfect gas solution obtained with the viscous shock-layer method. Large differences in calculated surface properties when different chemical models are used demonstrate the necessity of adequately representing the chemistry when making surface property predictions. Preliminary grid refinement studies make it possible to estimate the accuracy of the solutions.

Vibrations At Surfaces During Heterogeneous Catalytic Reactions

NASA Astrophysics Data System (ADS)

Aragno, A.; Basini, Luca; Marchionna, M.; Raffaelli, A.

1989-12-01

FTIR spectroscopies can be used in a wide range of temperature and pressure conditions to investigate on the chemistry and the physics of heterogeneous catalytic reactions. In this paper we have shortly discussed the spectroscopic results obtained during the study of two different reactions; the skeletal isomerization of 1-butene to obtain 2-methylpropene and the surface aggregation and fragmentation of rhodium carbonyl complexes during thermal treatments in N2, H2, CO, CH4 atmospheres. In the first case high temperature proton tran-sfer reactions are proposed to be responsible for the skeletal isomerization reaction. In the second case our experiments have shown a partial reversibility of the nucleation processes at the surfaces and revealed a low temperature reactivity of methane on rhodium car-bonyl surface complexes.

Chemistry and temperature-assisted dehydrogenation of C60H30 molecules on TiO2(110) surfaces

NASA Astrophysics Data System (ADS)

Sánchez-Sánchez, Carlos; Martínez, José Ignacio; Lanzilotto, Valeria; Biddau, Giulio; Gómez-Lor, Berta; Pérez, Rubén; Floreano, Luca; López, María Francisca; Martín-Gago, José Ángel

2013-10-01

The thermal induced on-surface chemistry of large polycyclic aromatic hydrocarbons (PAHs) deposited on dielectric substrates is very rich and complex. We evidence temperature-assisted (cyclo)dehydrogenation reactions for C60H30 molecules and the subsequent bottom-up formation of assembled nanostructures, such as nanodomes, on the TiO2(110) surface. To this aim we have deposited, under ultra-high vacuum, a submonolayer coverage of C60H30 and studied, by a combination of experimental techniques (STM, XPS and NEXAFS) and theoretical methods, the different chemical on-surface interaction stages induced by the increasing temperature. We show that room temperature adsorbed molecules exhibit a weak interaction and freely diffuse on the surface, as previously reported for other aromatics. Nevertheless, a slight annealing induces a transition from this (meta)stable configuration into chemisorbed molecules. This adsorbate-surface interaction deforms the C60H30 molecular structure and quenches surface diffusion. Higher annealing temperatures lead to partial dehydrogenation, in which the molecule loses some of the hydrogen atoms and LUMO levels spread in the gap inducing a net total energy gain. Further annealing, up to around 750 K, leads to complete dehydrogenation. At these temperatures the fully dehydrogenated molecules link between them in a bottom-up coupling, forming nanodomes or fullerene-like monodisperse species readily on the dielectric surface. This work opens the door to the use of on-surface chemistry to generate new bottom-up tailored structures directly on high-K dielectric surfaces.The thermal induced on-surface chemistry of large polycyclic aromatic hydrocarbons (PAHs) deposited on dielectric substrates is very rich and complex. We evidence temperature-assisted (cyclo)dehydrogenation reactions for C60H30 molecules and the subsequent bottom-up formation of assembled nanostructures, such as nanodomes, on the TiO2(110) surface. To this aim we have deposited, under ultra-high vacuum, a submonolayer coverage of C60H30 and studied, by a combination of experimental techniques (STM, XPS and NEXAFS) and theoretical methods, the different chemical on-surface interaction stages induced by the increasing temperature. We show that room temperature adsorbed molecules exhibit a weak interaction and freely diffuse on the surface, as previously reported for other aromatics. Nevertheless, a slight annealing induces a transition from this (meta)stable configuration into chemisorbed molecules. This adsorbate-surface interaction deforms the C60H30 molecular structure and quenches surface diffusion. Higher annealing temperatures lead to partial dehydrogenation, in which the molecule loses some of the hydrogen atoms and LUMO levels spread in the gap inducing a net total energy gain. Further annealing, up to around 750 K, leads to complete dehydrogenation. At these temperatures the fully dehydrogenated molecules link between them in a bottom-up coupling, forming nanodomes or fullerene-like monodisperse species readily on the dielectric surface. This work opens the door to the use of on-surface chemistry to generate new bottom-up tailored structures directly on high-K dielectric surfaces. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03706a

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

DOE PAGES

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

2017-12-06

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

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

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

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

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

The Importance of Protons in Reactive Transport Modeling

NASA Astrophysics Data System (ADS)

McNeece, C. J.; Hesse, M. A.

2014-12-01

The importance of pH in aqueous chemistry is evident; yet, its role in reactive transport is complex. Consider a column flow experiment through silica glass beads. Take the column to be saturated and flowing with solution of a distinct pH. An instantaneous change in the influent solution pH can yield a breakthrough curve with both a rarefaction and shock component (composite wave). This behavior is unique among aqueous ions in transport and is more complex than intuition would tell. Analysis of the hyperbolic limit of this physical system can explain these first order transport phenomenon. This analysis shows that transport behavior is heavily dependent on the shape of the adsorption isotherm. Hence it is clear that accurate surface chemistry models are important in reactive transport. The proton adsorption isotherm has nonconstant concavity due to the proton's ability to partition into hydroxide. An eigenvalue analysis shows that an inflection point in the adsorption isotherm allows the development of composite waves. We use electrostatic surface complexation models to calculate realistic proton adsorption isotherms. Surface characteristics such as specific surface area, and surface site density were determined experimentally. We validate the model by comparison against silica glass bead flow through experiments. When coupled to surface complexation models, the transport equation captures the timing and behavior of breakthrough curves markedly better than with commonly used Langmuir assumptions. Furthermore, we use the adsorption isotherm to predict, a priori, the transport behavior of protons across pH composition space. Expansion of the model to multicomponent systems shows that proton adsorption can force composite waves to develop in the breakthrough curves of ions that would not otherwise exhibit such behavior. Given the abundance of reactive surfaces in nature and the nonlinearity of chemical systems, we conclude that building a greater understanding of proton adsorption is of utmost importance to reactive transport modeling.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Progress in the Analysis of Complex Atmospheric Particles.

PubMed

Laskin, Alexander; Gilles, Mary K; Knopf, Daniel A; Wang, Bingbing; China, Swarup

2016-06-12

This article presents an overview of recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surface interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multimodal chemical characterization of particles with both molecular and lateral specificity. When combined, these approaches provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore the environmental effects of air-surface interactions.

Mimicking the surface and prebiotic chemistry of early Earth using flow chemistry.

PubMed

Ritson, Dougal J; Battilocchio, Claudio; Ley, Steven V; Sutherland, John D

2018-05-08

When considering life's aetiology, the first questions that must be addressed are "how?" and "where?" were ostensibly complex molecules, considered necessary for life's beginning, constructed from simpler, more abundant feedstock molecules on primitive Earth. Previously, we have used multiple clues from the prebiotic synthetic requirements of (proto)biomolecules to pinpoint a set of closely related geochemical scenarios that are suggestive of flow and semi-batch chemistries. We now wish to report a multistep, uninterrupted synthesis of a key heterocycle (2-aminooxazole) en route to activated nucleotides starting from highly plausible, prebiotic feedstock molecules under conditions which mimic this scenario. Further consideration of the scenario has uncovered additional pertinent and novel aspects of prebiotic chemistry, which greatly enhance the efficiency and plausibility of the synthesis.

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

In-Package Chemistry Abstraction

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

E. Thomas

2004-11-09

This report was developed in accordance with the requirements in ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, amore » batch reactor model that uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model that is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed waste packages that contain both high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor that diffuses into the waste package, and (2) seepage water that enters the waste package from the drift as a liquid. (1) Vapor Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H2O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Water Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package. TSPA-LA uses the vapor influx case for the nominal scenario for simulations where the waste package has been breached but the drip shield remains intact, so all of the seepage flow is diverted from the waste package. The chemistry from the vapor influx case is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion, and to determine the degradation rates for the waste forms. TSPA-LA uses the water influx case for the seismic scenario, where the waste package has been breached and the drip shield has been damaged such that seepage flow is actually directed into the waste package. The chemistry from the water influx case that is a function of the flow rate is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion and advection, and to determine the degradation rates for the CSNF and HLW glass. TSPA-LA does not use this model for the igneous scenario. Outputs from the in-package chemistry model implemented inside TSPA-LA include pH, ionic strength, and total carbonate concentration. These inputs to TSPA-LA will be linked to the following principle factors: dissolution rates of the CSNF and HLWG, dissolved concentrations of radionuclides, and colloid generation.« less

Complex Protostellar Chemistry

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Johnson, Natasha M.

2012-01-01

Two decades ago, our understanding chemistry in protostars was simple -- matter either fell into the central star or was trapped in planetary-scale objects. Some minor chemical changes might occur as the dust and gas fell inward, but such effects were overwhelmed by the much larger-scale processes that occurred even in bodies as small as asteroids. The chemistry that did occur in the nebula was relatively easy to model because the fall from the cold molecular cloud into the growing star was a one-way trip down a well-known temperature pressure gradient; the only free variable was time. However, just over 10 years ago it was suggested that some material could be processed in the inner nebula, flow outward, and become incorporated into comets. This outward flow was confirmed when the Stardust mission returned crystalline mineral fragments from Comet Wild 2 that must have been processed close to the Sun before they were incorporated into the comet. In this week's Science Express, Ciesla and Sandford demonstrate that even the outermost regions of the solar nebula can be a chemically active environment. Their finding could have consequences for the rest of the nebula. Our understanding of the chemistry in protostellar systems has made enormous progress over the last few decades, fueled by an increased awareness of the complex dynamics of these evolving energetic nebulae. We can no longer consider just the simple local environment to explain the composition of a planet, asteroid, or comet as was done in the past, but must now consider chemical processes that might take place within the nebula as a whole as well as the probability of transport and mixing the products of such reactions throughout the system. just as we now find it impossible to explain the complex chemistry of the terrestrial atmosphere without reference to detailed transport models that interconnect highly dissimilar chemical environments, so chemical models of protostars and of the solar nebula must eventually treat these environments as tightly coupled, interactive systems. The demonstration that the chemistry on the surfaces of outward-flowing, dynamically mixing icy grain surfaces both mimics the chemistry in cold cloud cores and strikes at the central assumption of the photochemical self-shielding model for oxygen isotopes in solar system solids only adds emphasis to this conclusion.

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

NASA Astrophysics Data System (ADS)

Fabrikant, Ilya I.

2018-05-01

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

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

PubMed

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

2018-05-29

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

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Surface-Sensitive and Bulk Studies on the Complexation and Photosensitized Degradation of Catechol by Iron(III) as a Model for Multicomponent Aerosol Systems

NASA Astrophysics Data System (ADS)

Al-abadleh, H. A.; Tofan-Lazar, J.; Situm, A.; Ruffolo, J.; Slikboer, S.

2013-12-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

Sunlight-initiated chemistry of aqueous pyruvic acid: building complexity in the origin of life.

PubMed

Griffith, Elizabeth C; Shoemaker, Richard K; Vaida, Veronica

2013-10-01

Coupling chemical reactions to an energy source is a necessary step in the origin of life. Here, we utilize UV photons provided by a simulated sun to activate aqueous pyruvic acid and subsequently prompt chemical reactions mimicking some of the functions of modern metabolism. Pyruvic acid is interesting in a prebiotic context due to its prevalence in modern metabolism and its abiotic availability on early Earth. Here, pyruvic acid (CH3COCOOH, a C3 molecule) photochemically reacts to produce more complex molecules containing four or more carbon atoms. Acetoin (CH3CHOHCOCH3), a C4 molecule and a modern bacterial metabolite, is produced in this chemistry as well as lactic acid (CH3CHOHCOOH), a molecule which, when coupled with other abiotic chemical reaction pathways, can provide a regeneration pathway for pyruvic acid. This chemistry is discussed in the context of plausible environments on early Earth such as near the ocean surface and atmospheric aerosol particles. These environments allow for combination and exchange of reactants and products of other reaction environments (such as shallow hydrothermal vents). The result could be a contribution to the steady increase in chemical complexity requisite in the origin of life.

Transepithelial transport and toxicity of PAMAM dendrimers: implications for oral drug delivery.

PubMed

Sadekar, S; Ghandehari, H

2012-05-01

This article summarizes efforts to evaluate poly(amido amine) (PAMAM) dendrimers as carriers for oral drug delivery. Specifically, the effect of PAMAM generation, surface charge and surface modification on toxicity, cellular uptake and transepithelial transport is discussed. Studies on Caco-2 monolayers, as models of intestinal epithelial barrier, show that by engineering surface chemistry of PAMAM dendrimers, it is possible to minimize toxicity while maximizing transepithelial transport. It has been demonstrated that PAMAM dendrimers are transported by a combination of paracellular and transcellular routes. Depending on surface chemistry, PAMAM dendrimers can open the tight junctions of epithelial barriers. This tight junction opening is in part mediated by internalization of the dendrimers. Transcellular transport of PAMAM dendrimers is mediated by a variety of endocytic mechanisms. Attachment or complexation of cytotoxic agents to PAMAM dendrimers enhances the transport of such drugs across epithelial barriers. A remaining challenge is the design and development of linker chemistries that are stable in the gastrointestinal tract (GIT) and the blood stream, but amenable to cleavage at the target site of action. Recent efforts have focused on the use of PAMAM dendrimers as penetration enhancers. Detailed in vivo oral bioavailability of PAMAM dendrimer-drug conjugates, as a function of physicochemical properties will further need to be assessed. Copyright © 2011 Elsevier B.V. All rights reserved.

TRANSEPITHELIAL TRANSPORT AND TOXICITY OF PAMAM DENDRIMERS: IMPLICATIONS FOR ORAL DRUG DELIVERY

PubMed Central

Sadekar, S.; Ghandehari, H.

2011-01-01

This article summarizes efforts to evaluate poly(amido amine) (PAMAM) dendrimers as carriers for oral drug delivery. Specifically, the effect of PAMAM generation, surface charge and surface modification on toxicity, cellular uptake and transepithelial transport is discussed. Studies on Caco-2 monolayers, as models of intestinal epithelial barrier, show that by engineering surface chemistry of PAMAM dendrimers, it is possible to minimize toxicity while maximizing transepithelial transport. It has been demonstrated that PAMAM dendrimers are transported by a combination of paracellular and transcellular routes. Depending on surface chemistry, PAMAM dendrimers can open the tight junctions of epithelial barriers. This tight junction opening is in part mediated by internalization of the dendrimers. Transcellular transport of PAMAM dendrimers is mediated by a variety of endocytic mechanisms. Attachment or complexation of cytotoxic agents to PAMAM dendrimers enhances the transport of such drugs across epithelial barriers. A remaining challenge is the design and development of linker chemistries that are stable in the gastrointestinal tract (GIT) and the blood stream, but amenable to cleavage at the target site of action. Recent efforts have focused on the use of PAMAM dendrimers as penetration enhancers. Detailed in vivo oral bioavailability of PAMAM dendrimer – drug conjugates, as a function of physicochemical properties will further need to be assessed. PMID:21983078

Continuous Optical 3D Printing of Green Aliphatic Polyurethanes.

PubMed

Pyo, Sang-Hyun; Wang, Pengrui; Hwang, Henry H; Zhu, Wei; Warner, John; Chen, Shaochen

2017-01-11

Photosensitive diurethanes were prepared from a green chemistry synthesis pathway based on methacrylate-functionalized six-membered cyclic carbonate and biogenic amines. A continuous optical 3D printing method for the diurethanes was developed to create user-defined gradient stiffness and smooth complex surface microstructures in seconds. The green chemistry-derived polyurethane (gPU) showed high optical transparency, and we demonstrate the ability to tune the material stiffness of the printed structure along a gradient by controlling the exposure time and selecting various amine compounds. High-resolution 3D biomimetic structures with smooth curves and complex contours were printed using our gPU. High cell viability (over 95%) was demonstrated during cytocompatibility testing using C3H 10T1/2 cells seeded directly on the printed structures.

Discovery and development of microporous metal carboxylates.

PubMed

Mori, Wasuke; Sato, Tomohiko; Kato, Chika Nozaki; Takei, Tohru; Ohmura, Tetsushi

2005-01-01

We have found a form of copper(II) terephthalate that occluded an enormous amount of gases such as N2, Ar, O2, and Xe. Copper(II) terephthalate is the first metal complex found capable of adsorbing gases. This complex has opened a new field of adsorbent chemistry and is recognized as a leader in the construction of microporous metal complexes. In extending the route for the synthesis of microporous complexes, we obtained many new porous materials that are widely recognized as useful materials for applications in areas such as gas storage, molecular sieves, catalysis, inclusion complexes, and surface science. 2005 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

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

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.

Progress in the Analysis of Complex Atmospheric Particles

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

Laskin, Alexander; Gilles, Mary K.; Knopf, Daniel A.

2016-06-16

This manuscript presents an overview on recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surfaces interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multi-modal chemical characterization of particles with both molecularmore » and lateral specificity. When combined, they provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore environmental effects of air-surface interactions.« less

Progress in the analysis of complex atmospheric particles

DOE PAGES

Laskin, Alexander; Gilles, Mary K.; Knopf, Daniel A.; ...

2016-06-01

This study presents an overview of recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surface interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multimodal chemical characterization of particles with both molecularmore » and lateral specificity. When combined, these approaches provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore the environmental effects of air-surface interactions.« less

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

NASA Astrophysics Data System (ADS)

Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

2017-03-01

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

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

NASA Astrophysics Data System (ADS)

Garrod, Robin

2015-08-01

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

Adsorption of Phosphate on Goethite: An Undergraduate Research Laboratory Project

ERIC Educational Resources Information Center

Tribe, Lorena; Barja, Beatriz C.

2004-01-01

A laboratory experiment on the adsorption of phosphate on goethite is presented, which also includes discussion on surface properties, interfaces, acid-base equilibrium, molecular structure and solid state chemistry. It was seen that many students were able to produce qualitatively correct results for a complex system of real interest and they…

The consequences of human-driven ocean acidification for marine life.

PubMed

Doney, Scott

2009-05-08

Rising atmospheric carbon dioxide is causing a wholesale shift in surface seawater chemistry, potentially threatening many marine organisms that form shells and skeletons from calcium carbonate. Recent papers suggest that the biological consequences of ocean acidification already may be underway and may be more complex, nuanced and widespread than previously thought.

Characteristics of biochar: Microchemical properties

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

Amonette, James E.; Joseph, Stephen

2009-03-13

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

Molecular-level spectroscopic investigations of the complexation and photodegradation of catechol to/by iron(III)

NASA Astrophysics Data System (ADS)

Al-Abadleh, Hind; Tofan-Lazar, Julia; Situm, Arthur; Slikboer, Samantha

2014-05-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination Processes

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

Satish C. B. Myneni

2005-12-13

Siderophores are biological macromolecules (400-2000 Da) released by bacteria in iron limiting situations to sequester Fe from iron oxyhydroxides and silicates in the natural environment. These molecules contain hydroxamate and phenolate functional groups, and exhibit very high affinity for Fe{sup 3+}. While several studies were conducted to understand the behavior of siderophores and their application to the metal sequestration and mineral dissolution, only a few of them have examined the molecular structure of siderophores and their interactions with metals and mineral surfaces in aqueous solutions. Improved understanding of the chemical state of different functional moieties in siderophores can assist inmore » the application of these biological molecules in actinide separation, sequestration and decontamination processes. The focus of our research group is to evaluate the (a) functional group chemistry of selected siderophores and their metal complexes in aqueous solutions, and (b) the nature of siderophore interactions at the mineral-water interfaces. We selected desferrioxamine B (desB), a hydroxamate siderophore, and its small structural analogue, acetohydroxamic acid (aHa), for this investigation. We examined the functional group chemistry of these molecules as a function of pH, and their complexation with aqueous and solid phase Fe(III). For solid phase Fe, we synthesized all naturally occurring Fe(III)-oxyhydroxides (goethite, lepidocrocite, akaganeite, feroxyhite) and hematite. We also synthesized Fe-oxides (goethite and hematite) of different sizes to evaluate the influence of particle size on mineral dissolution kinetics. We used a series of molecular techniques to explore the functional group chemistry of these molecules and their complexes. Infrared spectroscopy is used to specifically identify the variations in oxime group as a function of pH and Fe(III) complexation. Resonance Raman spectroscopy was used to evaluate the nature of hydroxamate binding in the case of Fe(III)-siderophore complexes and model ligands. Soft and hard X-ray spectroscopy techniques were used to examine the electronic structure of binding groups, and their local structural environment. The synchrotron X-ray studies were conducted at the Stanford Synchrotron Radiation Laboratory and at the Advanced Light Source (Lawrence Berkeley National Laboratory). These experimental vibrational and X-ray spectroscopy studies were complemented with density functional theory calculations. The highlight of this study is the evaluation of the fundamental electronic state information of the hydroxamate moiety in siderophores during deprotonation and Fe(III) complexation. The applications of soft X-ray studies are also new, and were applied, for the first time, to examine the chemistry of organic macromolecules in aqueous solutions.« less

Intensive Titan exploration begins.

PubMed

Mahaffy, Paul R

2005-05-13

The Cassini Orbiter spacecraft first skimmed through the tenuous upper atmosphere of Titan on 26 October 2004. This moon of Saturn is unique in our solar system, with a dense nitrogen atmosphere that is cold enough in places to rain methane, the feedstock for the atmospheric chemistry that produces hydrocarbons, nitrile compounds, and Titan's orange haze. The data returned from this flyby supply new information on the magnetic field and plasma environment around Titan, expose new facets of the dynamics and chemistry of Titan's atmosphere, and provide the first glimpses of what appears to be a complex, fluid-processed, geologically young Titan surface.

Deconvoluting the effects of surface chemistry and nanoscale topography: Pseudomonas aeruginosa biofilm nucleation on Si-based substrates.

PubMed

Zhang, Jing; Huang, Jinglin; Say, Carmen; Dorit, Robert L; Queeney, K T

2018-06-01

The nucleation of biofilms is known to be affected by both the chemistry and topography of the underlying substrate, particularly when topography includes nanoscale (<100 nm) features. However, determining the role of topography vs. chemistry is complicated by concomitant variation in both as a result of typical surface modification techniques. Analyzing the behavior of biofilm-forming bacteria exposed to surfaces with systematic, independent variation of both topography and surface chemistry should allow differentiation of the two effects. Silicon surfaces with reproducible nanotopography were created by anisotropic etching in deoxygenated water. Surface chemistry was varied independently to create hydrophilic (OH-terminated) and hydrophobic (alkyl-terminated) surfaces. The attachment and proliferation of Psuedomonas aeruginosa to these surfaces was characterized over a period of 12 h using fluorescence and confocal microscopy. The number of attached bacteria as well as the structural characteristics of the nucleating biofilm were influenced by both surface nanotopography and surface chemistry. In general terms, the presence of both nanoscale features and hydrophobic surface chemistry enhance bacterial attachment and colonization. However, the structural details of the resulting biofilms suggest that surface chemistry and topography interact differently on each of the four surface types we studied. Copyright © 2018 Elsevier Inc. All rights reserved.

Polymer-Based Protein Engineering: Synthesis and Characterization of Armored, High Graft Density Polymer-Protein Conjugates.

PubMed

Carmali, Sheiliza; Murata, Hironobu; Cummings, Chad; Matyjaszewski, Krzysztof; Russell, Alan J

2017-01-01

Atom transfer radical polymerization (ATRP) from the surface of a protein can generate remarkably dense polymer shells that serve as armor and rationally tune protein function. Using straightforward chemistry, it is possible to covalently couple or display multiple small molecule initiators onto a protein surface. The chemistry is fine-tuned to be sequence specific (if one desires a single targeted site) at controlled density. Once the initiator is anchored on the protein surface, ATRP is used to grow polymers on protein surface, in situ. The technique is so powerful that a single-protein polymer conjugate molecule can contain more than 90% polymer coating by weight. If desired, stimuli-responsive polymers can be "grown" from the initiated sites to prepare enzyme conjugates that respond to external triggers such as temperature or pH, while still maintaining enzyme activity and stability. Herein, we focus mainly on the synthesis of chymotrypsin-polymer conjugates. Control of the number of covalently coupled initiator sites by changing the stoichiometric ratio between enzyme and the initiator during the synthesis of protein-initiator complexes allowed fine-tuning of the grafting density. For example, very high grafting density chymotrypsin conjugates were prepared from protein-initiator complexes to grow the temperature-responsive polymers, poly(N-isopropylacrylamide), and poly[N,N'-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate]. Controlled growth of polymers from protein surfaces enables one to predictably manipulate enzyme kinetics and stability without the need for molecular biology-dependent mutagenesis. © 2017 Elsevier Inc. All rights reserved.

Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the change distribution model.

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

Ridley, Mora K.; Hiemstra, T; Machesky, Michael L.

2012-01-01

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3 11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Sternmore » layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (110) rutile surface (Zhang et al., 2004b). TheMDsimulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs) should aid in elucidating a fundamental understating of ion-adsorption reactions.« less

Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the charge distribution model

NASA Astrophysics Data System (ADS)

Ridley, Moira K.; Hiemstra, Tjisse; Machesky, Michael L.; Wesolowski, David J.; van Riemsdijk, Willem H.

2012-10-01

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3-11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 °C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (1 1 0) rutile surface (Zhang et al., 2004b). The MD simulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs) should aid in elucidating a fundamental understating of ion-adsorption reactions.

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.

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

NASA Astrophysics Data System (ADS)

Langdon, Blake Brianna

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

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) as a probe of macromolecule adsorption kinetics at functionalized interfaces.

PubMed

O'Connell, Michael A; de Cuendias, Anne; Gayet, Florence; Shirley, Ian M; Mackenzie, Stuart R; Haddleton, David M; Unwin, Patrick R

2012-05-01

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) has been employed to study the interfacial adsorption kinetics of coumarin-tagged macromolecules onto a range of functionalized planar surfaces. Such studies are valuable in designing polymers for complex systems where the degree of interaction between the polymer and surface needs to be tailored. Three tagged synthetic polymers with different functionalities are examined: poly(acrylic acid) (PAA), poly(3-sulfopropyl methacrylate, potassium salt) (PSPMA), and a mannose-modified glycopolymer. Adsorption transients at the silica/water interface are found to be characteristic for each polymer, and kinetics are deduced from the initial rates. The chemistry of the adsorption interfaces has been varied by, first, manipulation of silica surface chemistry via the bulk pH, followed by surfaces modified by poly(L-glutamic acid) (PGA) and cellulose, giving five chemically different surfaces. Complementary atomic force microscopy (AFM) imaging has been used for additional surface characterization of adsorbed layers and functionalized interfaces to allow adsorption rates to be interpreted more fully. Adsorption rates for PSPMA and the glycopolymer are seen to be highly surface sensitive, with significantly higher rates on cellulose-modified surfaces, whereas PAA shows a much smaller rate dependence on the nature of the adsorption surface.

Supersonic molecular beam experiments on surface chemical reactions.

PubMed

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conformer Hunting: An Open-Ended Computational Chemistry Exercise That Expresses Real-World Complexity and Student Forethought

NASA Astrophysics Data System (ADS)

Lipkowitz, Kenny B.; Robertson, Daniel

2000-02-01

A computational chemistry project suitable for both graduate and undergraduate classes has been developed, tested, and implemented successfully over the course of 10 years. In this project we ask students the following simple question: "Which conformer searching strategy in Spartan is the best?" To answer this question the students need to develop a working definition of what "best" means within the context of the project, design their own experiments that can address that question most suitably, carry out the calculations to derive a compelling answer, and then write their results in the form of a research paper. In addition to teaching students about potential energy surfaces, molecular modeling techniques, and stereochemistry, the pedagogical advantages of this computational chemistry exercise compared to others published in this Journal are that it (i) requires a significant amount of student forethought in addition to afterthought by forcing students to design their own experiments, (ii) demonstrates real-world levels of complexity by using molecules having multiple rotatable bonds, (iii) allows for student creativity that is missing in most other published exercises, (iv) focuses on writing in the curriculum.

Surface grafted antibodies: controlled architecture permits enhanced antigen detection.

PubMed

Sebra, Robert P; Masters, Kristyn S; Bowman, Christopher N; Anseth, Kristi S

2005-11-22

The attachment of antibodies to substrate surfaces is useful for achieving specific detection of antigens and toxins associated with clinical and field diagnostics. Here, acrylated whole antibodies were produced through conjugation chemistry, with the goal of covalently photografting these proteins from surfaces in a controlled fashion, to facilitate rapid and sensitive antigenic detection. A living radical photopolymerization chemistry was used to graft the acrylated whole antibodies on polymer surfaces at controlled densities and spatial locations by controlling the exposure time and area, respectively. Copolymer grafts containing these antibodies were synthesized to demonstrate two principles. First, PEG functionalities were introduced to prevent nonspecific protein interactions and improve the reaction kinetics by increasing solvation and mobility of the antibody-containing chains. Both of these properties lead to sensitive (pM) and rapid (<20 min) detection of antigens with this surface modification technique. Second, graft composition was tailored to include multiple antibodies on the same grafted chains, establishing a means for simultaneously detecting multiple antigens on one grafted surface area. Finally, the addition of PEG spacers between the acrylate functionality and the pendant detection antibodies was tuned to enhance the detection of a short-half-life molecule, glucagon, in a complex biological environment, plasma.

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

PubMed

Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin

2016-01-01

Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of organic complexing agents which are ubiquitous in the environment.

78 FR 20661 - Agency Information Collection Activities; Submission for Office of Management and Budget Review...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-05

... Category: For a food additive petition without complex chemistry, manufacturing, efficacy, or safety issues...) Complex Category: For a food additive petition with complex chemistry, manufacturing, efficacy, and/or... additive file without complex chemistry, manufacturing, efficacy, or safety issues, the estimated time...

Final Technical Report. Reactivity of Iron-Bearing Minerals and CO 2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

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

Strongin, Daniel

2014-12-31

Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO 2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO 2 (scCO 2 ) with H 2 S and/or SO 2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO 2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with anmore » atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO 2 in the presence of sulfide led to reactions that formed siderite (FeCO 3). The results have important implications for the sequestration of CO 2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the adsorption of phospholipid on the surface to selectively suppress the reactivity of these sites could of potential importance for suppressing acid mine drainage in the environment (a problem common to coal-mining sites). Biotic studies showed that microbial activity that promotes the oxidation of pyrite to produce AMD could also be suppressed by the adsorption of phospholipid.« less

New Tools for the Study of Combustion Chemistry and Complex Gas-Surface Interactions from First Principles

DTIC Science & Technology

2007-10-06

Proffen, A. M. Rappe, S. Scott, and R. Seshadri, "BaCel-xPd,O 3-8 (0<xɘ.1): Redox controlled ingress and egress of palladium in a perovskite...methyl and the surface rhodium atoms. Such multi-center bonding leads to C-H bond depletion and is the cause of experimentally observed mode-softening...The Pd 2 - containing perovskite phases extrude elemental face-centered cubic palladium nanoparticles when heated in a reducing atmosphere. This

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Hydrodynamic observations in support of Moored Autonomous pCO2 buoy efforts at La Parguera Marine Reserve

NASA Astrophysics Data System (ADS)

Rodriguez-Abudo, S.; Melendez, M.; Morell, J. M.; Padilla, A.; Salisbury, J.

2016-02-01

Time series of near-reef carbonate chemistry obtained through the National Coral Reef Monitoring Program (NCRMP) at La Parguera Marine Reserve, Puerto Rico exhibit seasonal and diurnal variations modulated by diverse processes including coral community metabolism, thermodynamics and hydrodynamics. While surface CO2 dynamics have been fairly well characterized with moored pCO2 efforts, detailed hydrodynamic information resulting from La Parguera's complex morphological, meteorological, and oceanographic processes is currently lacking. This project focuses on a one-month-long hydrodynamic assessment near a fore reef site located within 100 m of the NCRMP pCO2 buoy. Current profiles spanning 12 m of depth were resolved with a bottom-mounted ADCP. Preliminary results show that under no wind conditions, dominant currents are tidally driven and aligned with the reef channel. Depth-averaged currents exhibit diurnal and semidiurnal peaks, not inconsistent with tidal and wind forcing. The analysis also shows that at times surface current direction can differ from near-reef currents by as much as 200 degrees, suggesting a possible mismatch between carbonate chemistry resolved at the surface and that felt by the reef structure. Moreover, buoy measurements are potentially resolving carbonate chemistry from both, oceanic and inshore water masses. Our findings suggest that monitoring and potentially predicting near-reef CO2 dynamics require interdisciplinary expertise and integrated approaches. This project provides new insights into the effects of tidal and meteorological forcing on the carbonate chemistry of near-reef coral ecosystems.

The Effect of Solution Chemistry on Nucleation of Nesquehonite

NASA Astrophysics Data System (ADS)

Zhao, L.; Zhu, C.; Wang, Z.

2016-12-01

The interfaces between minerals and aqueous solutions are key to important Earth surface processes, including chemical weathering, mineral dissolution/precipitation, and pollutant absorption/release. Mineral surface properties, such as the surface structure and the surface energy, determine the outcomes of many geochemical reactions. Several factors could affect surface energy, but the effect of solution chemistry, particularly the solution stoichiometry, on the surface energy and nucleation process is poorly understood. The goal of this study is to understand the effect of solution chemistry on the nucleation of nesquehonite. Nesquehonite nucleation experiments were conducted in aqueous solutions having similar Mg2+/ CO32- activity ratios, but different saturation states and solution pH. The experimental results show that induction-time estimates from our precipitation experiments with similar Mg2+/CO32- activity ratios are consistent with classical nucleation theory (CNT), while the surface energy derived from CNT varies with Mg2+/CO32- activity ratios. Our observations can be explained by the different absorption behaviors of Mg2+ and CO32- and and/or reduced Gibbs free energies through better screening of the electric double layer. A surface energy model involving solution composition is developed that combines surface complexation with electrostatic models. The new model takes into account how surface charge may affect surface energy. It implies that the highest surface energy may occur around the point of zero charge (p.z.c), where the nucleation is fastest (or conversely, where the induction time is shortest) under low saturation states, but not under high saturation states. An accelerated attachment rate of monomers at the p.z.c. is consistent with high surface energy, since it represents higher reactivity of surface ions and less work needed to break the solvated water molecules. This study provides deeper insights into mechanisms of nesquehonite nucleation in nature, and guidelines for accelerating the precipitation rates of nesquehonite.

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

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

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

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

DOE PAGES

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

2016-10-17

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

Approach to Rapid Synthesis and Functionalization of Iron Oxide Nanoparticles for High Gene Transfection.

PubMed

Stephen, Zachary R; Dayringer, Christopher J; Lim, Josh J; Revia, Richard A; Halbert, Mackenzie V; Jeon, Mike; Bakthavatsalam, Arvind; Ellenbogen, Richard G; Zhang, Miqin

2016-03-01

Surface functionalization of theranostic nanoparticles (NPs) typically relies on lengthy, aqueous postsynthesis labeling chemistries that have limited ability to fine-tune surface properties and can lead to NP heterogeneity. The need for a rapid, simple synthesis approach that can provide great control over the display of functional moieties on NP surfaces has led to increased use of highly selective bioorthoganol chemistries including metal-affinity coordination. Here we report a simple approach for rapid production of a superparamagnetic iron oxide NPs (SPIONs) with tunable functionality and high reproducibility under aqueous conditions. We utilize the high affinity complex formed between catechol and Fe((III)) as a means to dock well-defined catechol modified polymer modules on the surface of SPIONs during sonochemical coprecipitation synthesis. Polymer modules consisted of chitosan and poly(ethylene glycol) (PEG) copolymer (CP) modified with catechol (CCP), and CCP functionalized with cationic polyethylenimine (CCP-PEI) to facilitate binding and delivery of DNA for gene therapy. This rapid synthesis/functionalization approach provided excellent control over the extent of PEI labeling, improved SPION magnetic resonance imaging (MRI) contrast enhancement and produced an efficient transfection agent.

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.

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.

The Gas-Grain Chemistry of Galactic Translucent Clouds

NASA Astrophysics Data System (ADS)

Maffucci, Dominique M.; Herbst, Eric

2016-01-01

We employ a combination of traditional and modified rate equation approaches to simulate the time-dependent gas-grain chemistry that pertains to molecular species observed in absorption in Galactic translucent clouds towards Sgr B2(N). We solve the kinetic rate laws over a range of relevant physical conditions (gas and grain temperatures, particle density, visual extinction, cosmic ray ionization rate) characteristic of translucent clouds by implementing a new grid module that allows for parallelization of the astrochemical simulations. Gas-phase and grain-surface synthetic pathways, chemical timescales, and associated physical sensitivities are discussed for selected classes of species including the cyanopolyynes, complex cyanides, and simple aldehydes.

Global Ozone and Reactive Nitrogen : Composition, Chemistry and Sources

NASA Technical Reports Server (NTRS)

Sing, Hanwant B.; Bradshaw, J.; Davis, D.; Gregory, G.; Talbot, R.

1994-01-01

Ozone plays a central role in the chemistry of the atmosphere both as an ultraviolet shield and as a source of hydroxyl radicals (OH), a potent initiator of atmospheric chemistry. There is evidence to suggest that the ozone abundance in the troposphere (0-10 km) has doubled since the industrial revolution and continues to increase to date. The principle reason for this increase is thought to be the increasing emissions of nitrogen oxides (NO(x)) from anthropogenic activities. Although NO(x) is highly reactive and its products such as HN03 are easily removed by deposition, it now appears that its chemistry is quite complex and it can be transported over long distances via its conversion to a variety of nitrates and penetrates. The sources of atmospheric NO(x) include free tropospheric sources such as lightning and subsonic aircraft, as well as surface emissions which are transported to the free troposphere via convective processes. Recent experimental and theoretical studies have tried to unravel the chemistry of reactive nitrogen species, its sources, and their role in ozone formation. In this presentation we shall describe the results from these studies.

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

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

Song, Wentao; Leung, Kevin; Shao, Qian

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

DOE PAGES

Song, Wentao; Leung, Kevin; Shao, Qian; ...

2016-09-15

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

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.

Theoretical Modeling of Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Charnley, Steven

2009-01-01

The chemistry of complex interstellar organic molecules will be described. Gas phase processes that may build large carbon-chain species in cold molecular clouds will be summarized. Catalytic reactions on grain surfaces can lead to a large variety of organic species, and models of molecule formation by atom additions to multiply-bonded molecules will be presented. The subsequent desorption of these mixed molecular ices can initiate a distinctive organic chemistry in hot molecular cores. The general ion-molecule pathways leading to even larger organics will be outlined. The predictions of this theory will be compared with observations to show how possible organic formation pathways in the interstellar medium may be constrained. In particular, the success of the theory in explaining trends in the known interstellar organics, in predicting recently-detected interstellar molecules, and, just as importantly, non-detections, will be discussed.

Laboratory study of hyper-elocity impact-driven chemical reactions and surface evolution in icy targets.

NASA Astrophysics Data System (ADS)

Ulibarri, Z.; Munsat, T.; Dee, R.; Horanyi, M.; James, D.; Kempf, S.; Nagle, M.; Sternovsky, Z.

2017-12-01

Although ice is prevalent in the solar system and the long-term evolution of many airless icy bodies is affected by hypervelocity micrometeoroid bombardment, there has been little experimental investigation into these impact phenomena, especially at the impact speeds encountered in space. For example, there is little direct information about how dust impacts alter the local chemistry, and dust impacts may be an important mechanism for creating complex organic molecules necessary for life. Laser ablation and light-gas gun experiments simulating dust impacts have successfully created amino acid precursors from base components in ice surfaces. Additionally, the Cassini mission revealed CO2 deposits in icy satellites of Saturn, which may have been created by dust impacts. With the creation of a cryogenically cooled ice target for the dust accelerator facility at the NASA SSERVI-funded Institute for Modeling Plasma, Atmospheres, and Cosmic Dust (IMPACT), it is now possible to study the effects of micrometeoroid impacts in a controlled environment under conditions and at energies typically encountered in nature. Complex ice-target mixtures are created with a flash-freezing target which allows for homogeneous mixtures to be frozen in place even with salt mixtures that otherwise would form inhomogeneous ice surfaces. Coupled with the distinctive capabilities of the IMPACT dust facility, highly valuable data concerning the evolution of icy bodies under hypervelocity bombardment and the genesis of complex organic chemistry on these icy bodies can be gathered in unique and tightly controlled experiments. Results from recent and ongoing investigations will be presented.

Sol-Gel Chemistry for Carbon Dots.

PubMed

Malfatti, Luca; Innocenzi, Plinio

2018-03-14

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

Bio-inspired reversible underwater adhesive.

PubMed

Zhao, Yanhua; Wu, Yang; Wang, Liang; Zhang, Manman; Chen, Xuan; Liu, Minjie; Fan, Jun; Liu, Junqiu; Zhou, Feng; Wang, Zuankai

2017-12-20

The design of smart surfaces with switchable adhesive properties in a wet environment has remained a challenge in adhesion science and materials engineering. Despite intense demands in various industrial applications and exciting progress in mimicking the remarkable wet adhesion through the delicate control of catechol chemistry, polyelectrolyte complex, and supramolecular architectures, the full recapitulation of nature's dynamic function is limited. Here, we show a facile approach to synthesize bioinspired adhesive, which entails the reversible, tunable, and fast regulation of the wet adhesion on diverse surfaces. The smart wet adhesive takes advantage of the host-guest molecular interaction and the adhesive nature of catechol chemistry, as well as the responsive polymer, allowing for screening and activation of the interfacial interaction simply by a local temperature trigger in an on-demand manner. Our work opens up an avenue for the rational design of bioinspired adhesives with performances even beyond nature.

Characterization of low thermal conductivity PAN-based carbon fibers

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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

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

Rappe, Andrew

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

Vacuum Ultraviolet Photoabsorption Spectra of Nitrile Ices for their Identification on Pluto

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.; Raja Sekhar, B. N.; Hill, H.; Cheng, B.-M.; Mason, N. J.

2016-07-01

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N2), methane (CH4), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH3CN), propionitrile (CH3CH2CN), butyronitrile (CH3CH2CH2CN), and isobutyronitrile ((CH3)2CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compounds we propose that such nitriles may be identified from the ALICE payload on board New Horizons.

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater.

PubMed

Kim, Ja-Myung; Baars, Oliver; Morel, François M M

2016-11-28

A poorly studied but potentially important consequence of the CO 2 -induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis , demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

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

NASA Astrophysics Data System (ADS)

Ganapatibhotla, Lalitha V. N. R.

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

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

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-02-01

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

Complex Autocatalysis in Simple Chemistries.

PubMed

Virgo, Nathaniel; Ikegami, Takashi; McGregor, Simon

2016-01-01

Life on Earth must originally have arisen from abiotic chemistry. Since the details of this chemistry are unknown, we wish to understand, in general, which types of chemistry can lead to complex, lifelike behavior. Here we show that even very simple chemistries in the thermodynamically reversible regime can self-organize to form complex autocatalytic cycles, with the catalytic effects emerging from the network structure. We demonstrate this with a very simple but thermodynamically reasonable artificial chemistry model. By suppressing the direct reaction from reactants to products, we obtain the simplest kind of autocatalytic cycle, resulting in exponential growth. When these simple first-order cycles are prevented from forming, the system achieves superexponential growth through more complex, higher-order autocatalytic cycles. This leads to nonlinear phenomena such as oscillations and bistability, the latter of which is of particular interest regarding the origins of life.

Contact Angle of Drops Measured on Nontransparent Surfaces and Capillary Flow Visualized

NASA Technical Reports Server (NTRS)

Chao, David F.; Zhang, Nengli

2003-01-01

The spreading of a liquid on a solid surface is important for various practical processes, and contact-angle measurements provide an elegant method to characterize the interfacial properties of the liquid with the solid substrates. The complex physical processes occurring when a liquid contacts a solid play an important role in determining the performance of chemical processes and materials. Applications for these processes are in printing, coating, gluing, textile dyeing, and adhesives and in the pharmaceutical industry, biomedical research, adhesives, flat panel display manufacturing, surfactant chemistry, and thermal engineering.

Dragonfly: Investigating the Surface Composition of Titan

NASA Technical Reports Server (NTRS)

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

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

PubMed

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

2011-11-01

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

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

Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry.

PubMed

Fashina, Adedayo; Amuhaya, Edith; Nyokong, Tebello

2015-04-05

This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine-silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

Sensitivity of Ocean Chemistry and Oxygen Change to the Uncertainty in Climate Change

NASA Astrophysics Data System (ADS)

Cao, L.; Wang, S.; Zheng, M.; Zhang, H.

2014-12-01

With increasing atmospheric CO2 and climate change, global ocean is undergoing substantial physical and biogeochemical changes. In particular, changes in ocean oxygen and carbonate chemistry have great implication for marine biota. There is considerable uncertainty in the projections of future climate change, and it is unclear how the uncertainty in climate change would affect the projection of ocean oxygen and carbonate chemistry. To examine the effect of climate change on ocean oxygen and carbonate chemistry, we used an Earth system model of intermediate complexity to perform simulations that are driven by atmospheric CO2 concentration pathway of RCP 8.5 with climate sensitivity varying from 0.0°C to 4.5 °C. Climate change affects carbonate chemistry and oxygen mainly through its impact on ocean temperature, ocean ventilation, and concentration of dissolved inorganic carbon and alkalinity. Our simulations show that climate change mitigates the decrease of carbonate ions at the ocean surface but has negligible effect on surface ocean pH. Averaged over the whole ocean, climate change acts to decrease oxygen concentration but mitigates the CO2-induced reduction of carbonate ion and pH. In our simulations, by year 2500, every degree increase of climate sensitivity warms the ocean by 0.8 °C and reduces ocean-mean dissolved oxygen concentration by 5.0%. Meanwhile, every degree increase of climate sensitivity buffers CO2-induced reduction in ocean-mean carbonate ion concentration and pH by 3.4% and 0.02 units, respectively. Our study demonstrates different sensitivities of ocean temperature, carbonate chemistry, and oxygen, in terms of both the sign and magnitude, to the amount of climate change, which have great implications for understanding the response of ocean biota to climate change.

Bio-Orthogonal Mediated Nucleic Acid Transfection of Cells via Cell Surface Engineering.

PubMed

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

2017-05-24

The efficient delivery of foreign nucleic acids (transfection) into cells is a critical tool for fundamental biomedical research and a pillar of several biotechnology industries. There are currently three main strategies for transfection including reagent, instrument, and viral based methods. Each technology has significantly advanced cell transfection; however, reagent based methods have captured the majority of the transfection market due to their relatively low cost and ease of use. This general method relies on the efficient packaging of a reagent with nucleic acids to form a stable complex that is subsequently associated and delivered to cells via nonspecific electrostatic targeting. Reagent transfection methods generally use various polyamine cationic type molecules to condense with negatively charged nucleic acids into a highly positively charged complex, which is subsequently delivered to negatively charged cells in culture for association, internalization, release, and expression. Although this appears to be a straightforward procedure, there are several major issues including toxicity, low efficiency, sorting of viable transfected from nontransfected cells, and limited scope of transfectable cell types. Herein, we report a new strategy (SnapFect) for nucleic acid transfection to cells that does not rely on electrostatic interactions but instead uses an integrated approach combining bio-orthogonal liposome fusion, click chemistry, and cell surface engineering. We show that a target cell population is rapidly and efficiently engineered to present a bio-orthogonal functional group on its cell surface through nanoparticle liposome delivery and fusion. A complementary bio-orthogonal nucleic acid complex is then formed and delivered to which chemoselective click chemistry induced transfection occurs to the primed cell. This new strategy requires minimal time, steps, and reagents and leads to superior transfection results for a broad range of cell types. Moreover the transfection is efficient with high cell viability and does not require a postsorting step to separate transfected from nontransfected cells in the cell population. We also show for the first time a precision transfection strategy where a single cell type in a coculture is target transfected via bio-orthogonal click chemistry.

Deciphering the Complex Chemistry of Deep-Ocean Particles Using Complementary Synchrotron X-ray Microscope and Microprobe Instruments.

PubMed

Toner, Brandy M; German, Christopher R; Dick, Gregory J; Breier, John A

2016-01-19

The reactivity and mobility of natural particles in aquatic systems have wide ranging implications for the functioning of Earth surface systems. Particles in the ocean are biologically and chemically reactive, mobile, and complex in composition. The chemical composition of marine particles is thought to be central to understanding processes that convert globally relevant elements, such as C and Fe, among forms with varying bioavailability and mobility in the ocean. The analytical tools needed to measure the complex chemistry of natural particles are the subject of this Account. We describe how a suite of complementary synchrotron radiation instruments with nano- and micrometer focusing, and X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) capabilities are changing our understanding of deep-ocean chemistry and life. Submarine venting along mid-ocean ridges creates hydrothermal plumes where dynamic particle-forming reactions occur as vent fluids mix with deep-ocean waters. Whether plumes are net sources or sinks of elements in ocean budgets depends in large part on particle formation, reactivity, and transport properties. Hydrothermal plume particles have been shown to host microbial communities and exhibit complex size distributions, aggregation behavior, and composition. X-ray microscope and microprobe instruments can address particle size and aggregation, but their true strength is in measuring chemical composition. Plume particles comprise a stunning array of inorganic and organic phases, from single-crystal sulfides to poorly ordered nanophases and polymeric organic matrices to microbial cells. X-ray microscopes and X-ray microprobes with elemental imaging, XAS, and XRD capabilities are ideal for investigating these complex materials because they can (1) measure the chemistry of organic and inorganic constituents in complex matrices, usually within the same particle or aggregate, (2) provide strong signal-to-noise data with exceedingly small amounts of material, (3) simplify the chemical complexity of particles or sets of particles with a focused-beam, providing spatial resolution over 6 orders of magnitude (nanometer to millimeter), (4) provide elemental specificity for elements in the soft-, tender-, and hard-X-ray energies, (5) switch rapidly among elements of interest, and (6) function in the presence of water and gases. Synchrotron derived data sets are discussed in the context of important advances in deep-ocean technology, sample handling and preservation, molecular microbiology, and coupled physical-chemical-biological modeling. Particle chemistry, size, and morphology are all important in determining whether particles are reactive with dissolved constituents, provide substrates for microbial respiration and growth, and are delivered to marine sediments or dispersed by deep-ocean currents.

Ionic-Liquid-Infused Nanostructures as Repellent Surfaces.

PubMed

Galvan, Yaraset; Phillips, Katherine R; Haumann, Marco; Wasserscheid, Peter; Zarraga, Ramon; Vogel, Nicolas

2018-06-12

In order to prepare lubricant-infused repellent coatings on silica nanostructures using low vapor pressure ionic liquids as lubricants, we study the wetting behavior of a set of imidazolium-based ionic liquids with different alkyl side chains as a function of the applied surface functionalities. We take advantage of the structural color of inverse opals prepared from a colloidal coassembly technique to study the infiltration of ionic liquids into these nanoporous structures. We find that the more hydrophobic ionic liquids with butyl and hexyl side chains can completely infiltrate inverse opals functionalized with mixed self-assembled monolayers composed of imidazole groups and aliphatic hydrocarbon chains, which we introduce via silane chemistry. These molecular species reflect the chemical nature of the ionic liquid, thereby increasing the affinity between the liquid and solid surface. The mixed surface chemistry provides sufficiently small contact angles with the ionic liquid to infiltrate the nanopores while maximizing the contact angle with water. As a result, the mixed monolayers enable the design of a stable ionic liquid/solid interface that is able to repel water as a test liquid. Our results underline the importance of matching chemical affinities to predict and control the wetting behavior in complex, multiphase systems.

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

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

PubMed

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

2002-12-15

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

Modular syntheses of H₄octapa and H₂dedpa, and yttrium coordination chemistry relevant to ⁸⁶Y/⁹⁰Y radiopharmaceuticals.

PubMed

Price, Eric W; Cawthray, Jacqueline F; Adam, Michael J; Orvig, Chris

2014-05-21

The ligands H2dedpa, H4octapa, p-SCN-Bn-H2dedpa, and p-SCN-Bn-H4octapa were synthesized using a new protection chemistry approach, with labile tert-butyl esters replacing the previously used methyl esters as protecting groups for picolinic acid moieties. Additionally, the ligands H2dedpa and p-SCN-Bn-H2dedpa were synthesized using nosyl protection chemistry for the first time. The use of tert-butyl esters allows for deprotection at room temperature in trifluoroacetic acid (TFA), which compares favorably to the harsh conditions of refluxing HCl (6 M) or LiOH that were previously required for methyl ester cleavage. H4octapa has recently been shown to be a very promising (111)In and (177)Lu ligand for radiopharmaceutical applications; therefore, coordination chemistry studies with Y(3+) are described to assess its potential for use with (86)Y/(90)Y. The solution chemistry of H4octapa with Y(3+) is shown to be suitable via solution NMR studies of the [Y(octapa)](-) complex and density functional theory (DFT) calculations of the predicted structure, suggesting properties similar to those of the analogous In(3+) and Lu(3+) complexes. The molecular electrostatic potential (MEP) was mapped onto the molecular surface of the DFT-calculated coordination structures, suggesting very similar and even charge distributions between both the Lu(3+) and Y(3+) complexes of octapa(4-), and coordinate structures between 8 (ligand only) and 9 (ligand and one H2O). Potentiometric titrations determined H4octapa to have a formation constant (log K(ML)) with Y(3+) of 18.3 ± 0.1, revealing high thermodynamic stability. This preliminary work suggests that H4octapa may be a competent ligand for future (86)Y/(90)Y radiopharmaceutical applications.

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes via Photoclick Chemistry for Alkene Epoxidation.

PubMed

Ghosh, Dwaipayan; Febriansyah, Benny; Gupta, Disha; Ng, Leonard Kia-Sheun; Xi, Shibo; Du, Yonghua; Baikie, Tom; Dong, ZhiLi; Soo, Han Sen

2018-05-22

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.

Understanding the nanoparticle-protein corona complexes using computational and experimental methods.

PubMed

Kharazian, B; Hadipour, N L; Ejtehadi, M R

2016-06-01

Nanoparticles (NP) have capability to adsorb proteins from biological fluids and form protein layer, which is called protein corona. As the cell sees corona coated NPs, the protein corona can dictate biological response to NPs. The composition of protein corona is varied by physicochemical properties of NPs including size, shape, surface chemistry. Processing of protein adsorption is dynamic phenomena; to that end, a protein may desorb or leave a surface vacancy that is rapidly filled by another protein and cause changes in the corona composition mainly by the Vroman effect. In this review, we discuss the interaction between NP and proteins and the available techniques for identification of NP-bound proteins. Also we review current developed computational methods for understanding the NP-protein complex interactions. Copyright © 2016. Published by Elsevier Ltd.

Ice Chemistry in Starless Molecular Cores

NASA Astrophysics Data System (ADS)

Kalvāns, J.

2015-06-01

Starless molecular cores are natural laboratories for interstellar molecular chemistry research. The chemistry of ices in such objects was investigated with a three-phase (gas, surface, and mantle) model. We considered the center part of five starless cores, with their physical conditions derived from observations. The ice chemistry of oxygen, nitrogen, sulfur, and complex organic molecules (COMs) was analyzed. We found that an ice-depth dimension, measured, e.g., in monolayers, is essential for modeling of chemistry in interstellar ices. Particularly, the H2O:CO:CO2:N2:NH3 ice abundance ratio regulates the production and destruction of minor species. It is suggested that photodesorption during the core-collapse period is responsible for the high abundance of interstellar H2O2 and O2H and other species synthesized on the surface. The calculated abundances of COMs in ice were compared to observed gas-phase values. Smaller activation barriers for CO and H2CO hydrogenation may help explain the production of a number of COMs. The observed abundance of methyl formate HCOOCH3 could be reproduced with a 1 kyr, 20 K temperature spike. Possible desorption mechanisms, relevant for COMs, are gas turbulence (ice exposure to interstellar photons) or a weak shock within the cloud core (grain collisions). To reproduce the observed COM abundances with the present 0D model, 1%-10% of ice mass needs to be sublimated. We estimate that the lifetime for starless cores likely does not exceed 1 Myr. Taurus cores are likely to be younger than their counterparts in most other clouds.

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.

Metrology in physics, chemistry, and biology: differing perceptions.

PubMed

Iyengar, Venkatesh

2007-04-01

The association of physics and chemistry with metrology (the science of measurements) is well documented. For practical purposes, basic metrological measurements in physics are governed by two components, namely, the measure (i.e., the unit of measurement) and the measurand (i.e., the entity measured), which fully account for the integrity of a measurement process. In simple words, in the case of measuring the length of a room (the measurand), the SI unit meter (the measure) provides a direct answer sustained by metrological concepts. Metrology in chemistry, as observed through physical chemistry (measures used to express molar relationships, volume, pressure, temperature, surface tension, among others) follows the same principles of metrology as in physics. The same basis percolates to classical analytical chemistry (gravimetry for preparing high-purity standards, related definitive analytical techniques, among others). However, certain transition takes place in extending the metrological principles to chemical measurements in complex chemical matrices (e.g., food samples), as it adds a third component, namely, indirect measurements (e.g., AAS determination of Zn in foods). This is a practice frequently used in field assays, and calls for additional steps to account for traceability of such chemical measurements for safeguarding reliability concerns. Hence, the assessment that chemical metrology is still evolving.

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

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

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

2015-03-30

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

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

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

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

2015-09-15

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

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

Strain-induced alignment and phase behavior of blue phase liquid crystals confined to thin films.

PubMed

Bukusoglu, Emre; Martinez-Gonzalez, Jose A; Wang, Xiaoguang; Zhou, Ye; de Pablo, Juan J; Abbott, Nicholas L

2017-12-06

We report on the influence of surface confinement on the phase behavior and strain-induced alignment of thin films of blue phase liquid crystals (BPs). Confining surfaces comprised of bare glass, dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP)-functionalized glass, or polyvinyl alcohol (PVA)-coated glass were used with or without mechanically rubbing to influence the azimuthal anchoring of the BPs. These experiments reveal that confinement can change the phase behavior of the BP films. For example, in experiments performed with rubbed-PVA surfaces, we measured the elastic strain of the BPs to change the isotropic-BPII phase boundary, suppressing formation of BPII for film thicknesses incommensurate with the BPII lattice. In addition, we observed strain-induced alignment of the BPs to exhibit a complex dependence on both the surface chemistry and azimuthal alignment of the BPs. For example, when using bare glass surfaces causing azimuthally degenerate and planar anchoring, BPI oriented with (110) planes of the unit cell parallel to the contacting surfaces for thicknesses below 3 μm but transitioned to an orientation with (200) planes aligned parallel to the contacting surfaces for thicknesses above 4 μm. In contrast, BPI aligned with (110) planes parallel to confining surfaces for all other thicknesses and surface treatments, including bare glass with uniform azimuthal alignment. Complementary simulations based on minimization of the total free energy (Landau-de Gennes formalism) confirmed a thickness-dependent reorientation due to strain of BPI unit cells within a window of surface anchoring energies and in the absence of uniform azimuthal alignment. In contrast to BPI, BPII did not exhibit thickness-dependent orientations but did exhibit orientations that were dependent on the surface chemistry, a result that was also captured in simulations by varying the anchoring energies. Overall, the results in this paper reveal that the orientations assumed by BPs in thin films reflect a complex interplay of surface interactions and elastic energies associated with strain of the BP lattice. The results also provide new principles and methods to control the structure and properties of BP thin films, which may find use in BP-templated material synthesis, and BP-based optical and electronic devices.

From Titan's chemistry and exobiology to Titan's astrobiology

NASA Astrophysics Data System (ADS)

Raulin, François

2015-04-01

When the IDS proposal « Titan's chemistry and exobiology » was submitted to ESA 25 years ago, in the frame of what will become the Cassini-Huygens mission, Titan was already seen as a quite interesting planetary object in the solar system for Exobiology. Several organic compounds of prebiotic interest were identified in its atmosphere, which was thus was expected to be chemically very active, especially in term of organic processes. Atmospheric aerosols seemed to play a key role in this chemistry. Moreover, the presence of an internal aqueous ocean, compatible with life was suspected. A few years later, when astrobiology was (re)invented, Titan became one of the most interesting planetary target for this new (but very similar to exobiology) field. With the Cassini-Huygens mission, the exo/astrobiological interest of Titan has become more and more important. However, the mission has been providing a vision of Titan quite different from what it was supposed. Its atmospheric organic chemistry is very complex and starts in much higher zones than it was believed before, involving high molecular weight species in the ionosphere. Titan's surface appears to be far from homogeneous: instead of been covered by a global methane-ethane ocean, it is very diversified, with dunes, lakes, bright and dark areas, impact and volcanic craters with potential cryovolcanic activity. These various geological areas are continuously feeded by atmospheric aerosols, which represent an important step in the complexity of Titan's organic chemistry, but probably not the final one. Indeed, after being deposited on the surface, in the potential cryovolvanic zones, these particles may react with water ice and form compounds of exo/astrobiological interest, such as amino acids, purine and pyrimidine bases. Moreover, The Cassini-Huygens data strongly support the potential presence of an internal water ocean, which becomes less and less hypothetical and of great interest for exobiology. These various exobiological aspects of Titan, revealed from Cassini-Huygens observations, especially from the data of the Huygens instruments, coupled to laboratory works, both experimental simulations and modeling, will be quickely reviewed and summarized. References : Raulin, F. (2008), Astrobiology and habitability of Titan, Space Science Reviews 135 (1-4), 37-48 ; Raulin, F. et al. (2012), Prebiotic-like chemistry on Titan. Chemical Society Reviews. 41, 5380-5393 Acknowledgement: Supports from the European Space Agency (ESA) and the French Space Agency (CNES) is deeply acknowledged.

Interstellar Ice Chemistry: From Water to Complex Organics

NASA Astrophysics Data System (ADS)

Oberg, Karin I.; Fayolle, E.; Linnartz, H.; van Dishoeck, E.; Fillion, J.; Bertin, M.

2013-06-01

Molecular cloud cores, protostellar envelopes and protoplanetary disk midplanes are all characterized by freeze-out of atoms and molecules (other than H and H2) onto interstellar dust grains. On the grain surface, atom addition reactions, especially hydrogenation, are efficient and H2O forms readily from O, CH3OH from CO etc. The result is an icy mantle typically dominated by H2O, but also rich in CO2, CO, NH3, CH3OH and CH4. These ices are further processed through interactions with radiation, electrons and energetic particles. Because of the efficiency of the freeze-out process, and the complex chemistry that succeeds it, these icy grain mantles constitute a major reservoir of volatiles during star formation and are also the source of much of the chemical evolution observed in star forming regions. Laboratory experiments allow us to explore how molecules and radicals desorb, dissociate, diffuse and react in ices when exposed to different sources of energy. Changes in ice composition and structure is constrained using infrared spectroscopy and mass spectrometry. By comparing ice desorption, segregation, and chemistry efficiencies under different experimental conditions, we can characterize the basic ice processes, e.g. diffusion of different species, that underpin the observable changes in ice composition and structure. This information can then be used to predict the interstellar ice chemical evolution. I will review some of the key laboratory discoveries on ice chemistry during the past few years and how they have been used to predict and interpret astronomical observations of ice bands and gas-phase molecules associated with ice evaporation. These include measurements of thermal diffusion in and evaporation from ice mixtures, non-thermal diffusion efficiencies (including the recent results on frequency resolved UV photodesorption), and the expected temperature dependencies of the complex ice chemistry regulated by radical formation and diffusion. Based on these examples I will argue that the combination of laboratory experiments and observations is crucial to formulate and to test hypotheses on key processes that regulate the interstellar ice chemistry.

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

Why Interstellar Ices Can Be Considered As Precursors For Prebiotic Chemistry

NASA Astrophysics Data System (ADS)

Hendecourt, Louis Le Sergeant d.; de Marcellus, Pierre; Meinert, Cornelia; Myrgorodska, Iuliia; Nahon, Laurent; Modica, Paola; Buhse, Thomas; Meierhenrich, Uwe J.

2015-08-01

Interstellar ices made of simple molecules (H2O, CO, CO2, CH3OH, NH3, CH4…) are abundant species observed in molecular clouds where stars and planetary systems form. Since the constitutive elements (H, O, C, N, S, P) are the most cosmically abundant and condensible, they favor the making of ices on grains. In the mantles formed, a rich organic chemistry develops, thanks to the protective nature of the grains. This chemistry leads to a high complexity. Radical chemistry generated by photo/thermo-chemical processes on the surfaces, leaves to the formation of organic residues as those produced in our laboratory using ice templates, and further studied, using methods that pertain mostly to analytical chemistry. The organic material formed may resemble the Soluble Organic Matter observed in pristine meteorites. From numerous amino acids [1], aldehydes and sugars [2] detected in these residues to chiral molecules and enantiomeric excesses produced by Vacuum Ultra-Violet Circularly Polarized Light from synchrotron radiation [3], one might seriously ask whether the chemistry of molecular clouds out of which stars, planetary systems and debris form, may not be seriously considered as the precursor of prebiotic chemistry in a given environment such as the surface of a telluric planet. I will present the general frame of these experiments in relation to the possibillity of feeding of the necessary prebiotic chemistry for the origin of life. Certainly, prebiotic chemistry is very different in itself than astrochemistry but the starting bricks issued from astrochemistry may well be necessary for the possibility of the emergence of life on planets under certain assumptions I will briefly discuss.REFERENCES[1] Meinert, C., Filippi, J.-J., de Marcellus, P., Le Sergeant d’Hendecourt, L. and Meierhenrich, U.J., ChemPlusChem, 77, 186-191 (2012).[2] de Marcellus, P., Meinert, C., Myrgorodska, I., Nahon, L., Buhse, T., Le Sergeantd’Hendecourt, L., Meierhenrich, U.J., PNAS, January 12th, 2015[3] Modica, P., Meinert, C. de Marcellus, Nahon, L., Meierhenrich, U.J., Le Sergeant d’Hendecourt, L. Astrophys.J, 788, 79

Organic chemistry in Titan's upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

NASA Astrophysics Data System (ADS)

Ali, A.; Sittler, E. C.; Chornay, D.; Rowe, B. R.; Puzzarini, C.

2015-05-01

The discovery of carbocations and carbanions by Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) instruments onboard the Cassini spacecraft in Titan's upper atmosphere is truly amazing for astrochemists and astrobiologists. In this paper we identify the reaction mechanisms for the growth of the complex macromolecules observed by the CAPS Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS). This identification is based on a recently published paper (Ali et al., 2013. Planet. Space Sci. 87, 96) which emphasizes the role of Olah's nonclassical carbonium ion chemistry in the synthesis of the organic molecules observed in Titan's thermosphere and ionosphere by INMS. The main conclusion of that work was the demonstration of the presence of the cyclopropenyl cation - the simplest Huckel's aromatic molecule - and its cyclic methyl derivatives in Titan's atmosphere at high altitudes. In this study, we present the transition from simple aromatic molecules to the complex ortho-bridged bi- and tri-cyclic hydrocarbons, e.g., CH2+ mono-substituted naphthalene and phenanthrene, as well as the ortho- and peri-bridged tri-cyclic aromatic ring, e.g., perinaphthenyl cation. These rings could further grow into tetra-cyclic and the higher order ring polymers in Titan's upper atmosphere. Contrary to the pre-Cassini observations, the nitrogen chemistry of Titan's upper atmosphere is found to be extremely rich. A variety of N-containing hydrocarbons including the N-heterocycles where a CH group in the polycyclic rings mentioned above is replaced by an N atom, e.g., CH2+ substituted derivative of quinoline (benzopyridine), are found to be dominant in Titan's upper atmosphere. The mechanisms for the formation of complex molecular anions are discussed as well. It is proposed that many closed-shell complex carbocations after their formation first, in Titan's upper atmosphere, undergo the kinetics of electron recombination to form open-shell neutral radicals. These radical species subsequently might form carbanions via radiative electron attachment at low temperatures with thermal electrons. The classic example is the perinaphthenyl anion in Titan's upper atmosphere. Therefore, future astronomical observations of selected carbocations and corresponding carbanions are required to settle the key issue of molecular anion chemistry on Titan. Other than earth, Titan is the only planetary body in our solar system that is known to have reservoirs of permanent liquids on its surface. The synthesis of complex biomolecules either by organic catalysis of precipitated solutes “on hydrocarbon solvent” on Titan or through the solvation process indeed started in its upper atmosphere. The most notable examples in Titan's prebiotic atmospheric chemistry are conjugated and aromatic polycyclic molecules, N-heterocycles including the presence of imino >Cdbnd N-H functional group in the carbonium chemistry. Our major conclusion in this paper is that the synthesis of organic compounds in Titan's upper atmosphere is a direct consequence of the chemistry of carbocations involving the ion-molecule reactions. The observations of complexity in the organic chemistry on Titan from the Cassini-Huygens mission clearly indicate that Titan is so far the only planetary object in our solar system that will most likely provide an answer to the question of the synthesis of complex biomolecules on the primitive earth and the origin of life.

Photosystem I assembly on chemically tailored SAM/ Au substrates for bio-hybrid device fabrication

NASA Astrophysics Data System (ADS)

Mukherjee, Dibyendu; Khomami, Bamin

2011-03-01

Photosystem I (PS I), a supra-molecular protein complex and a biological photodiode responsible for driving natural photosynthesis mechanism, charge separates upon exposure to light. Effective use of the photo-electrochemical activities of PS I for future bio-hybrid electronic devices requires controlled attachment of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface topography of PS I deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate SAM /Au substrates, thereby resulting in complex columnar structures that affect the electron capture pathway of PS I. Specifically, solution phase characterizations indicate that specific detergents used for PS I stabilization in buffer solutions drive the unique colloidal chemistry to tune protein-protein interactions and prevent aggregation, thereby allowing us to tailor the morphology of surface immobilized PS I. We present surface topographical, adsorption, and electrochemical characterizations of PSI /SAM/Au substrates to elucidate protein-surface attachment dynamics and its effect on the photo-activated electronic activities of surface immobilized PS I. Sustainable Energy Education and Research Center (SEERC).

Special Advanced Studies for Pollution Prevention. Delivery Order 0058: The Monitor - Spring 2000

DTIC Science & Technology

2001-04-01

Process complexity ➨ Strippability ➨ Maturity ➨ Process type and chemistry ➨ Licensing requirements ➨ Vendor information ➨ Niplate 700 (Surface...Courses of Action 4 Identify & Evaluate Potential Alternatives 5 Select Best Alternative & Develop Project 6 Prioritize Projects by Commodity 7 Rank...Burden CS Priority Process Specific P2 OASolution Selection Solution Planning Solution Implementation Solution Evaluation Phase 2 Phase 3 Phase 1

Research and Development in support of the Surface Chemistry Branch. Volume 1

DTIC Science & Technology

1988-06-01

reactions could occur in the melt and/or gas phase-and (2) formation of HCN from RDX pyrolysis followed by hydrolysis with atmospheric/RDX decomposition ...interest is the development of electrochemically active transition metal complexes for the catalytic conversion/ decomposition of dissolved gases, such...impregnated charcoals for the collection and catalytic decomposition of toxic vapors (2), and the evaluation of Navy shipboard environments (3). For the

The astrobiology of Titan

NASA Astrophysics Data System (ADS)

Raulin, F.; Coll, P.; Cabane, M.; Hebrard, E.; Israel, G.; Nguyen, M.-J.; Szopa, C.; Gpcos Team

Largest satellite of Saturn and the only satellite in the solar system having a dense atmosphere, Titan is one of the key planetary bodies for astrobiological studies, due to several aspects: Its analogies with planet Earth, in spite of much lower temperatures, The Cassini-Huygens data have largely confirmed the many analogies between Titan and our own planet. Both have similar vertical temperature profiles, (although much colder, of course, on Titan). Both have condensable and non condensable greenhouse gases in their atmosphere. Both are geologically very active. Furthermore, the data also suggest strongly the presence of a methane cycle on Titan analogous to the water cycle on Earth. The presence of an active organic chemistry, involving several of the key compounds of prebiotic chemistry. The recent data obtained from the Huygens instruments show that the organic matter in Titan low atmosphere (stratosphere and troposphere) is mainly concentrated in the aerosol particles. Because of the vertical temperature profile in this part of the atmosphere, most of the volatile organics are probably mainly condensed on the aerosol particles. The nucleus of these particles seems to be made of complex macromolecular organic matter, well mimicked in the laboratory by the "Titan's tholins". Now, laboratory tholins are known to release many organic compounds of biological interest, such as amino acids and purine and pyrimidine bases, when they are in contact with liquid water. Such hydrolysis may have occurred on the surface of Titan, in the bodies of liquid water which episodically may form on Titan's surface from meteoritic and cometary impacts. The formation of biologically interesting compounds may also occur in the deep water ocean, from the hydrolysis of complex organic material included in the chrondritic matter accreted during the formation of Titan. The possible emergence and persistence of Life on Titan 1 All ingredients which seems necessary for Life are present on Titan : • liquid water : permanently as a deep sub-surface ocean, and even episodically on the surface, • organic matter : in the internal structure, from chondritic materials, and in the atmosphere and on the surface, from the atmospheric organic chemistry • and energy : in the atmosphere (solar UV photons, energetic electrons from Saturn magnetosphere and cosmic rays) and, probably, in the environment of the sub-surface ocean (radioactive nuclei in the deep interior and tidal energy dissipation) as also supported by the likely presence of cryovolcanism on the surface Thus, it cannot be excluded that life may have emerged on or in Titan. In spite of the extreme conditions in this environment life may have been able to adapt and to persist. Many data are still expected from the Cassini-Huygens mission and future astrobiological exploration mission of Titan are now under consideration. Nevertheless, Titan already looks like another word, with an active prebiotic-like chemistry, but in the absence of permanent liquid water, on the surface: a natural laboratory for prebiotic-like chemistry. References. Fortes, A.D. (2000), `Exobiological implications of a possible ammonia-water ocean inside Titan', Icarus 146, 444-452 Raulin, F. (2005), `Exo-Astrobiological Aspects of Europa and Titan: From Observations to Speculations', Space Science Review 116 (1-2), 471-496. Nature, (2005), `The Huygens probe on Titan', 8 News & Views, Articles and Letters 438, 756-802 Schulze-Makuch, D., and Grinspoon D.H. (2005), `Biologically enhanced energy and carbon cycling on Titan?',Astrobiology 5, 560-567. 2

Combinatorial computational chemistry approach for materials design: applications in deNOx catalysis, Fischer-Tropsch synthesis, lanthanoid complex, and lithium ion secondary battery.

PubMed

Koyama, Michihisa; Tsuboi, Hideyuki; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A; Miyamoto, Akira

2007-02-01

Computational chemistry can provide fundamental knowledge regarding various aspects of materials. While its impact in scientific research is greatly increasing, its contributions to industrially important issues are far from satisfactory. In order to realize industrial innovation by computational chemistry, a new concept "combinatorial computational chemistry" has been proposed by introducing the concept of combinatorial chemistry to computational chemistry. This combinatorial computational chemistry approach enables theoretical high-throughput screening for materials design. In this manuscript, we review the successful applications of combinatorial computational chemistry to deNO(x) catalysts, Fischer-Tropsch catalysts, lanthanoid complex catalysts, and cathodes of the lithium ion secondary battery.

Understanding the Reaction Chemistry of 2,2':5',2''-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

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

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding the Reaction Chemistry of 2,2':5',2"-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

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

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Aeolian Dust and Forest Fire Smoke in Urban Air

NASA Astrophysics Data System (ADS)

Brimblecombe, P.

2006-12-01

Particles of aeolian dust and forest fire smoke are now regularly detected in urban air. Although dusts are common on the Asian Pacific Rim and forest fire smoke characteristic of South East Asia they also frequently detected elsewhere. In the past dust was treated as though it was fairly inert and reactions on the surface limited to the neutralizing ability of alkaline minerals. More recent work shows that that dust has a complex organic chemistry. Observations in China found fatty acids from urban areas (oleic acid and linoleic acid from cooking) on dust derived aerosols. The fatty acids and PAHs decreased sharply after dust storms, suggesting a role for dust in removal processes. When silica particles absorb unsaturated compounds they can react with ozone and release compounds such as formaldehyde. Particles from forest fires have a similarly complex chemistry and the acid-alkaline balance may vary depend on the balance of removal rates of alkaline materials (ammonia, potassium carbonate) and inorganic and organic acids. Airborne dust and forest fire soot can contain humic like substances (HULIS) either as primary material or as secondary oxidation products of the surface of soot. This paper will report on the role polluted air masses in the generation humic materials, particularly those that are surface active. These materials of high molecular weight oxygen rich organic compounds, which exhibit a range of properties of importance in aerosols: they can form complexes with metal ions and thus enhance their solubility, photosensitize the oxidation of organic compounds and lower the surface tension of aqueous aerosols. HULIS can be oxidized to form a range of simpler acids such as formic, acetic and oxalic acid. Dust and forest fire smoke particles have a different composition and size range to that of typical urban combustion particles, so it is likely that the health impacts will be different, yet current regulation often does not recognize any significant difference.

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

DOE PAGES

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

2016-07-27

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

Hierarchical micron-sized mesoporous/macroporous graphene with well-tuned surface oxygen chemistry for high capacity and cycling stability Li-O2 battery.

PubMed

Zhou, Wei; Zhang, Hongzhang; Nie, Hongjiao; Ma, Yiwen; Zhang, Yining; Zhang, Huamin

2015-02-11

Nonaqueous Li-O2 battery is recognized as one of the most promising energy storage devices for electric vehicles due to its super-high energy density. At present, carbon or catalyst-supporting carbon materials are widely used for cathode materials of Li-O2 battery. However, the unique electrode reaction and complex side reactions lead to numerous hurdles that have to be overcome. The pore blocking caused by the solid products and the byproducts generated from the side reactions severely limit the capacity performance and cycling stability. Thus, there is a great need to develop carbon materials with optimized pore structure and tunable surface chemistry to meet the special requirement of Li-O2 battery. Here, we propose a strategy of vacuum-promoted thermal expansion to fabricate one micron-sized graphene matrix with a hierarchical meso-/macroporous structure, combining with a following deoxygenation treatment to adjust the surface chemistry by reducing the amount of oxygen and selectively removing partial unstable groups. The as-made graphene demonstrates dramatically tailored pore characteristics and a well-tuned surface chemical environment. When applied in Li-O2 battery as cathode, it exhibits an outstanding capacity up to 19 800 mA h g(-1) and is capable of enduring over 50 cycles with a curtaining capacity of 1000 mA h g(-1) at a current density of 1000 mA g(-1). This will provide a novel pathway for the design of cathodes for Li-O2 battery.

Tuning Wettability and Adhesion of Structured Surfaces

NASA Astrophysics Data System (ADS)

Badge, Ila

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

Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution

NASA Technical Reports Server (NTRS)

Brown, Paul D.; Charnley, S. B.

1991-01-01

The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.

Characterization of the surface charge distribution on kaolinite particles using high resolution atomic force microscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Zhao, Cunlu; Klaassen, Aram; van den Ende, Dirk; Mugele, Frieder; Siretanu, Igor

2016-02-01

Most solid surfaces, in particular clay minerals and rock surfaces, acquire a surface charge upon exposure to an aqueous environment due to adsorption and/or desorption of ionic species. Macroscopic techniques such as titration and electrokinetic measurements are commonly used to determine the surface charge and ζ -potential of these surfaces. However, because of the macroscopic averaging character these techniques cannot do justice to the role of local heterogeneities on the surfaces. In this work, we use dynamic atomic force microscopy (AFM) to determine the distribution of surface charge on the two (gibbsite-like and silica-like) basal planes of kaolinite nanoparticles immersed in aqueous electrolyte with a lateral resolution of approximately 30 nm. The surface charge density is extracted from force-distance curves using DLVO theory in combination with surface complexation modeling. While the gibbsite-like and the silica-like facet display on average positive and negative surface charge values as expected, our measurements reveal lateral variations of more than a factor of two on seemingly atomically smooth terraces, even if high resolution AFM images clearly reveal the atomic lattice on the surface. These results suggest that simple surface complexation models of clays that attribute a unique surface chemistry and hence homogeneous surface charge densities to basal planes may miss important aspects of real clay surfaces.

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

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.

Surface chemistry and microscopy of food powders

NASA Astrophysics Data System (ADS)

Burgain, Jennifer; Petit, Jeremy; Scher, Joël; Rasch, Ron; Bhandari, Bhesh; Gaiani, Claire

2017-12-01

Despite high industrial and scientific interest, a comprehensive review of the surface science of food powders is still lacking. There is a real gap between scientific concerns of the field and accessible reviews on the subject. The global description of the surface of food powders by multi-scale microscopy approaches seems to be essential in order to investigate their complexity and take advantage of their high innovation potential. Links between these techniques and the interest to develop a multi-analytical approach to investigate scientific questions dealing with powder functionality are discussed in the second part of the review. Finally, some techniques used in others fields and showing promising possibilities in the food powder domain will be highlighted.

P-polarized reflectance spectroscopy: A high sensitive real-time monitoring technique to study surface kinetics under steady state epitaxial deposition conditions

NASA Technical Reports Server (NTRS)

Dietz, Nikolaus; Bachmann, Klaus J.

1995-01-01

This paper describes the results of real-time optical monitoring of epitaxial growth processes by p-polarized reflectance spectroscopy (PRS) using a single wavelength application under pulsed chemical beam epitaxy (PCBE) condition. The high surface sensitivity of PRS allows the monitoring of submonolayer precursors coverage on the surface as shown for GaP homoepitaxy and GaP on Si heteroepitaxy as examples. In the case of heteroepitaxy, the growth rate and optical properties are revealed by PRS using interference oscillations as they occur during growth. Super-imposed on these interference oscillations, the PRS signal exhibits a fine structure caused by the periodic alteration of the surface chemistry by the pulsed supply of chemical precursors. This fine structure is modeled under conditions where the surface chemistry cycles between phosphorus supersaturated and phosphorus depleted surfaces. The mathematical model describes the fine structure using a surface layer that increases during the tertiarybutyl phosphine (TBP) supply and decreases during and after the triethylgallium (TEG) pulse, which increases the growing GaP film thickness. The imaginary part of the dielectric function of the surface layer is revealed from the turning points in the fine structure, where the optical response to the first precursor pulse in the cycle sequence changes sign. The amplitude of the fine structure is determined by the surface layer thickness and the complex dielectric functions for the surface layer with the underlying bulk film. Surface kinetic data can be obtained by analyzing the rise and decay transients of the fine structure.

Ferritins: dynamic management of biological iron and oxygen chemistry.

PubMed

Liu, Xiaofeng; Theil, Elizabeth C

2005-03-01

Ferritins are spherical, cage-like proteins with nanocavities formed by multiple polypeptide subunits (four-helix bundles) that manage iron/oxygen chemistry. Catalytic coupling yields diferric oxo/hydroxo complexes at ferroxidase sites in maxi-ferritin subunits (24 subunits, 480 kDa; plants, animals, microorganisms). Oxidation occurs at the cavity surface of mini-ferritins/Dps proteins (12 subunits, 240 kDa; bacteria). Oxidation products are concentrated as minerals in the nanocavity for iron-protein cofactor synthesis (maxi-ferritins) or DNA protection (mini-ferritins). The protein cage and nanocavity characterize all ferritins, although amino acid sequences diverge, especially in bacteria. Catalytic oxidation/di-iron coupling in the protein cage (maxi-ferritins, 480 kDa; plants, bacteria and animal cell-specific isoforms) or on the cavity surface (mini-ferritins/Dps proteins, 280 kDa; bacteria) initiates mineralization. Gated pores (eight or four), symmetrically arranged, control iron flow. The multiple ferritin functions combine pore, channel, and catalytic functions in compact protein structures required for life and disease response.

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

Geochemistry of Rock Samples Collected from the Iron Hill Carbonatite Complex, Gunnison County, Colorado

USGS Publications Warehouse

Van Gosen, Bradley S.

2008-01-01

A study conducted in 2006 by the U.S. Geological Survey collected 57 surface rock samples from nine types of intrusive rock in the Iron Hill carbonatite complex. This intrusive complex, located in Gunnison County of southwestern Colorado, is known for its classic carbonatite-alkaline igneous geology and petrology. The Iron Hill complex is also noteworthy for its diverse mineral resources, including enrichments in titanium, rare earth elements, thorium, niobium (columbium), and vanadium. This study was performed to reexamine the chemistry and metallic content of the major rock units of the Iron Hill complex by using modern analytical techniques, while providing a broader suite of elements than the earlier published studies. The report contains the geochemical analyses of the samples in tabular and digital spreadsheet format, providing the analytical results for 55 major and trace elements.

Investigations of nitrogen oxide plasmas: Fundamental chemistry and surface reactivity and monitoring student perceptions in a general chemistry recitation

NASA Astrophysics Data System (ADS)

Blechle, Joshua M.

Part I of this dissertation focuses on investigations of nitrogen oxide plasma systems. With increasing concerns over the environmental presence of NxOy species, there is growing interest in utilizing plasma-assisted conversion techniques. Advances, however, have been limited because of the lack of knowledge regarding the fundamental chemistry of these plasma systems. Understanding the kinetics and thermodynamics of processes in these systems is vital to realizing their potential in a range of applications. Unraveling the complex chemical nature of these systems, however, presents numerous challenges. As such, this work serves as a foundational step in the diagnostics and assessment of these NxOy plasmas. The partitioning of energy within the plasma system is essential to unraveling these complications as it provides insight into both gas and surface reactivity. To obtain this information, techniques such as optical emission spectroscopy (OES), broadband absorption spectroscopy (BAS), and laser induced fluorescence (LIF) were utilized to determine species energetics (vibrational, rotational, translational temperatures). These temperature data provide mechanistic insight and establish the relationships between system parameters and energetic outcomes. Additionally, these data are also correlated to surface reactivity data collected with the Imaging of Radicals Interacting with Surfaces (IRIS) technique. IRIS data demonstrate the relationship between internal temperatures of radicals and their observed surface scatter coefficients (S), the latter of which is directly related to surface reactivity (R) [R = 1-S]. Furthermore, time-resolved (TR) spectroscopic techniques, specifically TR-OES, revealed kinetic trends in NO and N2 formation from a range of precursors (NO, N2O, N2/O2). By examining the rate constants associated with the generation and destruction of various plasma species we can investigate possible mechanistic implications. All told, such data provides unparalleled insight into the chemistry of these plasma systems. Part II of this work is focused on understanding the efficacy of a general chemistry recitation program. Such programs can be an valuable tool for improving students' problem solving skills and understanding using methods that are difficult to implement in large lecture settings. Here, general chemistry students at Colorado State University participated in a variety of recitation activities throughout the first semester of a 2-semester general chemistry sequence, including peer-led exercises, games, and scaffolded worksheets. Through weekly surveys, students were asked to evaluate and assess recitation activities for both interest and effectiveness as part of their course homework. Also included in these survey assignments were content questions relevant to the weekly themes, providing a measure of student learning of recitation topics. Student opinions were correlated with content retention, and these data were compared against student responses to a pre-survey administered before the first recitation session. This analysis allows for monitoring students' expectations of recitation courses and how well those expectations are met through the various types of activities employed. Ultimately, this work has found that students have positive feeling with respect to individual assignments, but that perspectives on chemistry and the course in general decrease dramatically from the beginning to the end of the semester. Thus, this work can serve as a significant starting points for future efforts to monitor and record student perceptions in the general chemistry recitation classroom, leading to further investigation into the source of changing attitudes and the role that week-to-week activities have on global course attitudes.

Simulating the formation of carbon-rich molecules on an idealized graphitic surface

NASA Astrophysics Data System (ADS)

Marshall, David W.; Sadeghpour, H. R.

2016-01-01

There is accumulating evidence for the presence of complex molecules, including carbon-bearing and organic molecules, in the interstellar medium. Much of this evidence comes to us from studies of chemical composition, photo- and mass spectroscopy in cometary, meteoritic and asteroid samples, indicating a need to better understand the surface chemistry of astrophysical objects. There is also considerable interest in the origins of life-forming and life-sustaining molecules on the Earth. Here, we perform reactive molecular dynamics simulations to probe the formation of carbon-rich molecules and clusters on carbonaceous surfaces resembling dust grains and meteoroids. Our results show that large chains form on graphitic surfaces at low temperatures (100-500 K) and smaller fullerene-like molecules form at higher temperatures (2000-3000 K). The formation is faster on the surface than in the gas at low temperatures but slower at high temperatures as surface interactions prevent small clusters from coagulation. We find that for efficient formation of molecular complexity, mobility about the surface is important and helps to build larger carbon chains on the surface than in the gas phase at low temperatures. Finally, we show that the temperature of the surface strongly determines what kind of structures forms and that low turbulent environments are needed for efficient formation.

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

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

2017-02-17

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

VACUUM ULTRAVIOLET PHOTOABSORPTION SPECTRA OF NITRILE ICES FOR THEIR IDENTIFICATION ON PLUTO

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

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N{sub 2}), methane (CH{sub 4}), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH{sub 3}CN), propionitrile (CH{sub 3}CH{sub 2}CN), butyronitrile (CH{sub 3}CH{sub 2}CH{sub 2}CN), and isobutyronitrile ((CH{sub 3}){sub 2}CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compoundsmore » we propose that such nitriles may be identified from the ALICE payload on board New Horizons .« less

Multiscale Simulations of ALD in Cross Flow Reactors

DOE PAGES

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

2014-08-13

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

Chemical Control of Charge Trapping and Charge Transfer Processes at the Organic-Inorganic Interface within Quantum Dot-Organic Complexes

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

Weiss, Emily A.

Within the research program funded through the Early Career Research Award we designed complexes of colloidal semiconductor quantum dots (QDs) and organic molecules in which the interfacial chemistry controls the electronic structure and dynamics of the excitonic state of the QD. The program included two main projects; (1) investigation of the mechanisms by which organic surfactants control the quantum confinement of excitonic charge carriers; and (2) development of models for electron transfer between QDs and adsorbed molecules as a function of interfacial chemistry. This project was extremely successful in that our achievements in those two areas addressed the great majoritymore » of questions we outlined in the original proposal and answered questions I did not think to ask in that original proposal. Our work led to the discovery of “exciton delocalizing ligands”, which change the electronic structure of colloidal semiconductor nanocrystals by altering, with small synthetic modifications to their surfaces, their most defining characteristic – the quantum confinement of their excited states. It also led to detailed, quantitative descriptions of how the surface chemistry of a QD dictates, thermodynamically and kinetically, the probability of exchange of electrons between the QD and a small molecule. We used two of the three major techniques in the proposal (transient photoluminescence and transient absorption). Electrogenerated chemiluminescence was also proposed, but was too technically difficult with these systems to be useful. Instead, NMR spectroscopy emerged as a major analytical tool in our studies. With the fundamental advancements we made with this project, we believe that we can design QDs to be the next great class of visible-light photocatalysts.« less

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.

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.

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

Toward selective, sensitive, and discriminative detection of Hg(2+) and Cd(2+)via pH-modulated surface chemistry of glutathione-capped gold nanoclusters.

PubMed

Huang, Pengcheng; Li, Sha; Gao, Nan; Wu, Fangying

2015-11-07

Heavy metal pollution can exert severe effects on the environment and human health. Simple, selective, and sensitive detection of heavy metal ions, especially two or more, using a single probe, is thereby of great importance. In this study, we report a new and facile strategy for discriminative detection of Hg(2+) and Cd(2+) with high selectivity and sensitivity via pH-modulated surface chemistry of the glutathione-capped gold NCs (GSH-Au NCs). By simply adjusting pH values of the colloidal solution of the NCs, Hg(2+) could specifically turn off the fluorescence under acidic pH, however, Cd(2+) could exclusively turn on the fluorescence under alkaline pH. This enables the NCs to serve as a dual fluorescent sensor for Hg(2+) and Cd(2+). We demonstrate that these two opposing sensing modes are presumably due to different interaction mechanisms: Hg(2+) induces aggregation by dissociating GSH from the Au surface via robust coordination and, Cd(2+) could passivate the Au surface by forming a Cd-GSH complex with a compact structure. Finally, the present strategy is successfully exploited to separately determine Hg(2+) and Cd(2+) in environmental water samples.

Reversible Immobilization of Proteins in Sensors and Solid-State Nanopores.

PubMed

Ananth, Adithya; Genua, María; Aissaoui, Nesrine; Díaz, Leire; Eisele, Nico B; Frey, Steffen; Dekker, Cees; Richter, Ralf P; Görlich, Dirk

2018-05-01

The controlled functionalization of surfaces with proteins is crucial for many analytical methods in life science research and biomedical applications. Here, a coating for silica-based surfaces is established which enables stable and selective immobilization of proteins with controlled orientation and tunable surface density. The coating is reusable, retains functionality upon long-term storage in air, and is applicable to surfaces of complex geometry. The protein anchoring method is validated on planar surfaces, and then a method is developed to measure the anchoring process in real time using silicon nitride solid-state nanopores. For surface attachment, polyhistidine tags that are site specifically introduced into recombinant proteins are exploited, and the yeast nucleoporin Nsp1 is used as model protein. Contrary to the commonly used covalent thiol chemistry, the anchoring of proteins via polyhistidine tag is reversible, permitting to take proteins off and replace them by other ones. Such switching in real time in experiments on individual nanopores is monitored using ion conductivity. Finally, it is demonstrated that silica and gold surfaces can be orthogonally functionalized to accommodate polyhistidine-tagged proteins on silica but prevent protein binding to gold, which extends the applicability of this surface functionalization method to even more complex sensor devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

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

2017-05-02

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

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.

Metal dependent motif transition in a self-assembled monolayer of bipyridine derivatives via coordination: An STM study.

PubMed

Wang, Yi; Yuan, Qunhui; Xu, Hongbo; Zhu, Xuefeng; Gan, Wei

2016-07-21

Low-dimensional molecular motifs with diversity developed via the on-surface chemistry are attracting growing interest for their potential in advanced nanofabrication. In this work, scanning tunneling microscopy was employed to investigate the in situ and ex situ metal coordinations between 4,4'-ditetradecyl-2,2'-bipyridine (bpy) and Zn(ii) or Cu(ii) ions at a highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface under ambient conditions. The results demonstrate that the bpy adopts a flat-lying orientation with its substituted alkyl chains in a tail-to-tail arrangement in a bpy monolayer. For the in situ coordination, the bpy/Zn(ii) and bpy/Cu(ii) complexes are aligned in edge-on fashions, wherein the bpy stands vertically on the HOPG surface and interdigitates at the alkyl chains. In the two-dimensional arrays of ex situ coordinated complexes, metal dependent motifs have been observed with Zn(ii) and Cu(ii), wherein the bipyridine moieties are parallel to the graphite surface. These results suggest that the desired on-surface coordination architectures may be achieved by the intentional selection of the metal centers.

Effect of adsorbed films on friction of Al2O3-metal systems

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1976-01-01

The kinetic friction of polycrystalline Al2O3 sliding on Cu, Ni, and Fe in ultrahigh vacuum was studied as a function of the surface chemistry of the metal. Clean metal surfaces were exposed to O2, Cl2, C2H4, and C2H3Cl, and the change in friction due to the adsorbed species was observed. Auger electron spectroscopy assessed the elemental composition of the metal surface. It was found that the systems exposed to Cl2 exhibited low friction, interpreted as the van der Waals force between the Al2O3 and metal chloride. The generation of metal oxide by oxygen exposures resulted in an increase in friction, interpreted as due to strong interfacial bonds established by reaction of metal oxide with Al2O3 to form the complex oxide (spinel). The only effect of C2H4 was to increase the friction of the Fe system, but C2H3Cl exposures decreases friction in both Ni and Fe systems, indicating the dominance of the chlorine over the ethylene complex on the surface

Design and functionalization of photocatalytic systems within mesoporous silica.

PubMed

Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

2014-06-01

In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

2017-05-19

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

Chemical studies of elements with Z ⩾ 104 in gas phase

NASA Astrophysics Data System (ADS)

Türler, Andreas; Eichler, Robert; Yakushev, Alexander

2015-12-01

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

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

NASA Astrophysics Data System (ADS)

Montero, J. M.; Isaacs, M. A.; Lee, A. F.; Lynam, J. M.; Wilson, K.

2016-04-01

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 - sites to OH- and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C-H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

Nano-Bio Interactions of Porous and Nonporous Silica Nanoparticles of Varied Surface Chemistry: A Structural, Kinetic, and Thermodynamic Study of Protein Adsorption from RPMI Culture Medium.

PubMed

Lehman, Sean E; Mudunkotuwa, Imali A; Grassian, Vicki H; Larsen, Sarah C

2016-01-26

Understanding complex chemical changes that take place at nano-bio interfaces is of great concern for being able to sustainably implement nanomaterials in key applications such as drug delivery, imaging, and environmental remediation. Typical in vitro assays use cell viability as a proxy to understanding nanotoxicity but often neglect how the nanomaterial surface can be altered by adsorption of solution-phase components in the medium. Protein coronas form on the nanomaterial surface when incubated in proteinaceous solutions. Herein, we apply a broad array of techniques to characterize and quantify protein corona formation on silica nanoparticle surfaces. The porosity and surface chemistry of the silica nanoparticles have been systematically varied. Using spectroscopic tools such as FTIR and circular dichroism, structural changes and kinetic processes involved in protein adsorption were evaluated. Additionally, by implementing thermogravimetric analysis, quantitative protein adsorption measurements allowed for the direct comparison between samples. Taken together, these measurements enabled the extraction of useful chemical information on protein binding onto nanoparticles in solution. Overall, we demonstrate that small alkylamines can increase protein adsorption and that even large polymeric molecules such as poly(ethylene glycol) (PEG) cannot prevent protein adsorption in these systems. The implications of these results as they relate to further understanding nano-bio interactions are discussed.

Convection and chemistry effects in CVD: A 3-D analysis for silicon deposition

NASA Technical Reports Server (NTRS)

Gokoglu, S. A.; Kuczmarski, M. A.; Tsui, P.; Chait, A.

1989-01-01

The computational fluid dynamics code FLUENT has been adopted to simulate the entire rectangular-channel-like (3-D) geometry of an experimental CVD reactor designed for Si deposition. The code incorporated the effects of both homogeneous (gas phase) and heterogeneous (surface) chemistry with finite reaction rates of important species existing in silane dissociation. The experiments were designed to elucidate the effects of gravitationally-induced buoyancy-driven convection flows on the quality of the grown Si films. This goal is accomplished by contrasting the results obtained from a carrier gas mixture of H2/Ar with the ones obtained from the same molar mixture ratio of H2/He, without any accompanying change in the chemistry. Computationally, these cases are simulated in the terrestrial gravitational field and in the absence of gravity. The numerical results compare favorably with experiments. Powerful computational tools provide invaluable insights into the complex physicochemical phenomena taking place in CVD reactors. Such information is essential for the improved design and optimization of future CVD reactors.

Self-organizing biochemical cycles

NASA Technical Reports Server (NTRS)

Orgel, L. E.; Bada, J. L. (Principal Investigator)

2000-01-01

I examine the plausibility of theories that postulate the development of complex chemical organization without requiring the replication of genetic polymers such as RNA. One conclusion is that theories that involve the organization of complex, small-molecule metabolic cycles such as the reductive citric acid cycle on mineral surfaces make unreasonable assumptions about the catalytic properties of minerals and the ability of minerals to organize sequences of disparate reactions. Another conclusion is that data in the Beilstein Handbook of Organic Chemistry that have been claimed to support the hypothesis that the reductive citric acid cycle originated as a self-organized cycle can more plausibly be interpreted in a different way.

A Review of Hypersonics Aerodynamics, Aerothermodynamics and Plasmadynamics Activities within NASA's Fundamental Aeronautics Program

NASA Technical Reports Server (NTRS)

Salas, Manuel D.

2007-01-01

The research program of the aerodynamics, aerothermodynamics and plasmadynamics discipline of NASA's Hypersonic Project is reviewed. Details are provided for each of its three components: 1) development of physics-based models of non-equilibrium chemistry, surface catalytic effects, turbulence, transition and radiation; 2) development of advanced simulation tools to enable increased spatial and time accuracy, increased geometrical complexity, grid adaptation, increased physical-processes complexity, uncertainty quantification and error control; and 3) establishment of experimental databases from ground and flight experiments to develop better understanding of high-speed flows and to provide data to validate and guide the development of simulation tools.

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

NASA Astrophysics Data System (ADS)

Elder, Robert M.

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

Humic Acid Effects on the Transport of Colloidal Particles in Unsaturated Porous Media: Humic Acid Dosage, pH, and Ionic Strength Dependence

NASA Astrophysics Data System (ADS)

Morales, V. L.; Gao, B.; Steenhuis, T. S.

2008-12-01

Soil colloids and biocolloids can facilitate contaminant transport within the soil profile through the complexation of pollutants previously thought to have limited mobility. Dissolved organic substances are qualitatively known to alter the behavior of colloids and surface chemistry of soil particles in aquatic environments when adsorbed to their surfaces. Specifically, it has been observed that even small amounts of adsorbed humic acids result in a pronounced increase in colloid mobility in saturated porous systems, presumably by a combination of electrostatic and steric stabilization. However, the degree to which adsorbed humic acids stabilize colloidal suspension is highly sensitive to the system's solution chemistry; mainly in terms of pH, ionic strength, and metal ions present. The objective of this study is to expound quantitatively on the role that combined stabilizing and destabilizing solution chemistry components have on humic acid-colloid transport in unsaturated media by isolating experimentally some underlying mechanisms that regulate colloid transport in realistic aquatic systems. We hypothesize that in chemically heterogeneous porous media, with ionic strength values above 0 and pH ranges from 4 to 9, the effect of humic acid on colloid suspensions cannot be simply characterized by increased stability and mobility. That a critical salt concentration must exists for a given humic acid concentration and pH, above which the network of humic acid collapses by forming coordination complexes with other suspended or adsorbed humic acids, thus increasing greatly the retention of colloids in the porous medium by sweep flocculation. In addition, capillary forces in unsaturated media may contribute further to overcome repulsive forces that prevent flocculation of humic acid-colloid complexes. The experimental work in this study will include: jar tests to determine critical solution concentration combinations for desired coagulation/flocculation rates, column experiments to obtain effluent breakthrough data, in-situ visualization of internal processes with bright field microscopy, batch adsorption measurements, and changes in hydrophobic interaction energy of colloid and media surfaces for realistic aqueous ionic strength and pH ranges. Such experimental results are expected to provide sufficient evidence to corroborate our speculations that under natural soil water conditions, humic acids may greatly contribute to the immobilization of colloidal particles.

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1998-01-01

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where pH (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as pH increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Toward self-organization and complex matter.

PubMed

Lehn, Jean-Marie

2002-03-29

Beyond molecular chemistry based on the covalent bond, supramolecular chemistry aims at developing highly complex chemical systems from components interacting through noncovalent intermolecular forces. Over the past quarter century, supramolecular chemistry has grown into a major field and has fueled numerous developments at the interfaces with biology and physics. Some of the conceptual advances and future challenges are profiled here.

A Valid and Reliable Instrument for Cognitive Complexity Rating Assignment of Chemistry Exam Items

ERIC Educational Resources Information Center

Knaus, Karen; Murphy, Kristen; Blecking, Anja; Holme, Thomas

2011-01-01

The design and use of a valid and reliable instrument for the assignment of cognitive complexity ratings to chemistry exam items is described in this paper. Use of such an instrument provides a simple method to quantify the cognitive demands of chemistry exam items. Instrument validity was established in two different ways: statistically…

Pedagogy-Based-Technology and Chemistry Students' Performance in Higher Institutions: A Case of Debre Berhan University

ERIC Educational Resources Information Center

Demissie, Tesfaye; Ochonogor, Chukunoye E.; Engida, Temechegn

2011-01-01

Many students have difficulty in learning abstract and complex lessons of chemistry. This study investigated how students develop their understandings of abstract and complex lessons in chemistry with the aid of visualizing tools: animation, simulation and video that allow them to build clear concepts. Animation, simulation and video enable…

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

PubMed

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

2018-03-07

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

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.

Composition and chemistry of Titan's thermosphere and ionosphere.

PubMed

Vuitton, V; Yelle, R V; Lavvas, P

2009-02-28

Titan has long been known to harbour the richest atmospheric chemistry in the Solar System. Until recently, it had been believed that complex hydrocarbons and nitriles were produced through neutral chemistry that would eventually lead to the formation of micrometre sized organic aerosols. However, recent measurements by the Cassini spacecraft are drastically changing our understanding of Titan's chemistry. The Ion and Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) revealed an extraordinary complex ionospheric composition. INMS detected roughly 50 positive ions with m/z<100 and a density higher than 0.1cm-3. CAPS provided evidence for heavy (up to 350amu) positively and negatively charged (up to 4000amu) ions. These observations all indicate that Titan's ionospheric chemistry is incredibly complex and that molecular growth starts in the upper atmosphere rather than at lower altitude. Here, we review the recent progress made on ionospheric chemistry. The presence of heavy neutrals in the upper atmosphere has been inferred as a direct consequence of the presence of complex positive ions. Benzene (C6H6) is created by ion chemistry at high altitudes and its main photolysis product, the phenyl radical (C6H5), is at the origin of the formation of aromatic species at lower altitude.

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

Geochemistry of the Birch Creek Drainage Basin, Idaho

USGS Publications Warehouse

Swanson, Shawn A.; Rosentreter, Jeffrey J.; Bartholomay, Roy C.; Knobel, LeRoy L.

2003-01-01

The U.S. Survey and Idaho State University, in cooperation with the U.S. Department of Energy, are conducting studies to describe the chemical character of ground water that moves as underflow from drainage basins into the eastern Snake River Plain aquifer (ESRPA) system at and near the Idaho National Engineering and Environmental Laboratory (INEEL) and the effects of these recharge waters on the geochemistry of the ESRPA system. Each of these recharge waters has a hydrochemical character related to geochemical processes, especially water-rock interactions, that occur during migration to the ESRPA. Results of these studies will benefit ongoing and planned geochemical modeling of the ESRPA at the INEEL by providing model input on the hydrochemical character of water from each drainage basin. During 2000, water samples were collected from five wells and one surface-water site in the Birch Creek drainage basin and analyzed for selected inorganic constituents, nutrients, dissolved organic carbon, tritium, measurements of gross alpha and beta radioactivity, and stable isotopes. Four duplicate samples also were collected for quality assurance. Results, which include analyses of samples previously collected from four other sites, in the basin, show that most water from the Birch Creek drainage basin has a calcium-magnesium bicarbonate character. The Birch Creek Valley can be divided roughly into three hydrologic areas. In the northern part, ground water is forced to the surface by a basalt barrier and the sampling sites were either surface water or shallow wells. Water chemistry in this area was characterized by simple evaporation models, simple calcite-carbon dioxide models, or complex models involving carbonate and silicate minerals. The central part of the valley is filled by sedimentary material and the sampling sites were wells that are deeper than those in the northern part. Water chemistry in this area was characterized by simple calcite-dolomite-carbon dioxide models. In the southern part, ground water enters the ESRPA. In this area, the sampling sites were wells with depths and water levels much deeper than those in the northern and central parts of the valley. The calcium and carbon water chemistry in this area was characterized by a simple calcite-carbon dioxide model, but complex calcite-silicate models more accurately accounted for mass transfer in these areas. Throughout the geochemical system, calcite precipitated if it was an active phase in the models. Carbon dioxide either precipitated (outgassed) or dissolved depending on the partial pressure of carbon dioxide in water from the modeled sites. Dolomite was an active phase only in models from the central part of the system. Generally the entire geochemical system could be modeled with either evaporative models, carbonate models, or carbonate-silicate models. In both of the latter types of models, a significant amount of calcite precipitated relative to the mass transfer to and from the other active phases. The amount of calcite precipitated in the more complex models was consistent with the amount of calcite precipitated in the simpler models. This consistency suggests that, although the simpler models can predict calcium and carbon concentrations in Birch Creek Valley ground and surface water, silicate-mineral-based models are required to account for the other constituents. The amount of mass transfer to and from the silicate mineral phases was generally small compared with that in the carbonate phases. It appears that the water chemistry of well USGS 126B represents the chemistry of water recharging the ESRPA by means of underflow from the Birch Creek Valley.

The low salinity effect at high temperatures

DOE PAGES

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

2017-04-05

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

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, J.; Haggerty, R.; Stoliker, D.L.; Kent, D.B.; Istok, J.D.; Greskowiak, J.; Zachara, J.M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry. Copyright 2011 by the American Geophysical Union.

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

The low salinity effect at high temperatures

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

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

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

Versatile derivatives of carbohydrate-binding modules for imaging of complex carbohydrates approaching the molecular level of resolution.

PubMed

Ding, Shi-You; Xu, Qi; Ali, Mursheda K; Baker, John O; Bayer, Edward A; Barak, Yoav; Lamed, Raphael; Sugiyama, Junji; Rumbles, Garry; Himmel, Michael E

2006-10-01

The innate binding specificity of different carbohydrate-binding modules (CBMs) offers a versatile approach for mapping the chemistry and structure of surfaces that contain complex carbohydrates. We have employed the distinct recognition properties of a double His-tagged recombinant CBM tagged with semiconductor quantum dots for direct imaging of crystalline cellulose at the molecular level of resolution, using transmission and scanning transmission electron microscopy. In addition, three different types of CBMs from families 3, 6, and 20 that exhibit different carbohydrate specificities were each fused with either green fluorescent protein (GFP) or red fluorescent protein (RFP) and employed for double-labeling fluorescence microscopy studies of primary cell walls and various mixtures of complex carbohydrate target molecules. CBM probes can be used for characterizing both native complex carbohydrates and engineered biomaterials.

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.

Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

PubMed

Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

2015-10-14

Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

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

NASA Astrophysics Data System (ADS)

Bokarev, Valery P.; Krasnikov, Gennady Ya

2018-02-01

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

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

PubMed

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

2001-04-18

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

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.

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.

Magnetic purification of curcumin from Curcuma longa rhizome by novel naked maghemite nanoparticles.

PubMed

Magro, Massimiliano; Campos, Rene; Baratella, Davide; Ferreira, Maria Izabela; Bonaiuto, Emanuela; Corraducci, Vittorino; Uliana, Maíra Rodrigues; Lima, Giuseppina Pace Pereira; Santagata, Silvia; Sambo, Paolo; Vianello, Fabio

2015-01-28

Naked maghemite nanoparticles, namely, surface active maghemite nanoparticles (SAMNs), characterized by a diameter of about 10 nm, possessing peculiar colloidal stability, surface chemistry, and superparamagnetism, present fundamental requisites for the development of effective magnetic purification processes for biomolecules in complex matrices. Polyphenolic molecules presenting functionalities with different proclivities toward iron chelation were studied as probes for testing SAMN suitability for magnetic purification. Thus, the binding efficiency and reversibility on SAMNs of phenolic compounds of interest in the pharmaceutical and food industries, namely, catechin, tyrosine, hydroxytyrosine, ferulic acid, coumaric acid, rosmarinic acid, naringenin, curcumin, and cyanidin-3-glucoside, were evaluated. Curcumin emerged as an elective compound, suitable for magnetic purification by SAMNs from complex matrices. A combination of curcumin, demethoxycurcumin, and bis-demethoxycurcumin was recovered by a single magnetic purification step from extracts of Curcuma longa rhizomes, with a purity >98% and a purification yield of 45%, curcumin being >80% of the total purified curcuminoids.

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

PubMed Central

Han, Lili; Meng, Qingping; Wang, Deli; Zhu, Yimei; Wang, Jie; Du, Xiwen; Stach, Eric A.; Xin, Huolin L.

2016-01-01

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. This work characterizes the pathways that can control the morphology in binary oxide materials. PMID:27928998

Red mud carbonation using carbon dioxide: Effects of carbonate and calcium ions on goethite surface properties and settling.

PubMed

Liang, Gaojie; Chen, Wenmi; Nguyen, Anh V; Nguyen, Tuan A H

2018-05-01

Carbonation using CO 2 appears as an attractive solution for disposing of red mud suspensions, an aluminum industry hazardous waste since it also offers an option for CO 2 sequestration. Here we report the novel findings that CO 3 2- together with Ca 2+ can significantly affect the surface properties and settling of goethite, a major component of red mud. Specifically, their effects on the goethite surface chemistry, colloidal interaction forces and settling in alkaline solutions are investigated. The surface potential becomes more negative by the formation of carbonate inner-sphere complexes on goethite surface. It is consistent with the strong repulsion, decreased particle size and settling velocity with increased carbonate concentrations as measured by atomic force microscopy, particle size analysis, and particle settling. Adding Ca 2+ that forms outer-sphere complexes with pre-adsorbed carbonate changes goethite surface charge negligibly. Changing repulsion to the attraction between goethite surfaces by increasing calcium dosage indicates the surface bridging, in accordance with the increased settling velocity. The adverse effect of carbonate on goethite flocculation is probably due to its specific chemisorption and competition with flocculants. By forming outer-sphere complexes together with the flocculant-calcium bridging effect, calcium ions can eliminate the negative influence of carbonate and improve the flocculation of goethite particles. These findings contribute to a better understanding of goethite particle interaction with salt ions and flocculants in controlling the particle behavior in the handling processes, including the red mud carbonation. Copyright © 2018 Elsevier Inc. All rights reserved.

Quantum chemistry study of dielectric materials deposition

NASA Astrophysics Data System (ADS)

Widjaja, Yuniarto

The drive to continually decrease the device dimensions of integrated circuits in the microelectronics industry requires that deposited films approach subnanometer thicknesses. Hence, a fundamental understanding of the physics and chemistry of film deposition is important to obtain better control of the properties of the deposited film. We use ab initio quantum chemistry calculations to explore chemical reactions at the atomic level. Important thermodynamic and kinetic parameters are then obtained, which can then be used as inputs in constructing first-principles based reactor models. Studies of new systems for which data are not available can be conducted as well. In this dissertation, we use quantum chemistry simulations to study the deposition of gate dielectrics for metal-oxide-semiconductor (MOS) devices. The focus of this study is on heterogeneous reactions between gaseous precursors and solid surfaces. Adsorbate-surface interactions introduce additional degrees of complexity compared to the corresponding gas-phase or solid-state reactions. The applicability and accuracy of cluster approximations to represent solid surfaces are first investigated. The majority of our results are obtained using B3LYP density functional theory (DFT). The structures of reactants, products, and transition states are obtained, followed by calculations of thermochemical and kinetic properties. Whenever experimental data are available, qualitative and/or quantitative comparisons are drawn. Atomistic mechanisms and the energetics of several reactions leading to the deposition of SiO2, Si3N4, and potential new high-kappa materials such as ZrO2, HfO2, and Al 2O3 have been explored in this dissertation. Competing reaction pathways are explored for each of the deposition reactions studied. For example, the potential energy surface (PES) for ZrO2 ALD shows that the reactions proceed through a trapping-mediated mechanism, which results in a competition between desorption and decomposition of the gaseous reactants, i.e. ZrCl4 and H2O, on the ZrO2 surface. This competition results in relatively low saturation coverage, which consequently leads to a slow growth rate and possibly affects the thickness uniformity and conformality. The insights gained are then used to systematically improve deposition reactions. For instance, from the ZrO2 ALD PES, we are able to suggest the use of high temperature and pressure to obtain higher surface coverage.

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

EPA Science Inventory

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

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

DTIC Science & Technology

1988-06-30

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

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Investigation of anticancer properties of caffeinated complexes via computational chemistry methods

NASA Astrophysics Data System (ADS)

Sayin, Koray; Üngördü, Ayhan

2018-03-01

Computational investigations were performed for 1,3,7-trimethylpurine-2,6-dione, 3,7-dimethylpurine-2,6-dione, their Ru(II) and Os(III) complexes. B3LYP/6-311 ++G(d,p)(LANL2DZ) level was used in numerical calculations. Geometric parameters, IR spectrum, 1H-, 13C and 15N NMR spectrum were examined in detail. Additionally, contour diagram of frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) maps, MEP contour and some quantum chemical descriptors were used in the determination of reactivity rankings and active sites. The electron density on the surface was similar to each other in studied complexes. Quantum chemical descriptors were investigated and the anticancer activity of complexes were more than cisplatin and their ligands. Additionally, molecular docking calculations were performed in water between related complexes and a protein (ID: 3WZE). The most interact complex was found as Os complex. The interaction energy was calculated as 342.9 kJ/mol.

Mineralogical transformations controlling acid mine drainage chemistry

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

Peretyazhko, Tetyana; Zachara, John M.; Boily, Jean F.

2009-05-30

The role of Fe(III) minerals in controlling acid mine drainage (AMD) chemistry was studied using samples from two AMD sites [Gum Boot (GB) and Fridays-2 (FR)] located in northern Pennsylvania. Chemical extractions, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were used to identify and characterize Fe(III) phases. The mineralogical analysis revealed that schwertmannite and goethite were the principal Fe(III) phases in the sediments. Schwertmannite transformation occurred at the GB site where poorly-crystallized goethite rich in surface-bound sulfate was initially formed. In contrast, no schwertmannite transformation occurred at the FR site. The goethite in GBmore » sediments had spherical morphology due to preservation of schwertmannite structure by adsorbed sulfate. Results of chemical extractions showed that poorly-crystallized goethite was subject to further crystallization accompanied by sulfate desorption. Changes in sulfate speciation preceded its desorption, with a conversion of bidentate- to monodentate-bound sulfate surface complexes. Laboratory sediment incubation experiments were conducted to evaluate the effect of mineral transformation on water chemistry. Incubation experiments were carried out with schwertmannite-containing sediments and AMD waters with different pH and chemical composition. The pH decreased to 1.9-2.2 in all suspensions and the concentrations of dissolved Fe and S increased significantly. Regardless of differences in the initial water composition, pH, Fe and S were similar in suspensions of the same sediment. XRD measurements revealed that schwertmannite transformed into goethite in GB and FR sediments during laboratory incubation. The incubation experiment demonstrated that schwertmannite transformation controlled AMD water chemistry during “closed system” laboratory contact.« less

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 Impact of Different Complexity on Numerical Weather Predictions within the Coupled Global Online Modeling System

NASA Astrophysics Data System (ADS)

Zhang, L.; Grell, G. A.; McKeen, S. A.; Ahmadov, R.

2017-12-01

The global Flow-following finite-volume Icosahedra Model (FIM), which was developed in the Global Systems Division of NOAA/ESRL and the Finite-volume cubed-sphere dynamical core (FV3) developed by GFDL, have been coupled online with aerosol and gas-phase chemistry schemes (FIM-Chem and FV3-Chem). Within the aerosol and chemistry modules, the models handle wet and dry deposition, chemical reactions, aerosol direct and semi-direct effect, anthropogenic emissions, biogenic emissions, biomass burning, dust and sea-salt emissions. They are able to provide chemical weather predictions at various spatial resolutions and with different levels of complexity. FIM-Chem is also able to quantify the impact of aerosol on numerical weather predictions (NWP). Currently, three different chemical schemes have been coupled with the FIM model. The simplest aerosol modules are from the GOCART model with its simplified parameterization of sulfur/sulfate chemistry. The photochemical gas-phase mechanism RACM was included to determine the impact of additional complexity on the aerosol and gas simulations. We have also implemented a more sophisticated aerosol scheme that includes secondary organic aerosols (SOA) based on the VBS approach. The model performance has been evaluated by comparing with the ATom-1 observations. FIM-Chem is able to reproduce many observed aerosol and gas features very well. A five-day NWP on 120 km horizontal resolution using FIM-Chem has been done for the end of July, 2016 to quantify the impact of the three different chemical schemes on weather forecasts. Compared to a meteorological run that excludes the model chemical schemes, and is driven only by background AODs from the GFS model, the 5-day forecast results shows significant impact on weather predictions when including the prognostic aerosol schemes. This includes convective precipitation, surface temperature, and 700 hPa air temperature. We also use FIM-Chem to investigate the 2012 South American Biomass Burning Analysis (SAMBBA) campaign period to determine whether more complex chemistry provides benefits for global numerical weather prediction.

Astrochemistry

NASA Astrophysics Data System (ADS)

Millar, T. J.

2015-08-01

In the last 40 years a wide range of molecules, including neutrals, cations and anions, containing up to 13 atoms—in addition to detections of {{\\text{C}}60} and {{\\text{C}}70} —have been found in the harsh environment of the interstellar medium. The exquisite sensitivity and very high spectral and, more recently, spatial resolution, of modern telescopes has enabled the physics of star formation to be probed through rotational line emission. In this article, I review the basic properties of interstellar clouds and the processes that initiate the chemistry and generate chemical complexity, particularly in regions of star and planet formation. Our understanding of astrochemistry has evolved over the years. Before 1990, the general consensus was that molecules were formed in binary, gas-phase, or volume, reactions, most importantly ion-neutral reactions despite the very low ionization in clouds. Since then, observations have indicated unambiguously that there is also a contribution from surface processes, particularly on the icy mantles that form around refractory grain cores in cold, dense gas. The balance between these two processes depends on particular physical conditions and can vary during the life cycle of a particular volume of interstellar cloud. The complex chemistry that occurs in space is driven mostly through interaction of the gas with cosmic ray protons, a source of ionization that enables a rich ion-neutral chemistry. In addition, I show that the interaction between the gas and the dust in cold, dense regions also leads to additional chemical complexity through reactions that take place in ices at only a few tens of degrees above absolute zero. Although densities are low compared to those in terrestrial environments, the extremely long life times of interstellar clouds and their enormous sizes, enable complex molecules to be synthesised and detected. I show that in some instances, particularly in reactions involving deuterium, the rotational populations of reactants, together with spin-selection rules, can determine the detailed abundances. Although the review is mainly focused on regions associated with star formation, I also consider chemistry in other interesting astronomical regions—in the early Universe and in the envelopes formed by mass loss during the final stages of stellar evolution.

Automated discovery and construction of surface phase diagrams using machine learning

DOE PAGES

Ulissi, Zachary W.; Singh, Aayush R.; Tsai, Charlie; ...

2016-08-24

Surface phase diagrams are necessary for understanding surface chemistry in electrochemical catalysis, where a range of adsorbates and coverages exist at varying applied potentials. These diagrams are typically constructed using intuition, which risks missing complex coverages and configurations at potentials of interest. More accurate cluster expansion methods are often difficult to implement quickly for new surfaces. We adopt a machine learning approach to rectify both issues. Using a Gaussian process regression model, the free energy of all possible adsorbate coverages for surfaces is predicted for a finite number of adsorption sites. Our result demonstrates a rational, simple, and systematic approachmore » for generating accurate free-energy diagrams with reduced computational resources. Finally, the Pourbaix diagram for the IrO 2(110) surface (with nine coverages from fully hydrogenated to fully oxygenated surfaces) is reconstructed using just 20 electronic structure relaxations, compared to approximately 90 using typical search methods. Similar efficiency is demonstrated for the MoS 2 surface.« less

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.

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1988-01-01

Tribology, the study of adhesion, friction and wear of materials is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture and friction are discussed.

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1989-01-01

Tribology, the study of adhesion, friction and wear of materials, is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science, and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid-state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture, and friction are discussed.

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

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

2017-02-01

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

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…

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

USGS Publications Warehouse

Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

1999-01-01

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Towards Eco-reflexive Science Education. A Critical Reflection About Educational Implications of Green Chemistry

NASA Astrophysics Data System (ADS)

Sjöström, Jesper; Eilks, Ingo; Zuin, Vânia G.

2016-05-01

The modern world can be described as a globalized risk society. It is characterized by increasing complexity, unpredictable consequences of techno-scientific innovations and production, and its environmental consequences. Therefore, chemistry, just like many other knowledge areas, is in an ongoing process of environmentalization. For example, green chemistry has emerged as a new chemical metadiscipline and movement. The philosophy of green chemistry was originally based on a suggestion of twelve principles for environment-friendly chemistry research and production. The present article problematizes limitations in green chemistry when it comes to education. It argues that the philosophy of green chemistry in the context of education needs to be extended with socio-critical perspectives to form educated professionals and citizens who are able to understand the complexity of the world, to make value-based decisions, and to become able to engage more thoroughly in democratic decision-making on sustainability issues. Different versions of sustainability-oriented science/chemistry education are discussed to sharpen a focus on the most complex type, which is Bildung-oriented, focusing emancipation and leading to eco-reflexive education. The term eco- reflexive is used for a problematizing stance towards the modern risk society, an understanding of the complexity of life and society and their interactions, and a responsibility for individual and collective actions towards socio-ecojustice and global sustainability. The philosophical foundation and characteristics of eco-reflexive science education are sketched on in the article.

Climate, not atmospheric deposition, drives the biogeochemical mass-balance of a mountain watershed

USGS Publications Warehouse

Baron, Jill S.; Heath, Jared

2014-01-01

Watershed mass-balance methods are valuable tools for demonstrating impacts to water quality from atmospheric deposition and chemical weathering. Owen Bricker, a pioneer of the mass-balance method, began applying mass-balance modeling to small watersheds in the late 1960s and dedicated his career to expanding the literature and knowledge of complex watershed processes. We evaluated long-term trends in surface-water chemistry in the Loch Vale watershed, a 660-ha. alpine/subalpine catchment located in Rocky Mountain National Park, CO, USA. Many changes in surface-water chemistry correlated with multiple drivers, including summer or monthly temperature, snow water equivalent, and the runoff-to-precipitation ratio. Atmospheric deposition was not a significant causal agent for surface-water chemistry trends. We observed statistically significant increases in both concentrations and fluxes of weathering products including cations, SiO2, SO4 2−, and ANC, and in inorganic N, with inorganic N being primarily of atmospheric origin. These changes are evident in the individual months June, July, and August, and also in the combined June, July, and August summer season. Increasingly warm summer temperatures are melting what was once permanent ice and this may release elements entrained in the ice, stimulate chemical weathering with enhanced moisture availability, and stimulate microbial nitrification. Weathering rates may also be enhanced by sustained water availability in high snowpack years. Rapid change in the flux of weathering products and inorganic N is the direct and indirect result of a changing climate from warming temperatures and thawing cryosphere.

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

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

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

From single-site tantalum complexes to nanoparticles of Ta x N y and TaO x N y supported on silica: elucidation of synthesis chemistry by dynamic nuclear polarization surface enhanced NMR spectroscopy and X-ray absorption spectroscopy.

PubMed

Mohandas, Janet C; Abou-Hamad, Edy; Callens, Emmanuel; Samantaray, Manoja K; Gajan, David; Gurinov, Andrei; Ma, Tao; Ould-Chikh, Samy; Hoffman, Adam S; Gates, Bruce C; Basset, Jean-Marie

2017-08-01

Air-stable catalysts consisting of tantalum nitride nanoparticles represented as a mixture of Ta x N y and TaO x N y with diameters in the range of 0.5 to 3 nm supported on highly dehydroxylated silica were synthesized from TaMe 5 (Me = methyl) and dimeric Ta 2 (OMe) 10 with guidance by the principles of surface organometallic chemistry (SOMC). Characterization of the supported precursors and the supported nanoparticles formed from them was carried out by IR, NMR, UV-Vis, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopies complemented with XRD and high-resolution TEM, with dynamic nuclear polarization surface enhanced NMR spectroscopy being especially helpful by providing enhanced intensities of the signals of 1 H, 13 C, 29 Si, and 15 N at their natural abundances. The characterization data provide details of the synthesis chemistry, including evidence of (a) O 2 insertion into Ta-CH 3 species on the support and (b) a binuclear to mononuclear transformation of species formed from Ta 2 (OMe) 10 on the support. A catalytic test reaction, cyclooctene epoxidation, was used to probe the supported nanoparticles, with 30% H 2 O 2 serving as the oxidant. The catalysts gave selectivities up to 98% for the epoxide at conversions as high as 99% with a 3.4 wt% loading of Ta present as Ta x N y /TaO x N y .

Science Update: Inorganic Chemistry.

ERIC Educational Resources Information Center

Rawls, Rebecca

1981-01-01

Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

[Application of metal ions and their complexes in medicine II. Application of platina complexes in the treatment of tumor].

PubMed

Nagy, László; Csintalan, Gabriella; Kálmán, Eszter; Nagy, Eniko; Sipos, Pál

2004-01-01

The rapid development of inorganic medical chemistry opens enormous potential for various applications of a range of inorganic substances in the medicine. Thus inorganic chemistry offers real possibilities to pharmaceutical industries, which used to be dominated by organic chemistry alone. The field has particularly been stimulated by the success-story of cisplatin, which is the World's best selling anticancer drug. Nowadays orally administered Pt(IV) complexes with reduced toxicity, and activity against resistant tumors are on various phases of clinical trial.

Synthesis of Some "Cobaloxime" Derivatives: A Demonstration of "Umpolung" in the Reactivity of an Organometallic Complex

NASA Astrophysics Data System (ADS)

Jameson, Donald L.; Grzybowski, Joseph J.; Hammels, Deb E.; Castellano, Ronald K.; Hoke, Molly E.; Freed, Kimberly; Basquill, Sean; Mendel, Angela; Shoemaker, William J.

1998-04-01

This article describes a four-reaction sequence for the synthesis of two organometallic "cobaloxime" derivatives. The concept of "Umpolung" or reversal of reactivity is demonstrated in the preparation of complexes. The complex Co(dmgH)2(4-t-BuPy)Et is formed by the reaction of a cobalt (I) intermediate (cobalt in the role of nucleophile) with ethyl iodide. The complex Co(dmgH)2(4-t-BuPy)Ph is formed by the reaction of PhMgBr with a cobalt (III) intermediate (cobalt in the role of electrophile). All the products contain cobalt in the diamagnetic +3 oxidation state and are readily characterized by proton and carbon NMR. The four reaction sequence may be completed in two 4-hour lab periods. Cobaloximes are well known as model complexes for Vitamin B-12 and the experiment exposes students to aspects of classical coordination chemistry, organometallic chemistry and bioinorganic chemistry. The experiment also illustrates an important reactivity parallel between organic and organometallic chemistry.

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).

Single Aerosol Particle Studies Using Optical Trapping Raman And Cavity Ringdown Spectroscopy

NASA Astrophysics Data System (ADS)

Gong, Z.; Wang, C.; Pan, Y. L.; Videen, G.

2017-12-01

Due to the physical and chemical complexity of aerosol particles and the interdisciplinary nature of aerosol science that involves physics, chemistry, and biology, our knowledge of aerosol particles is rather incomplete; our current understanding of aerosol particles is limited by averaged (over size, composition, shape, and orientation) and/or ensemble (over time, size, and multi-particles) measurements. Physically, single aerosol particles are the fundamental units of any large aerosol ensembles. Chemically, single aerosol particles carry individual chemical components (properties and constituents) in particle ensemble processes. Therefore, the study of single aerosol particles can bridge the gap between aerosol ensembles and bulk/surface properties and provide a hierarchical progression from a simple benchmark single-component system to a mixed-phase multicomponent system. A single aerosol particle can be an effective reactor to study heterogeneous surface chemistry in multiple phases. Latest technological advances provide exciting new opportunities to study single aerosol particles and to further develop single aerosol particle instrumentation. We present updates on our recent studies of single aerosol particles optically trapped in air using the optical-trapping Raman and cavity ringdown spectroscopy.

DNA-mediated engineering of multicomponent enzyme crystals

PubMed Central

Brodin, Jeffrey D.; Auyeung, Evelyn; Mirkin, Chad A.

2015-01-01

The ability to predictably control the coassembly of multiple nanoscale building blocks, especially those with disparate chemical and physical properties such as biomolecules and inorganic nanoparticles, has far-reaching implications in catalysis, sensing, and photonics, but a generalizable strategy for engineering specific contacts between these particles is an outstanding challenge. This is especially true in the case of proteins, where the types of possible interparticle interactions are numerous, diverse, and complex. Herein, we explore the concept of trading protein–protein interactions for DNA–DNA interactions to direct the assembly of two nucleic-acid–functionalized proteins with distinct surface chemistries into six unique lattices composed of catalytically active proteins, or of a combination of proteins and DNA-modified gold nanoparticles. The programmable nature of DNA–DNA interactions used in this strategy allows us to control the lattice symmetries and unit cell constants, as well as the compositions and habit, of the resulting crystals. This study provides a potentially generalizable strategy for constructing a unique class of materials that take advantage of the diverse morphologies, surface chemistries, and functionalities of proteins for assembling functional crystalline materials. PMID:25831510

DNA-mediated engineering of multicomponent enzyme crystals

DOE PAGES

Brodin, Jeffrey D.; Auyeung, Evelyn; Mirkin, Chad A.

2015-03-23

The ability to predictably control the coassembly of multiple nanoscale building blocks, especially those with disparate chemical and physical properties such as biomolecules and inorganic nanoparticles, has far-reaching implications in catalysis, sensing, and photonics, but a generalizable strategy for engineering specific contacts between these particles is an outstanding challenge. This is especially true in the case of proteins, where the types of possible interparticle interactions are numerous, diverse, and complex. In this paper, we explore the concept of trading protein–protein interactions for DNA–DNA interactions to direct the assembly of two nucleic-acid–functionalized proteins with distinct surface chemistries into six unique latticesmore » composed of catalytically active proteins, or of a combination of proteins and DNA-modified gold nanoparticles. The programmable nature of DNA–DNA interactions used in this strategy allows us to control the lattice symmetries and unit cell constants, as well as the compositions and habit, of the resulting crystals. Finally, this study provides a potentially generalizable strategy for constructing a unique class of materials that take advantage of the diverse morphologies, surface chemistries, and functionalities of proteins for assembling functional crystalline materials.« less

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

NASA Technical Reports Server (NTRS)

Hoenk, Michael

2011-01-01

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

A Simple "Boxed Molecular Kinetics" Approach To Accelerate Rare Events in the Stochastic Kinetic Master Equation.

PubMed

Shannon, Robin; Glowacki, David R

2018-02-15

The chemical master equation is a powerful theoretical tool for analyzing the kinetics of complex multiwell potential energy surfaces in a wide range of different domains of chemical kinetics spanning combustion, atmospheric chemistry, gas-surface chemistry, solution phase chemistry, and biochemistry. There are two well-established methodologies for solving the chemical master equation: a stochastic "kinetic Monte Carlo" approach and a matrix-based approach. In principle, the results yielded by both approaches are identical; the decision of which approach is better suited to a particular study depends on the details of the specific system under investigation. In this Article, we present a rigorous method for accelerating stochastic approaches by several orders of magnitude, along with a method for unbiasing the accelerated results to recover the "true" value. The approach we take in this paper is inspired by the so-called "boxed molecular dynamics" (BXD) method, which has previously only been applied to accelerate rare events in molecular dynamics simulations. Here we extend BXD to design a simple algorithmic strategy for accelerating rare events in stochastic kinetic simulations. Tests on a number of systems show that the results obtained using the BXD rare event strategy are in good agreement with unbiased results. To carry out these tests, we have implemented a kinetic Monte Carlo approach in MESMER, which is a cross-platform, open-source, and freely available master equation solver.

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.

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.

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.

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

Anisotropic surface physicochemical properties of spodumene and albite crystals: Implications for flotation separation

NASA Astrophysics Data System (ADS)

Xu, Longhua; Peng, Tiefeng; Tian, Jia; Lu, Zhongyuan; Hu, Yuehua; Sun, Wei

2017-12-01

Aluminosilicate minerals (e.g., spodumene, albite) have complex crystal structures and similar surface chemistries, but they have poor selectivity compared to traditional fatty acid collectors, making flotation separation difficult. Previous research has mainly considered the mineral crystal structure as a whole. In contrast, the surface characteristics at the atomic level and the effects of different crystal interfaces on the flotation behavior have rarely been investigated. This study focuses on investigating the surface anisotropy quantitatively, including the chemical bond characteristics, surface energies, and broken bond densities, using density functional theory and classical theoretical calculations. In addition, the anisotropy of the surface wettability and adsorption characteristics were examined using contact angle, zeta potential, and Fourier-transform infrared measurements. Finally, these surface anisotropies with different flotation behaviors were investigated and interpreted using molecular dynamics simulations, scanning electron microscopy, and X-ray photoelectron spectroscopy. This systematic research offers new ideas concerning the selective grinding and stage flotation of aluminosilicate minerals based on the crystal characteristics.

Recent advances in surface functionalization techniques on polymethacrylate materials for optical biosensor applications.

PubMed

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Koole, Leo H

2014-06-21

Biosensor chips for immune-based assay systems have been investigated for their application in early diagnostics. The development of such systems strongly depends on the effective protein immobilization on polymer substrates. In order to achieve this complex heterogeneous interaction the polymer surface must be functionalized with chemical groups that are reactive towards proteins in a way that surface functional groups (such as carboxyl, -COOH; amine, -NH2; and hydroxyl, -OH) chemically or physically anchor the proteins to the polymer platform. Since the proteins are very sensitive towards their environment and can easily lose their activity when brought in close proximity to the solid surface, effective surface functionalization and high level of control over surface chemistry present the most important steps in the fabrication of biosensors. This paper reviews recent developments in surface functionalization and preparation of polymethacrylates for protein immobilization. Due to their versatility and cost effectiveness, this particular group of plastic polymers is widely used both in research and in industry.

Attachment chemistry of aromatic compounds on a Silicon(100) surface

NASA Astrophysics Data System (ADS)

Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

2018-03-01

A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

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.

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

DOE PAGES

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

2017-05-08

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

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

PubMed

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

2009-05-01

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

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

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

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

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

PubMed

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

2003-12-01

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

Correlation between bulk- and surface chemistry of Cr-tanned leather and the release of Cr(III) and Cr(VI).

PubMed

Hedberg, Yolanda S; Lidén, Carola; Odnevall Wallinder, Inger

2014-09-15

About 1-3% of the adult general population in Europe is allergic to chromium (Cr). The assessment of the potential release of Cr(III) and Cr(VI) from leather is hence important from a human health and environmental risk perspective. The Cr(VI) content in leather was recently restricted in the European Union. The aim of this study was to assess possible correlations between the bulk and surface chemistry of leather, released Cr(III) and Cr(VI), and capacities of co-released leather specific species to reduce and complex released Cr. Four differently tanned leathers were characterized by scanning electron microscopy with energy dispersive spectroscopy, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and the diphenylcarbazide colorimetric method. Their characteristics were compared with results on Cr(III) and Cr(VI) release into artificial sweat (ASW, pH<6.5) and phosphate buffer (PB, pH 7.5-8.0), measured by means of spectrophotometry and atomic absorption spectroscopy. Co-released leather-specific species were shown to reduce Cr(VI), both in ASW and in PB. Their reduction capacities correlated with findings of the surface content of Cr and of released Cr. Leather samples without this capacity, and with less aromatic surface groups visible by ATR-FTIR, revealed Cr(VI) both at the surface and in solution (PB). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Chemical and physical effects on the adhesion, maturation, and survival of monocytes, macrophages, and foreign body giant cells

NASA Astrophysics Data System (ADS)

Collier, Terry Odell, III

Injury caused by biomedical device implantation initiates inflammatory and wound healing responses. Cells migrate to the site of injury to degrade bacteria and toxins, create new vasculature, and form new and repair injured tissue. Blood-proteins rapidly adsorb onto the implanted material surface and express adhesive ligands which mediate cell adhesion on the material surface. Monocyte-derived macrophages and multi-nucleated foreign body giant cells adhere to the surface and degrade the surface of the material. Due to the role of macrophage and foreign body giant cell on material biocompatibility and biostability, the effects of surface chemistry, surface topography and specific proteins on the maturation and survival of monocytes, macrophages and foreign body giant cells has been investigated. Novel molecularly designed materials were used to elucidate the dynamic interactions which occur between inflammatory cells, proteins and surfaces. The effect of protein and protein adhesion was investigated using adhesive protein depleted serum conditions on RGD-modified and silane modified surfaces. The effects of surface chemistry were investigated using temperature responsive surfaces of poly (N-isopropylacrylamide) and micropatterned surfaces of N-(2 aminoethyl)-3-aminopropyltrimethoxysilane regions on an interpenetrating polymer network of polyacrylamide and poly(ethylene glycol). The physical effects were investigated using polyimide scaffold materials and polyurethane materials with surface modifying end groups. The depletion of immunoglobulin G caused decreased levels of macrophage adhesion, foreign body giant cell formation and increased levels of apoptosis. The temporal nature of macrophage adhesion was observed with changing effectiveness of adherent cell detachment with time, which correlated to increased expression of beta1 integrin receptors on detached macrophages with time. The limited ability of the micropatterned surface, polyimide scaffold and surface modified polyurethane materials to control macrophage adhesion indicates the complexity of macrophage adhesion and protein adsorption onto a surface. These studies have indicated components and adhesive mechanisms which can be utilized to create materials with enhanced resistance to macrophage adhesion and/or degradative abilities.

The formation of prebiotic molecules in star-forming regions

NASA Astrophysics Data System (ADS)

Rivilla, V. M.

New sensitive observations using the current generation of (sub)millimeter telescopes have revealed in several star-forming regions molecular species of different chemical families (e.g. sugars, esters, isocyanates, phosphorus-bearing species) that may play an important role in prebiotic chemistry, and eventually in the origin of life. The observed molecular abundances of complex organic molecules (glycolaldehyde, ethylene glycol and ethyl formate) are better explained by surface-phase chemistry on dust grains, although gas-phase reactions can also play an important role, as in the case of methyl isocyanate. The PO molecule - a basic chemical bond to build-up the backbone of the DNA - has been detected for the first time in star-forming regions. These new observations indicate that phosphorus, a key element for the development of life, is much more abundant in star-forming regions than previously thought.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

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

De Yoreo, J; Orme, C; Dove, P

Since the dawn of life on earth, organisms have directed the crystallization of inorganic ions from solution to form minerals that meet specific biological needs. The resulting materials often exhibit remarkable properties, making the processes involved in biomineralization of interest to a wide array of scientific disciplines. From a geochemical standpoint, perhaps the most important consequence is that CaCO{sub 3} biomineral formation occurs in the Oceans on such a large scale that it influences many aspects of seawater chemistry and results in sequestration of carbon in the form of carbonate sediments. In this manner, the products of biomineralization are preservedmore » in the rock record and serve as an extensive chronicle of the interplay between biota and the earth system environment. From the point of view of materials synthesis, biological control over epitaxy is an elegant example of self-organization in complex molecular systems. Through selective introduction of peptides and proteins, living organisms deterministically modify nucleation, step kinetics, surface morphologies, and facet stabilities to produce nanophase materials, topologically complex single-crystals, and multi-layer composite. The resulting materials have biological functions as diverse as structural supports, porous filtration media, grinding and cutting tools, lenses, gravity sensors and magnetic guidance systems. As Table I shows, calcium carbonate minerals are ubiquitous amongst these biomineral structures. In addition , calcium carbonate is a well studied material that is easily crystallized and has known solution chemistry. Consequently, the calcium carbonate system provides an excellent model for investigating biomineralization processes. Surprisingly, in spite of the identification of carbonate biogenesis as a critical contributor to the carbon reservoir mediating climate change, and the enormous potential of biomimetic synthesis for production of tailored, crystalline nano- and micro-structured materials, the fundamental physical controls on carbonate biomineral formation remain poorly understood. Carbonates are formed in diverse environments almost exclusively by living organisms. These naturally occurring marine and fresh water minerals most commonly occur as the polymorphs of calcite, aragonite and vaterite which are nucleated and grown in the exoskeletons and tissues of marine and freshwater organisms ranging from simple bacteria and algae to crustaceans, molluscs, or sponges. It is known that the soluble fraction associated with mineralizing parts of organisms plays a primary role in crystal formation. In the formation of molluscan shells, this fraction is distinguished by the common presence of aspartic acid rich amino acid mixtures. It is also known that carbonates exposed to different polyamino acids exhibit different crystal habits. Belcher et al. showed that exposing growing CaCO{sub 3} crystals alternately to solutions containing polyanionic proteins associated with the aragonitic and calcitic layers of mollusc shells led to sequential switching of the crystal structure of the newly grown material between that of aragonite and calcite. Further work has demonstrated that these protein mixtures alter the morphology of the calcite growth surface and that they contain two fractions effecting growth: a step-binding fraction that inhibits step advancement on calcite surfaces, and a surface binding fraction that appears to lead to the subsequent nucleation of aragonite. Wierzbicki et al. found that polyaspartate molecules (ASP{sub 20}) bind to calcite surfaces. Finally, modeling of ASP{sub 15} binding to calcite planes predicts large binding energies for well defined orientations. This and related evidence shows that systematic relationships between crystal morphology and surface interactions with the reactive groups of the organic molecules must exist. However, the interplay between surface chemistry and the physical processes of nucleation and crystal growth are poorly understood because, until recently only ex situ biochemical studies focusing on the effect of changes in solution chemistry and/or surface stereo-chemistry on macroscopic crystal morphology had been performed.« less

Photo-Induced Click Chemistry for DNA Surface Structuring by Direct Laser Writing.

PubMed

Kerbs, Antonina; Mueller, Patrick; Kaupp, Michael; Ahmed, Ishtiaq; Quick, Alexander S; Abt, Doris; Wegener, Martin; Niemeyer, Christof M; Barner-Kowollik, Christopher; Fruk, Ljiljana

2017-04-11

Oligonucleotides containing photo-caged dienes were prepared and shown to react quantitatively in a light-induced Diels-Alder cycloaddition with functional maleimides in aqueous solution within minutes. Due to its high yield and fast rate, the reaction was exploited for DNA surface patterning with sub-micrometer resolution employing direct laser writing (DLW). Functional DNA arrays were written by direct laser writing (DLW) in variable patterns, which were further encoded with fluorophores and proteins through DNA directed immobilization. This mild and efficient light-driven platform technology holds promise for the fabrication of complex bioarrays with sub-micron resolution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis and Comparison of Aluminum Alloy Welded Joints Between Metal Inert Gas Welding and Tungsten Inert Gas Welding

NASA Astrophysics Data System (ADS)

Zhao, Lei; Guan, Yingchun; Wang, Qiang; Cong, Baoqiang; Qi, Bojin

2015-09-01

Surface contamination usually occurs during welding processing and it affects the welds quality largely. However, the formation of such contaminants has seldom been studied. Effort was made to study the contaminants caused by metal inert gas (MIG) welding and tungsten inert gas (TIG) welding processes of aluminum alloy, respectively. SEM, FTIR and XPS analysis was carried out to investigate the microstructure as well as surface chemistry. These contaminants were found to be mainly consisting of Al2O3, MgO, carbide and chromium complexes. The difference of contaminants between MIG and TIG welds was further examined. In addition, method to minimize these contaminants was proposed.

Ab initio theory of point defects in oxide materials: structure, properties, chemical reactivity

NASA Astrophysics Data System (ADS)

Pacchioni, Gianfranco

2000-05-01

Point defects play a fundamental role in determining the physical and chemical properties of inorganic materials. This holds not only for the bulk properties but also for the surface of oxides where several kinds of point defects exist and exhibit a rich and complex chemistry. A particularly important defect in oxides is the oxygen vacancy. Depending on the electronic structure of the material the nature of oxygen vacancies changes dramatically. In this article we provide a rationalization of the very different electronic structure of neutral and charged oxygen vacancies in SiO 2 and MgO, two oxide materials with completely different electronic structure (from very ionic, MgO, to largely covalent, SiO 2). We used methods of ab initio quantum chemistry, from density functional theory (DFT) to configuration interaction (CI), to determine the ground and excited state properties of these defects. The theoretical results are combined with recent spectroscopic measurements. A series of observable properties has been determined in this way: defect formation energies, hyperfine interactions in electron paramagnetic resonance (EPR) spectra of paramagnetic centers, optical spectra, surface chemical reactivity. The interplay between experimental and theoretical information allows one to unambiguously identify the structure of oxygen vacancies in these binary oxides and on their surfaces.

Role of surfaces and interfaces in controlling the mechanical properties of metallic alloys.

PubMed

Lee, Won-Jong; Chia, Wen-Jui; Wang, Jinliu; Chen, Yanfeng; Vaynman, Semyon; Fine, Morris E; Chung, Yip-Wah

2010-11-02

This article explores the subtle effects of surfaces and interfaces on the mechanical properties of bulk metallic alloys using three examples: environmental effects on fatigue life, hydrogen embrittlement effects on the ductility of intermetallics, and the role of coherent precipitates in the toughness of steels. It is demonstrated that the marked degradation of the fatigue life of metals is due to the strong chemisorption of adsorbates on exposed slip steps that are formed during fatigue deformation. These adsorbates reduce the reversibility of slip, thus accelerating fatigue damage in a chemically active gas environment. For certain intermetallic alloys such as Ni(3)Al and Ni(3)Fe, the ductility depends on the ambient gas composition and the atomic ordering in these alloys, both of which govern the complex surface chemical reactions taking place in the vicinity of crack tips. Finally, it is shown that local stresses at a coherent precipitate-matrix interface can activate dislocation motion at low temperatures, thus improving the fracture toughness of bulk alloys such as steels at cryogenic temperatures. These examples illustrate the complex interplay between surface chemistry and mechanics, often yielding unexpected results.

From Titan to the primitive Earth

NASA Astrophysics Data System (ADS)

Raulin, F.; Gpcos Team

Our knowledge of the conditions prevailing in the environment of the primitive Earth is still very limited, due to the lack of geological data. Fortunately, there are a few planetary objects in the solar system which present similarities with our planet, including during its early history. Titan is one of these. With a diameter of more than 5100 km, Titan, the largest moon of Saturn, is also the only one to have a dense atmosphere. This atmosphere, clearly evidenced by the presence of haze layers, extends to approximately 1500 km. Like the Earth, Titan's atmosphere is mainly composed of dinitrogen, N2 . The other main constituents are methane, CH4 , about 1.6% to 2.0% in the stratosphere, as measured by CIRS on Cassini and GC-MS on Huygens and dihydrogen (H2 , approximate 0.1%). With surface temperatures of approximately 94 K, and an average surface pressure of 1.5 bar, Titan's atmosphere is nearly five times denser than the Earth's. Despite of these differences between Titan and the Earth there are several analogies that can be drawn between the two planetary bodies. The first resemblances concern the vertical atmospheric structure. Although Titan is much colder, with a troposphere (˜94-˜70 K), a tropopause (70.4 K) and a stratosphere (˜70-175 K) its atmosphere presents a similar complex structure to that of the Earth. These analogies are linked to the presence in both atmospheres of greenhouse gases: CH4 and H2 on Titan, equivalent respectively to terrestrial condensable H2 O and non-condensable CO2 . In addition the haze particles and clouds in Titan's atmosphere play an antigreenhouse effect similar to that of the terrestrial atmospheric aerosols and clouds. Indeed, methane on Titan seems to play the role of water on the Earth, with a complex cycle, which still has to be understood. The possibility that Titan is covered with hydrocarbon oceans is now ruled out, but it is still possible that Titan's surface include lakes of methane and ethane. Moreover, the DISR instrument on Huygens has provided pictures of Titan's surface which clearly shows dentritic structures strongly suggesting recent liquid flow on the surface of Titan. In addition, the Huygens GCMS data show that methane mole fraction increases in the low troposphere (up to 5%) and reaches the saturation level at approximately 8 km altitude, allowing the possible formation of clouds and rain. Furthermore, GC-MS analyses recorded a 50% increase 1 in the methane mole fraction at Titan's surface, suggesting the presence of condensed methane on the surface near the lander. Other observations from the Cassini instruments clearly show the presence of various surface features of different origins indicative of volcanic, tectonic, sedimentological and meteorological processes.as we find on Earth .INMS on Cassini and GC-MS on Huygens have detected the presence of argon in the atmosphere. Similarly to the Earth atmosphere, the most abundant argon isotope is 40 Ar, which comes from the radioactive decay of 40 K. This strongly suggests that Titan's atmosphere is a secondary atmosphere, produced by the degassing of trapped gases. Analogies can also be made between the organic chemistry which is very active now on Titan and the prebiotic chemistry which was active on primitive Earth. In spite of the absence of permanent bodies of liquid water on Titan's surface, several of the organic processes which are occurring today on Titan imply some of the organic compounds which are considered as key molecules in the terrestrial prebiotic chemistry, such as hydrogen cyanide (HCN), cyanoacetylene (HC3 N) and cyanogen (C2 N2 ). A complex organic chemistry seems to be present in the three components of what one can call, always by analogy with our planet, the "geofluids" of Titan: air (gas atmosphere), aerosols (solid atmosphere) and surface (oceans). A recent study on the hydrogen escape from the primitive atmosphere of the Earth suggests that it may have been more reducing that we thought. If this is correct, the chemical processes involved in Titan's atmospheric chemistry may be even closer to those on the primitive Earth. References. Feng T., Owen B. T., Pavlov, A.A, and De Sterck, H. 2005. `A Hydrogen-Rich Early Earth Atmosphere'. Science 308, 1014-1017. Raulin, F. (2005), `Exo-Astrobiological Aspects of Europa and Titan: From Observations to Speculations', Space Science Review 116 (1-2), 471-496. Nature, (2005), `The Huygens probe on Titan', 8 News & Views, Articles and Letters 438, 756-802 2

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.

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…

Toward an understanding of "Legacy P" - phosphorus sorption mechanisms in stream sediments as influenced by organic matter

NASA Astrophysics Data System (ADS)

Audette, Yuki; O'Halloran, Ivan P.; Nowell, Peter M.; Congreves, Katelyn; Voroney, R. Paul

2017-04-01

Water chemistry and phosphorus (P) forms were analyzed to determine the nature of legacy P in sediments of the West Holland River and the adjacent drainage canals of the Holland Marsh drainage system, located in southern Ontario, Canada. The river and canals route water from the intensively cropped muck polders of the Holland Marsh and drain Lake Simcoe. Sediment samples were characterized for mineralogy using X-ray diffraction techniques (XRD); total P (TP); and Ca, Fe, Mn, and Mg contents, as well as cation exchange capacity and organic matter (OM) content. Forms of sediment P in five depth sections (ranging from 0-15 cm depth) were characterized and quantified by sequential P fractionation chemistry. At all study sites, mobile P forms including organic P forms were found to be higher in surface sediments than in deeper sediments. The major P form within the sediments of the two canal sites, where the concentration of TP in the surface water was within the Ontario Provincial Water Quality Objectives (PWQO) of 0.03 mg P L-1, was Ca-bound P, indicating a low risk of soluble reactive P (SRP) release. A trace of apatite (a stable Ca-P mineral) was also detected in these sediments. Conversely, sediments collected from the West Holland River at sites located within the Holland Marsh exhibited a high risk of SRP release, and redox-sensitive P was the dominant P form in the sediment despite the surface water exhibiting higher concentration of Ca and alkaline pH. In addition, the concentrations of TP as measured in surface water samples taken from the site were 8 times greater than PWQO. In the sediments where the risk of SRP release was high, OM contents were also relatively high and traces of brushite (a labile Ca-P mineral) were detected. The formation of OM and cation complexes, such as OM-Fe complexes, may play an important role in regulating the fate of sediment-P forms through the adsorption of SRP. These OM-Fe complexes may inhibit the formation of more stable Ca-P minerals, even under neutral to alkaline conditions. Thus, where OM-Fe-P forms predominate, we predict a high risk of SRP release from sediments when water chemistry changes. In addition, OM may inhibit the transformation of labile Ca-P forms to more stable Ca-P minerals. Loading of OM affects the development of hypoxia in aquatic systems, and the accumulation of OM can promote the release of both SRP and dissolved organic C to downstream environments. This study provides evidence that the presence of OM in stream sediments influences P sorption mechanisms and is critical in understanding P biogeochemistry in freshwater environments.

The Surface Chemistry of Metal Chalcogenide Nanocrystals

NASA Astrophysics Data System (ADS)

Anderson, Nicholas Charles

The surface chemistry of metal chalcogenide nanocrystals is explored through several interrelated analytical investigations. After a brief discussion of the nanocrystal history and applications, molecular orbital theory is used to describe the electronic properties of semiconductors, and how these materials behave on the nanoscale. Quantum confinement plays a major role in dictating the optical properties of metal chalcogenide nanocrystals, however surface states also have an equally significant contribution to the electronic properties of nanocrystals due to the high surface area to volume ratio of nanoscale semiconductors. Controlling surface chemistry is essential to functionalizing these materials for biological imaging and photovoltaic device applications. To better understand the surface chemistry of semiconducting nanocrystals, three competing surface chemistry models are presented: 1.) The TOPO model, 2.) the Non-stoichiometric model, and 3.) the Neutral Fragment model. Both the non-stoichiometric and neutral fragment models accurately describe the behavior of metal chalcogenide nanocrystals. These models rely on the covalent bond classification system, which divides ligands into three classes: 1.) X-type, 1-electron donating ligands that balance charge with excess metal at the nanocrystal surface, 2.) L-type, 2-electron donors that bind metal sites, and 3.) Z-type, 2-electron acceptors that bind chalcogenide sites. Each of these ligand classes is explored in detail to better understand the surface chemistry of metal chalcogenide nanocrystals. First, chloride-terminated, tri-n-butylphosphine (Bu 3P) bound CdSe nanocrystals were prepared by cleaving carboxylate ligands from CdSe nanocrystals with chlorotrimethylsilane in Bu3P solution. 1H and 31P{1H} nuclear magnetic resonance spectra of the isolated nanocrystals allowed assignment of distinct signals from several free and bound species, including surface-bound Bu3P and [Bu3P-H]+[Cl]- ligands as well as a Bu3P complex of cadmium chloride. Nuclear magnetic resonance spectroscopy supports complete cleavage of the X-type carboxylate ligands. Combined with measurements of the Se:Cd:Cl ratio using Rutherford backscattering spectrometry, these studies support a structural model of nanocrystals where chloride ligands terminate the crystal lattice by balancing the charges of excess Cd2+ ions. The adsorption of dative phosphine ligands leads to nanocrystals who's solubility is afforded by reversibly bound and readily exchanged L-type ligands, e.g. primary amines and phosphines. The other halides (Br and I) can also be used to prepare Bu 3P-bound, halide-terminated CdSe nanocrystals, however these nanocrystals are not soluble after exchange. The change in binding affinity of Bu 3P over the halide series is briefly discussed. Next, we report a series of L-type ligand exchanges using Bu3P-bound, chloride-terminated CdSe nanocrystals with several Lewis bases, including aromatic, cyclic, and non-cyclic sulfides, and ethers; primary, secondary, and tertiary amines and phosphines; tertiary phosphine chalcogenides; primary alcohols, isocyanides, and isothiocyanides. Using 31P nuclear magnetic resonance spectroscopy, we establish a relative binding affinity for these ligands that reflects electronic considerations but is dominated primarily by steric interactions, as determined by comparing binding affinity to Tolmann cone angles. We also used chloride-terminated CdSe nanocrystals to explore the reactivity of ionic salts at nanocrystal surfaces. These salts, particularly [Bu3P-H]+[Cl]-, bind nanocrystals surfaces as L-type ligands, making them soluble in polar solvents such as acetonitrile. This information should provide insight for rational ligand design for future applications involving metal chalcogenide nanocrystals. The strongest ligand, primary n-alkylamine, rapidly displace the Bu3P from halide-terminated CdSe nanocrystals, leading to amine-bound nanocrystals with higher dative ligand coverages and greatly increased photoluminescence quantum yields. The importance of ligand coverage to both the UV-visible absorption and photoluminescence spectra are discussed. (Abstract shortened by UMI.).

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.

Preliminary Analysis of the Performance of the Landsat 8/OLI Land Surface Reflectance Product

NASA Technical Reports Server (NTRS)

Vermote, Eric; Justice, Chris; Claverie, Martin; Franch, Belen

2016-01-01

The surface reflectance, i.e., satellite derived top of atmosphere (TOA) reflectance corrected for the temporally, spatially and spectrally varying scattering and absorbing effects of atmospheric gases and aerosols, is needed to monitor the land surface reliably. For this reason, the surface reflectance, and not TOA reflectance, is used to generate the greater majority of global land products, for example, from the Moderate Resolution Imaging Spectroradiometer (MODIS) and Visible Infrared Imaging Radiometer Suite (VIIRS) sensors. Even if atmospheric effects are minimized by sensor design, atmospheric effects are still challenging to correct. In particular, the strong impact of aerosols in the visible and near infrared spectral range can be difficult to correct, because they can be highly discrete in space and time (e.g., smoke plumes) and because of the complex scattering and absorbing properties of aerosols that vary spectrally and with aerosol size, shape, chemistry and density.

Potential sources of nitrous acid (HONO) and their impacts on ozone: A WRF-Chem study in a polluted subtropical region

NASA Astrophysics Data System (ADS)

Zhang, Li; Wang, Tao; Zhang, Qiang; Zheng, Junyu; Xu, Zheng; Lv, Mengyao

2016-04-01

Current chemical transport models commonly undersimulate the atmospheric concentration of nitrous acid (HONO), which plays an important role in atmospheric chemistry, due to the lack or inappropriate representations of some sources in the models. In the present study, we parameterized up-to-date HONO sources into a state-of-the-art three-dimensional chemical transport model (Weather Research and Forecasting model coupled with Chemistry: WRF-Chem). These sources included (1) heterogeneous reactions on ground surfaces with the photoenhanced effect on HONO production, (2) photoenhanced reactions on aerosol surfaces, (3) direct vehicle and vessel emissions, (4) potential conversion of NO2 at the ocean surface, and (5) emissions from soil bacteria. The revised WRF-Chem was applied to explore the sources of the high HONO concentrations (0.45-2.71 ppb) observed at a suburban site located within complex land types (with artificial land covers, ocean, and forests) in Hong Kong. With the addition of these sources, the revised model substantially reproduced the observed HONO levels. The heterogeneous conversions of NO2 on ground surfaces dominated HONO sources contributing about 42% to the observed HONO mixing ratios, with emissions from soil bacterial contributing around 29%, followed by the oceanic source (~9%), photochemical formation via NO and OH (~6%), conversion on aerosol surfaces (~3%), and traffic emissions (~2%). The results suggest that HONO sources in suburban areas could be more complex and diverse than those in urban or rural areas and that the bacterial and/or ocean processes need to be considered in HONO production in forested and/or coastal areas. Sensitivity tests showed that the simulated HONO was sensitive to the uptake coefficient of NO2 on the surfaces. Incorporation of the aforementioned HONO sources significantly improved the simulations of ozone, resulting in increases of ground-level ozone concentrations by 6-12% over urban areas in Hong Kong and the Pearl River Delta region. This result highlights the importance of accurately representing HONO sources in simulations of secondary pollutants over polluted regions.

Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

NASA Technical Reports Server (NTRS)

Beck, M.

1979-01-01

In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

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.

Evaluating the effects of variable water chemistry on bacterial transport during infiltration.

PubMed

Zhang, Haibo; Nordin, Nahjan Amer; Olson, Mira S

2013-07-01

Bacterial infiltration through the subsurface has been studied experimentally under different conditions of interest and is dependent on a variety of physical, chemical and biological factors. However, most bacterial transport studies fail to adequately represent the complex processes occurring in natural systems. Bacteria are frequently detected in stormwater runoff, and may present risk of microbial contamination during stormwater recharge into groundwater. Mixing of stormwater runoff with groundwater during infiltration results in changes in local solution chemistry, which may lead to changes in both bacterial and collector surface properties and subsequent bacterial attachment rates. This study focuses on quantifying changes in bacterial transport behavior under variable solution chemistry, and on comparing the influences of chemical variability and physical variability on bacterial attachment rates. Bacterial attachment rate at the soil-water interface was predicted analytically using a combined rate equation, which varies temporally and spatially with respect to changes in solution chemistry. Two-phase Monte Carlo analysis was conducted and an overall input-output correlation coefficient was calculated to quantitatively describe the importance of physiochemical variation on the estimates of attachment rate. Among physical variables, soil particle size has the highest correlation coefficient, followed by porosity of the soil media, bacterial size and flow velocity. Among chemical variables, ionic strength has the highest correlation coefficient. A semi-reactive microbial transport model was developed within HP1 (HYDRUS1D-PHREEQC) and applied to column transport experiments with constant and variable solution chemistries. Bacterial attachment rates varied from 9.10×10(-3)min(-1) to 3.71×10(-3)min(-1) due to mixing of synthetic stormwater (SSW) with artificial groundwater (AGW), while bacterial attachment remained constant at 9.10×10(-3)min(-1) in a constant solution chemistry (AGW only). The model matched observed bacterial breakthrough curves well. Although limitations exist in the application of a semi-reactive microbial transport model, this method represents one step towards a more realistic model of bacterial transport in complex microbial-water-soil systems. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

Water-stable fac-{TcO₃}⁺ complexes - a new field of technetium chemistry.

PubMed

Braband, Henrik

2011-01-01

The development of technetium chemistry has been lagging behind that of its heavier congener rhenium, primarily because the inherent radioactivity of all Tc isotopes has limited the number of laboratories that can study the chemistry of this fascinating element. Although technetium is an artificial element, it is not rare. Significant amounts of the isotope (99)Tc are produced every day as a fission byproduct in nuclear power plants. Therefore, a fundamental understanding of the chemistry of (99)Tc is essential to avoid its release into the environment. In this article the chemistry of technetium at its highest oxidation state (+VII) is reviewed with a special focus on recent developments which make water-stable complexes of the general type [TcO(3)(tacn-R)](+) (tacn-R = 1,4,7-triazacyclononane or derivatives) accessible. Complexes containing the fac-{TcO(3)}(+) core display a unique reactivity. In analogy to [OsO(4)] and [RuO(4)], complexes containing the fac-{TcO(3)}(+) core undergo with alkenes metal-mediated, vicinal cis-dihydroxylation reactions (alkene-glycol interconversion) in water via a (3+2)-cycloaddition reaction. Therefore, water-stable fac-{(99m)TcO(3)}(+) complexes pave the way for a new labeling strategy for radiopharmaceutical applications, based on (3+2)-cycloaddition reactions. This new concept for the labeling of biomolecules with small [(99m)TcO(3)(tacn-R)](+)-type complexes by way of a (3+2)-cycloaddition with alkenes is discussed in detail. The herein reported developments in high-valent technetium chemistry create a new field of research with this artificial element. This demonstrates the potential of fundamental research to provide new impetus of innovation for the development of new methods for radiopharmaceutical applications.

Mapping the Spatial Distribution of Metal-Bearing Oxides in VY Canis Majoris

NASA Astrophysics Data System (ADS)

Burkhardt, Andrew; Booth, S. Tom; Remijan, Anthony; Carroll, Brandon; Ziurys, Lucy M.

2015-06-01

The formation of silicate-based dust grains is not well constrained. Despite this, grain surface chemistry is essential to modern astrochemical formation models. In carbon-poor stellar envelopes, such as the red hypergiant VY Canis Majoris (VY CMa), metal-bearing oxides, the building blocks of silicate grains, dominate the grain formation, and thus are a key location to study dust chemistry. TiO_2, which was only first detected in the radio recently (Kaminski et al., 2013a), has been proposed to be a critical molecule for silicate grain formation, and not oxides containing more abundant metals (eg. Si, Fe, and Mg) (Gail and Sedlmayr, 1998). In addition, other molecules, such as SO_2, have been found to trace shells produced by numerous outflows pushing through the expanding envelope, resulting in a complex velocity structure (Ziurys et al., 2007). With the advanced capabilities of ALMA, it is now possible to individually resolve the velocity structure of each of these outflows and constrain the underlying chemistry in the region. Here, we present high resolution maps of rotational transitions of several metal-bearing oxides in VY CMa from the ALMA Band 7 and Band 9 Science Verification observations. With these maps, the physical parameters of the region and the formation chemistry of metal-bearing oxides will be studied.

Pulmonary toxicity of manufactured nanoparticles

NASA Astrophysics Data System (ADS)

Peebles, Brian Christopher

Manufactured nanomaterials have become ubiquitous in science, industry, and medicine. Although electron microscopy and surface probe techniques have improved understanding of the physicochemical properties of nanomaterials, much less is known about what makes nanomaterials toxic. Particulate matter less than 2.5 mum in effective aerodynamic diameter is easily inhaled and taken deep into the lungs. The toxicity of inhaled particulate matter is related to its size and surface chemistry; for instance, the smaller the size of particles, the greater their specific surface area. The chemistry and toxicity of insoluble particles depends on their surface area, since chemical reactions may happen with the environment on the surface. Oxidation and reduction may occur on the surfaces of particles after they are produced. For instance, it is known that carbonaceous particles from vehicle exhaust and industrial emission may interact with reactive species like ozone in their ambient environment, altering the surface chemistry of the particles. Reaction with species in the environment may cause changes in the chemical functionality of the surface and change the toxic properties of the particles when they are inhaled. Furthermore, metals on the surface of inhalable particles can contribute to their toxicity. Much attention has been given to the presence of iron on the surfaces of inhalable particles in the environment. After particle inhalation, particles are endocytosed by alveolar macrophages in the immune response to foreign matter. They are exposed to hydrogen peroxide in the oxidative burst, which can cause the iron-mediated production of hydroxyl free radicals via the Fenton reaction, causing oxidative stress that leads to inflammation and cell death. The toxicity of particles that contain metals depends on the redox activity and bioavailability of the metals, the causes of thich have not yet been adequately explored. In this thesis, electron paramagnetic spectroscopy showed that carbon blacks contain free radical and other surface functionality as manufactured, and that exposure to ozone further functionalizes the surface. Samples of carbon black that have been exposed to ozone react with their ambient environment so that acid anhydride and cyclic ether functionality hydrolyze to form carboxylic acid functionality, observable by transmission Fourier transform infrared spectroscopy. Persistent free radical content, but not free radical content from ozone exposure, may mediate the toxic response of cells to carbon blacks in vitro. Results showed that macrophages exposed to carbon blacks that had been exposed to ozone were not less viable in vitro than macrophages exposed to carbon blacks as manufactured because the free radical content that resulted from ozone exposure was not persistent in an aqueous medium. Furthermore, concurrent exposure to ozonated carbon blacks and ozone was less lethal to macrophages than carbon black exposure alone, possibly because the ozone oxidatively preconditioned the macrophages to resist oxidative stress. The nature of redox-active iron species on the surface of iron-loaded synthetic carbon particles was explored. The particles had been shown in previous studies to provoke an inflammatory response involving the release of tumor necrosis factor (TNF)-alpha, which was correlated with their production of hydroxyl free radicals via the Fenton reaction in the presence of hydrogen peroxide. It was found that the source of bioavailable Fenton-active iron on the surfaces of the particles was fluoride species that were byproducts of a step in the synthetic process. Fluoride ligated the iron already on the surface, forming a complex that resisted precipitation in the biological medium and thus made the iron more bioavailable. The results of this thesis aim to clarify whether the size and surface chemistry of nanoparticles should be considered more closely as criteria with which to develop better environmental controls for occupational health. Permissible exposure limits to micrometer-size particulate matter in the workplace are in place, but current limits do not specifically address the role of surface chemistry and the potentially higher toxicity of nanomaterials. The size, agglomeration characteristics, and surface chemistry of carbon nanoparticles are being studied and manipulated to explore the causes of their toxicity. Inflammatory response and cytotoxicity following exposure of human and murine macrophages to nanoparticles are being employed as indicators of the ability of particles to cause respiratory harm. The results are expected to lead to more effective standards for nanomaterial exposure in the workplace and pathways to toxicity mitigation.

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

USGS Publications Warehouse

Healy, R.W.; Bartos, T.T.; Rice, C.A.; McKinley, M.P.; Smith, B.D.

2011-01-01

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Novel diagnostics for direct measurements of radical densities in atmospheric pressure plasma jets

NASA Astrophysics Data System (ADS)

Wagenaars, Erik

2017-10-01

Atmospheric-pressure plasma jets (APPJs) are widely studied for potential applications in industry and healthcare, e.g. surface modification of plastics, plasma medicine and photoresist removal. These plasmas can operate in open air, remain at room temperature and still have a non-equilibrium chemistry. Even though the exact mechanisms through which APPJs affect target surfaces remain largely unknown, it is clear that reactive species play a pivotal role in the success of APPJs. Therefore, reactive species diagnostics of APPJs play an important role in further developing our understanding of the plasma chemistry and will enable increases in treatment efficacy. Two-photon Absorption Laser Induced Fluorescence (TALIF) is a well-known technique for the measurement of absolute densities of atomic radicals such as O, N and H. Unfortunately, application of this technique on APPJs that are operating under realistic conditions for applications, i.e. in open air and with complex admixtures, is not straightforward. The highly collisional environment of APPJs means that collisional quenching of the laser-excited state becomes significant and needs to be taken into account. For well-controlled atmospheres and simple admixtures the effect can be estimated using quenching coefficients, however under realistic operating conditions the identity and density of the quenching partners is unknown due to the complexity of the plasma chemistry. I will present a picosecond TALIF diagnostic which uses a sub-nanosecond laser and iCCD camera that allows the measurement of the quenching-affected fluorescence decay rate directly, enabling absolute measurements of O and N density maps in the open-air effluent of an APPJ. The author acknowledges his collaborators at UoY, A. West, J. Bredin, S. Schroeter, K. Niemi, T. Gans, J. Dedrick and D. O'Connell and support from the UK EPSRC (EP/K018388/1 & EP/H003797/1).

Contribution of radiation chemistry to the study of metal clusters.

PubMed

Belloni, J

1998-11-01

Radiation chemistry dates from the discovery of radioactivity one century ago by H. Becquerel and P. and M. Curie. The complex phenomena induced by ionizing radiation have been explained progressively. At present, the methodology of radiation chemistry, particularly in the pulsed mode, provides a powerful means to study not only the early processes after the energy absorption, but more generally a broad diversity of chemical and biochemical reaction mechanisms. Among them, the new area of metal cluster chemistry illustrates how radiation chemistry contributed to this field in suggesting fruitful original concepts, in guiding and controlling specific syntheses, and in the detailed elaboration of the mechanisms of complex and long-unsolved processes, such as the dynamics of nucleation, electron transfer catalysis and photographic development.

Chemistry of Bimetallic Linked Cyclopentadienyl Complexes: Progress Report, 1 December 1986 --30 November 1989

DOE R&D Accomplishments Database

Schrock, R. R.

1989-01-01

Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. (CBS)

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.

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

Overcoming heterologous protein interdependency to optimize P450-mediated Taxol precursor synthesis in Escherichia coli

PubMed Central

Biggs, Bradley Walters; Lim, Chin Giaw; Sagliani, Kristen; Shankar, Smriti; Stephanopoulos, Gregory; Ajikumar, Parayil Kumaran

2016-01-01

Recent advances in metabolic engineering have demonstrated the potential to exploit biological chemistry for the synthesis of complex molecules. Much of the progress to date has leveraged increasingly precise genetic tools to control the transcription and translation of enzymes for superior biosynthetic pathway performance. However, applying these approaches and principles to the synthesis of more complex natural products will require a new set of tools for enabling various classes of metabolic chemistries (i.e., cyclization, oxygenation, glycosylation, and halogenation) in vivo. Of these diverse chemistries, oxygenation is one of the most challenging and pivotal for the synthesis of complex natural products. Here, using Taxol as a model system, we use nature’s favored oxygenase, the cytochrome P450, to perform high-level oxygenation chemistry in Escherichia coli. An unexpected coupling of P450 expression and the expression of upstream pathway enzymes was discovered and identified as a key obstacle for functional oxidative chemistry. By optimizing P450 expression, reductase partner interactions, and N-terminal modifications, we achieved the highest reported titer of oxygenated taxanes (∼570 ± 45 mg/L) in E. coli. Altogether, this study establishes E. coli as a tractable host for P450 chemistry, highlights the potential magnitude of protein interdependency in the context of synthetic biology and metabolic engineering, and points to a promising future for the microbial synthesis of complex chemical entities. PMID:26951651

Overcoming heterologous protein interdependency to optimize P450-mediated Taxol precursor synthesis in Escherichia coli.

PubMed

Biggs, Bradley Walters; Lim, Chin Giaw; Sagliani, Kristen; Shankar, Smriti; Stephanopoulos, Gregory; De Mey, Marjan; Ajikumar, Parayil Kumaran

2016-03-22

Recent advances in metabolic engineering have demonstrated the potential to exploit biological chemistry for the synthesis of complex molecules. Much of the progress to date has leveraged increasingly precise genetic tools to control the transcription and translation of enzymes for superior biosynthetic pathway performance. However, applying these approaches and principles to the synthesis of more complex natural products will require a new set of tools for enabling various classes of metabolic chemistries (i.e., cyclization, oxygenation, glycosylation, and halogenation) in vivo. Of these diverse chemistries, oxygenation is one of the most challenging and pivotal for the synthesis of complex natural products. Here, using Taxol as a model system, we use nature's favored oxygenase, the cytochrome P450, to perform high-level oxygenation chemistry in Escherichia coli. An unexpected coupling of P450 expression and the expression of upstream pathway enzymes was discovered and identified as a key obstacle for functional oxidative chemistry. By optimizing P450 expression, reductase partner interactions, and N-terminal modifications, we achieved the highest reported titer of oxygenated taxanes (∼570 ± 45 mg/L) in E. coli. Altogether, this study establishes E. coli as a tractable host for P450 chemistry, highlights the potential magnitude of protein interdependency in the context of synthetic biology and metabolic engineering, and points to a promising future for the microbial synthesis of complex chemical entities.

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.

Lanthanide complexes of azidophenacyl-DO3A as new synthons for click chemistry and the synthesis of heterometallic lanthanide arrays.

PubMed

Tropiano, Manuel; Kenwright, Alan M; Faulkner, Stephen

2015-04-07

Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbohydrates in Supramolecular Chemistry.

PubMed

Delbianco, Martina; Bharate, Priya; Varela-Aramburu, Silvia; Seeberger, Peter H

2016-02-24

Carbohydrates are involved in a variety of biological processes. The ability of sugars to form a large number of hydrogen bonds has made them important components for supramolecular chemistry. We discuss recent advances in the use of carbohydrates in supramolecular chemistry and reveal that carbohydrates are useful building blocks for the stabilization of complex architectures. Systems are presented according to the scaffold that supports the glyco-conjugate: organic macrocycles, dendrimers, nanomaterials, and polymers are considered. Glyco-conjugates can form host-guest complexes, and can self-assemble by using carbohydrate-carbohydrate interactions and other weak interactions such as π-π interactions. Finally, complex supramolecular architectures based on carbohydrate-protein interactions are discussed.

Surface chemistry driven actuation in nanoporous gold

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

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

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

Molecular Rotors

DTIC Science & Technology

2006-10-31

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

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

Treesearch

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

2003-01-01

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

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

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

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

2015-02-02

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

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

PubMed

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

2016-07-01

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

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

PubMed Central

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

2016-01-01

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

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

Integrated immunoassay using tuneable surface acoustic waves and lensfree detection.

PubMed

Bourquin, Yannyk; Reboud, Julien; Wilson, Rab; Zhang, Yi; Cooper, Jonathan M

2011-08-21

The diagnosis of infectious diseases in the Developing World is technologically challenging requiring complex biological assays with a high analytical performance, at minimal cost. By using an opto-acoustic immunoassay technology, integrating components commonly used in mobile phone technologies, including surface acoustic wave (SAW) transducers to provide pressure driven flow and a CMOS camera to enable lensfree detection technique, we demonstrate the potential to produce such an assay. To achieve this, antibody functionalised microparticles were manipulated on a low-cost disposable cartridge using the surface acoustic waves and were then detected optically. Our results show that the biomarker, interferon-γ, used for the diagnosis of diseases such as latent tuberculosis, can be detected at pM concentrations, within a few minutes (giving high sensitivity at a minimal cost). This journal is © The Royal Society of Chemistry 2011

Surface Traps in Colloidal Quantum Dots: A Combined Experimental and Theoretical Perspective.

PubMed

Giansante, Carlo; Infante, Ivan

2017-10-19

Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their atomistic origin and manipulating them chemically have capital importance to design defect-free colloidal quantum dots and make a leap forward in the development of efficient optoelectronic devices. Recent advances in computing power established computational chemistry as a powerful tool to describe accurately complex chemical species and nowadays it became conceivable to model colloidal quantum dots with realistic sizes and shapes. In this Perspective, we combine the knowledge gathered in recent experimental findings with the computation of quantum dot electronic structures. We analyze three different systems: namely, CdSe, PbS, and CsPbI 3 as benchmark semiconductor nanocrystals showing how different types of trap states can form at their surface. In addition, we suggest experimental healing of such traps according to their chemical origin and nanocrystal composition.

Water and complex organic chemistry in the cold dark cloud Barnard 5: Observations and Models

NASA Astrophysics Data System (ADS)

Wirström, Eva; Charnley, Steven B.; Taquet, Vianney; Persson, Carina M.

2015-08-01

Studies of complex organic molecule (COM) formation have traditionally been focused on hot cores in regions of massive star formation, where chemistry is driven by the elevated temperatures - evaporating ices and allowing for endothermic reactions in the gas-phase. As more sensitive instruments have become available, the types of objects known to harbour COMs like acetaldehyde (CH3CHO), dimethyl ether (CH3OCH3), methyl formate (CH3OCHO), and ketene (CH2CO) have expanded to include low mass protostars and, recently, even pre-stellar cores. We here report on the first in a new category of objects harbouring COMs: the cold dark cloud Barnard 5 where non-thermal ice desorption induce complex organic chemistry entirely unrelated to local star-formation.Methanol, which only forms efficiently on the surfaces of dust grains, provide evidence of efficient non-thermal desorption of ices in the form of prominent emission peaks offset from protostellar activity and high density tracers in cold molecular clouds. A study with Herschel targeting such methanol emission peaks resulted in the first ever detection of gas-phase water offset from protostellar activity in a dark cloud, at the so called methanol hotspot in Barnard 5.To model the effect a transient injection of ices into the gas-phase has on the chemistry of a cold, dark cloud we have included gas-grain interactions in an existing gas-phase chemical model and connected it to a chemical reaction network updated and expanded to include the formation and destruction paths of the most common COMs. Results from this model will be presented.Ground-based follow-up studies toward the methanol hotspot in B5 have resulted in the detection of a number of COMs, including CH2CO, CH3CHO, CH3OCH3, and CH3OCHO, as well as deuterated methanol (CH2DOH). Observations have also confirmed that COM emission is extended and not localised to a core structure. The implications of these observational and theoretical studies of B5 will be discussed in the context of the gas-grain interaction in dark clouds and its relation to the chemistry of the earliest phases of low-mass star formation.

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)

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

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

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE PAGES

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; ...

2017-12-05

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

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

2017-02-16

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

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

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

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

Polynuclear Aromatic Hydrocarbons with Curved Surfaces: Buckyballs

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

Sygula, Andrzej

The discovery of a new allotropic form of elemental carbon – the fullerenes – and subsequently other novel forms of elemental carbon with pyramidalized surfaces, most notably single-walled and multi-walled carbon nanotubes, introduced a novel structural motif to the polycyclic aromatic hydrocarbons (PAHs) with nonplanar surfaces. Our research program supported by BES DOE grant DE-FG02-04ER15514 has dealt with the synthesis, structural studies, and chemistry of the novel curved-surface PAHs with carbon frameworks structurally related to fullerenes. They are referred to as “buckybowls”. We prepared several new buckybowls and, even more importantly, developed the efficient, gram-scale synthetic methodologies for the preparationmore » of small buckybowls, most notably corannulene (C20H10) and its derivatives. In addition, the employment of the corannulene-based synthons previously developed in our laboratory led to a number of highly nonplanar molecular architectures with two or more corannulene subunits with a potential for the applications as novel materials in separation sciences, nanoelectronics, photovoltaics and catalysis. In collaboration with Professor Angelici (Iowa State) we prepared and characterized several transition metal complexes of corannulene, providing the first structural characterization of η6 metal complexes of buckybowls by a single crystal X-ray diffraction. In addition to the definitive structural characterization of the complexes we demonstrated that the (η6-C6Me6)Ru2+ unit in some relatively stable complexes activate the corannulene ligand to react with proper nucleophiles suggesting that such complexex may be used in catalysis. (Section C). We have explored the efficiency of the dispersion-based interactions of curved-surface conjugated carbon networks by high-level computational models. We showed that the curvature of such networks does not reduce the van der Waals attractions as compared to the planar systems of similar size. We than concentrated on the design, synthesis and testing of the previously unknown molecular receptors with corannulene pincers which are capable of forming the strong ball-and-socket inclusion complexes with fullerenes in solution and in the solid state. Buckycatcher I (a molecular receptor with two corannulene pincers preorganized on a tetrabensocyclooctatetraene tether) inclusion complexes with fullerenes provided the first experimental evidence for the importance of concave-convex π – π interactions in the supramolecular chemistry of fullerene carbon cages with buckybowls. C60@Buckycatcher I has become the prototypical supramolecular system formed by the relatively weak (on the atom-to-atom bases) and has been extensively used by the computational community to test the quality of the theoretical models. In addition, Buckycatcher I shows an exceptional ability to adopt other guest molecules and several its inclusion complexes and/or solvates have been structurally characterized. These unusual structures show the potential of the buckycatchers to be tested as novel organic materials. “Intelligent design” of molecular receptors with corannulene receptors using computational approach allowing for a priori prediction of their binding potentials led to the preparation of other buckycatchers. Both bi- and tridentate corannulene pincers were tested and two of the bidentate receptors (Buckycatchers II and III) exhibited the outstanding affinity toward fullerenes, significantly exciding Buckycatcher I performance. Careful tailoring of the tethers resulted in the optimization of binding energies of the receptors with guest carbon cages and in the reduction of the entropy/solvation penalties. Practical preparation of dicorannulenopentacene opens a new avenue for the synthesis of a pool of bis-corannulene receptors possessing polar groups on their dibenzobarrelene tether. The polar “anchors” can be used to attach these efficient fullerene receptors to solid supports in order to modify their surfaces with the potential applications in separation sciences, catalysis and photovoltaic materials. additionally, the presence of such groups will improve the solubility of the receptors in polar solvents, expanding the scope of their supramolecular chemistry in solutions. Rigorous studies of thermodynamics of host-guest association of molecular clips and tweezers in organic solvents with C60/C70 inclusion complexes with Buckycatcher I as a model system have provided a full set of thermodynamical data including ΔG, ΔH, and –TΔS, for the formation of the inclusion complexes over a range of temperatures and in several solvents. Both 1H NMR and Isothermal Calorimetry (ITC) titrations provide virtually identical association constants, confirming the reliability of the results. WE have shown that thermodynamics of the host-guest complex formation is more complicated than anticipated and proposed by the existing computational models. These data are of premium importance for the testing of the computational solvation models and for a deeper understanding of the supramolecular interactions in organic solvents.« less

The birth and evolution of surface science: child of the union of science and technology.

PubMed

Duke, C B

2003-04-01

This article is an account of the birth and evolution of surface science as an interdisciplinary research area. Surface science emanated from the confluence of concepts and tools in physics and chemistry with technological innovations that made it possible to determine the structure and properties of surfaces and interfaces and the dynamics of chemical reactions at surfaces. The combination in the 1960s and 1970s of ultra-high-vacuum (i.e., P < 10(-7) Pascal or 10(-9) Torr) technology with the recognition that electrons in the energy range from 50 to 500 eV exhibited inelastic collision mean free paths of the order of a few angstroms fostered an explosion of activity. The results were a reformulation of the theory of electron solid scattering, the nearly universal use of electron spectroscopies for surface characterization, the rise of surface science as an independent interdisciplinary research area, and the emergence of the American Vacuum Society (AVS) as a major international scientific society. The rise of microelectronics in the 1970s and 1980s resulted in huge increases in computational power. These increases enabled more complex experiments and the utilization of density functional theory for the quantitative prediction of surface structure and dynamics. Development of scanning-probe microscopies in the 1990s led to atomic-resolution images of macroscopic surfaces and interfaces as well as videos of atoms moving about on surfaces during growth and diffusion. Scanning probes have since brought solid-liquid interfaces into the realm of atomic-level surface science, expanding its scope to more complex systems, including fragile biological materials and processes.

Innovative and water based stripping approach for thick and bulk photoresists

NASA Astrophysics Data System (ADS)

Rudolph, Matthias; Schumann, Dirk; Thrun, Xaver; Esche, Silvio; Hohle, Christoph

2014-10-01

The usage of phase fluid based stripping agents to remove photoresists from silicon substrates was studied. Photoresists are required for many silicon based technologies such as MEMS patterning, 3D-Integration or frontend and backend of line semiconductor applications [1]. Although the use of resists is very common, their successful integration often depends on the ability to remove the resist after certain processing steps. On the one hand the resist is changing during subsequent process steps that can cause a thermally activated cross-linking which increases the stripping complexity. Resist removal is also challenging after the formation of a hard polymer surface layer during plasma or implant processes which is called skin or crust [2]. On the other hand the choice of stripping chemistry is often limited due to the presence of functional materials such as metals which can be damaged by aggressive stripping chemistries [3].

Alloy chemistry and microstructural control to meet the demands of the automotive Stirling engine

NASA Technical Reports Server (NTRS)

Stephens, Joseph R.

1988-01-01

The automotive Stirling engine now under development by DOE/NASA as an alternative to the internal combustion engine, imposes severe materials requirements for the hot portion of the engine. Materials selected must be low cost and contain a minimum of strategic elements so that availability is not a problem. Heater head tubes contain high pressure hydrogen on the inside and are exposed to hot combustion gases on the outside surface. The cylinders and regenerator housings must be readily castable into complex shapes having varying wall thicknesses and be amenable to brazing and welding operations. Also, high strength, oxidation resistance, resistance to hydrogen permeation, cyclic operation, and long-life are required. A research program conducted by NASA Lewis focused on alloy chemistry and microstructural control to achieve the desired properties over the life of the engine. Results of alloy selection, characterization, evaluation, and actual engine testing of selected materials are presented.

Alloy chemistry and microstructural control to meet the demands of the automotive Stirling engine

NASA Technical Reports Server (NTRS)

Stephens, J. R.

1986-01-01

The automotive Stirling engine now under development by DOE/NASA as an alternative to the internal combustion engine, imposes severe materials requirements for the hot portion of the engine. Materials selected must be low cost and contain a minimum of strategic elements so that availability is not a problem. Heater head tubes contain high pressure hydrogen on the inside and are exposed to hot combustion gases on the outside surface. The cylinders and regenerator housings must be readily castable into complex shapes having varying wall thicknesses and be amenable to brazing and welding operations. Also, high strength, oxidation resistance, resistance to hydrogen permeation, cyclic operation, and long-life are required. A research program conducted by NASA Lewis focused on alloy chemistry and microstructural control to achieve the desired properties over the life of the engine. Results of alloy selection, characterization, evaluation, and actual engine testing of selected materials are presented.

MSL Chemistry and Mineralogy X-Ray Diffraction X-Ray Fluorescence (CheMin) Instrument

NASA Technical Reports Server (NTRS)

Zimmerman, Wayne; Blake, Dave; Harris, William; Morookian, John Michael; Randall, Dave; Reder, Leonard J.; Sarrazin, Phillipe

2013-01-01

This paper provides an overview of the Mars Science Laboratory (MSL) Chemistry and Mineralogy Xray Diffraction (XRD), X-ray Fluorescence (XRF) (CheMin) Instrument, an element of the landed Curiosity rover payload, which landed on Mars in August of 2012. The scientific goal of the MSL mission is to explore and quantitatively assess regions in Gale Crater as a potential habitat for life - past or present. The CheMin instrument will receive Martian rock and soil samples from the MSL Sample Acquisition/Sample Processing and Handling (SA/SPaH) system, and process it utilizing X-Ray spectroscopy methods to determine mineral composition. The Chemin instrument will analyze Martian soil and rocks to enable scientists to investigate geophysical processes occurring on Mars. The CheMin science objectives and proposed surface operations are described along with the CheMin hardware with an emphasis on the system engineering challenges associated with developing such a complex instrument.

Chemistry and evolution of Titan's atmosphere

NASA Technical Reports Server (NTRS)

Strobel, D. F.

1982-01-01

The chemistry and evolution of Titan's atmosphere are reviewed, in light of the scientific findings from the Voyager mission. It is argued that the present N2 atmosphere may be Titan's initial atmosphere, rather than one photochemically derived from an original NH3 atmosphere. The escape rate of hydrogen from Titan is controlled by photochemical production from hydrocarbons. CH4 is irreversibly converted to less hydrogen-rich hydrocarbons, which over geologic time accumulate on the surface to a layer thickness of about 0.5 km. Magnetospheric electrons interacting with Titan's exosphere may dissociate enough N2 into hot, escaping N atoms to remove about 0.2 of Titan's present atmosphere over geologic time. The energy dissipation of magnetospheric electrons exceeds solar EUV energy deposition in Titan's atmosphere by an order of magnitude, and is the principal driver of nitrogen photochemistry. The environmental conditions in Titan's upper atmosphere are favorable to building up complex molecules, particularly in the north polar cap region.

Using stable isotopes to understand hydrochemical processes in and around a Prairie Pothole wetland in the Northern Great Plains, USA

USGS Publications Warehouse

Mills, Christopher T.; Goldhaber, Martin B.; Stricker, Craig A.; Holloway, JoAnn M.; Morrison, Jean M.; Ellefsen, Karl J.; Rosenberry, Donald O.; Thurston, Roland S.

2011-01-01

Millions of internally drained wetland systems in the Prairie Potholes region of the northern Great Plains (USA and Canada) provide indispensable habitat for waterfowl and a host of other ecosystem services. The hydrochemistry of these systems is complex and a crucial control on wetland function, flora and fauna. Wetland waters can have high concentrations of SO2-4 due to the oxidation of large amounts of pyrite in glacial till that is in part derived from the Pierre shale. Water chemistry including δ18OH2O, δ2HH2O, and δ34SSO4 values, was determined for groundwater, soil pore water, and wetland surface water in and around a discharge wetland in North Dakota. The isotopic data for the first time trace the interaction of processes that affect wetland chemistry, including open water evaporation, plant transpiration, and microbial SO4 reduction.

Molecular growth from a Mo176 to a Mo248 cluster

NASA Astrophysics Data System (ADS)

Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

1999-01-01

In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

Mineralogy, petrology and chemistry of ANT-suite rocks from the lunar highlands

NASA Technical Reports Server (NTRS)

Prinz, M.; Keil, K.

1977-01-01

Anorthositic-noritic-troctolitic (ANT) rocks are the oldest and most abundant rocks of the lunar surface, and comprise about 90% of the suite of the lunar highlands. Consideration is given to the mineralogy, petrology, bulk chemistry, and origin of ANT-suite rocks. Problems associated in classifying and labeling lunar highland rocks because of textural complexities occurring from impact modifications are discussed. The mineralogy of ANT-suite rocks, dominated by plagioclase, olivine and pyrozene, and containing various minor minerals, is outlined. The petrology of ANT-suite rocks is reviewed along with the major element bulk composition of these rocks, noting that they are extremely depleted in K2O and P2O5. Various models describing the origin of ANT-suite rocks are summarized, and it is suggested that this origin involves a parental liquid of high-alumina basalt with low Fe/Fe+Mg.

Transition Metal Polypyridine Complexes: Studies of Mediation in Dye-Sensitized Solar Cells and Charge Separation

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

Elliott, C. Michael; Prieto, Amy L.

2017-02-08

The Elliott group has long been supported by DOE for studies of cobalt(II/III) trisbypiridine (DTB) mediator complexes in dye sensitized solar cells. Previous work demonstrated that Co(II/III) chemistry is sensitive to the environment, showing unprecedented electrode-surface and electrolyte dependant voltammetry. In electrolytes that have large lipophilic cations, voltammetry of the [Co(DTB) 3] 2+/3+ couple is nearly Nernstian in appearance on nominally oxide-free metal surfaces. In contrast, on semiconductor electrodes in electrolytes with small, hard cations such as Li +, the electron transfer rates are so slow that it is difficult to measure any Faradaic current even at overpotentials of ±1more » V. These studies are of direct relevance to the operation of cobalt-based mediators in solar cells. The research has also shown that these mediators are compatible with copper phenantroline based dyes, in contrast to I - due to the insolubility of CuI.« less

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

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

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

DOE PAGES

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; ...

2017-03-06

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying thesemore » methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.« less

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

DOE PAGES

Han, Lili; Meng, Qingping; Wang, Deli; ...

2016-12-08

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-inducedmore » chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. As a result, this work characterizes the pathways that can control the morphology in binary oxide materials.« less

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

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

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

The supramolecular chemistry of lipid oxidation and antioxidation in bulk oils

PubMed Central

Budilarto, Elizabeth S; Kamal-Eldin, Afaf

2015-01-01

The microenvironment formed by surface active compounds is being recognized as the active site of lipid oxidation. Trace amounts of water occupy the core of micro micelles and several amphiphilic minor components (e.g., phospholipids, monoacylglycerols, free fatty acids, etc.) act as surfactants and affect lipid oxidation in a complex fashion dependent on the structure and stability of the microemulsions in a continuous lipid phase such as bulk oil. The structures of the triacylglycerols and other lipid-soluble molecules affect their organization and play important roles during the course of the oxidation reactions. Antioxidant head groups, variably located near the water-oil colloidal interfaces, trap and scavenge radicals according to their location and concentration. According to this scenario, antioxidants inhibit lipid oxidation not only by scavenging radicals via hydrogen donation but also by physically stabilizing the micelles at the microenvironments of the reaction sites. There is a cut-off effect (optimum value) governing the inhibitory effects of antioxidants depending inter alias on their hydrophilic/lipophilic balance and their concentrations. These complex effects, previously considered as paradoxes in antioxidants research, are now better explained by the supramolecular chemistry of lipid oxidation and antioxidants, which is discussed in this review. PMID:26448722

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

DOE PAGES

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila; ...

2017-02-02

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

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.

Finding the chemistry in biomass pyrolysis: Millisecond chemical kinetics and visualization

NASA Astrophysics Data System (ADS)

Krumm, Christoph

Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first- ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Through this technique, a transition is identified, known as the reactive melting point, between low and high temperature depolymerization. The transition between two mechanisms of cellulose decompositions unifies the mechanisms that govern low temperature char formation, intermediate pyrolysis conditions, and high temperature gas formation. The conditions under which biomass undergoes pyrolysis, including modes of heat transfer, have been shown to significantly affect the distribution of biorenewable chemical and fuel products. High-speed photography is used to observe the liftoff of initially crystalline cellulose particles when impinged on a heated surface, known as the Leidenfrost effect for room-temperature liquids. Order-of-magnitude changes in the lifetime of cellulose particles are observed as a result of changing modes in heat transfer as cellulose intermediate liquid droplets wet and de-wet polished ceramic surfaces. Introduction of surface macroporosity is shown to completely inhibit the cellulose Leidenfrost effect, providing avenues for surface modification and reactor design to control particle heat transfer in industrial pyrolysis applications. Cellulosic particles on surfaces consisting of microstructured, asymmetric ratchets were observed to spontaneously move orthogonal to ratchet wells above the cellulose reactive Leidenfrost temperature (>750 °C). Evaluation of the accelerating particles supported the mechanism of propelling viscous forces (50-200 nN) from rectified pyrolysis vapors, thus providing the first example of biomass conveyors with no moving parts driven by high temperature for biofuel reactors. Combined knowledge of pyrolysis chemistry, kinetics, and heat and mass transport effects direct the design of the next generation pyrolysis reactors for tuning bio- oil quality and design of improved catalytic upgrading technology.

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.

Copolymer Synthesis and Characterization by Post-Polymerization Modification

NASA Astrophysics Data System (ADS)

Galvin, Casey James

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

Preparation, Analysis, and Characterization of Some Transition Metal Complexes--A Holistic Approach

ERIC Educational Resources Information Center

Blyth, Kristy M.; Mullings, Lindsay R.; Philips, David N.; Pritchard, David; van Bronswijk, Wilhelm

2005-01-01

The chemical and instrumental methods used in the study of transition-metal complexes provide a complete determination of their structure, bonding, and properties. It unites concepts of analytical, inorganic, and physical chemistry in a way that students might appreciate that these areas of chemistry are not different.

Hierarchical zwitterionic modification of a SERS substrate enables real-time drug monitoring in blood plasma

NASA Astrophysics Data System (ADS)

Sun, Fang; Hung, Hsiang-Chieh; Sinclair, Andrew; Zhang, Peng; Bai, Tao; Galvan, Daniel David; Jain, Priyesh; Li, Bowen; Jiang, Shaoyi; Yu, Qiuming

2016-11-01

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive analytical technique with molecular specificity, making it an ideal candidate for therapeutic drug monitoring (TDM). However, in critical diagnostic media including blood, nonspecific protein adsorption coupled with weak surface affinities and small Raman activities of many analytes hinder the TDM application of SERS. Here we report a hierarchical surface modification strategy, first by coating a gold surface with a self-assembled monolayer (SAM) designed to attract or probe for analytes and then by grafting a non-fouling zwitterionic polymer brush layer to effectively repel protein fouling. We demonstrate how this modification can enable TDM applications by quantitatively and dynamically measuring the concentrations of several analytes--including an anticancer drug (doxorubicin), several TDM-requiring antidepressant and anti-seizure drugs, fructose and blood pH--in undiluted plasma. This hierarchical surface chemistry is widely applicable to many analytes and provides a generalized platform for SERS-based biosensing in complex real-world media.

Hierarchical zwitterionic modification of a SERS substrate enables real-time drug monitoring in blood plasma

PubMed Central

Sun, Fang; Hung, Hsiang-Chieh; Sinclair, Andrew; Zhang, Peng; Bai, Tao; Galvan, Daniel David; Jain, Priyesh; Li, Bowen; Jiang, Shaoyi; Yu, Qiuming

2016-01-01

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive analytical technique with molecular specificity, making it an ideal candidate for therapeutic drug monitoring (TDM). However, in critical diagnostic media including blood, nonspecific protein adsorption coupled with weak surface affinities and small Raman activities of many analytes hinder the TDM application of SERS. Here we report a hierarchical surface modification strategy, first by coating a gold surface with a self-assembled monolayer (SAM) designed to attract or probe for analytes and then by grafting a non-fouling zwitterionic polymer brush layer to effectively repel protein fouling. We demonstrate how this modification can enable TDM applications by quantitatively and dynamically measuring the concentrations of several analytes—including an anticancer drug (doxorubicin), several TDM-requiring antidepressant and anti-seizure drugs, fructose and blood pH—in undiluted plasma. This hierarchical surface chemistry is widely applicable to many analytes and provides a generalized platform for SERS-based biosensing in complex real-world media. PMID:27834380

Crossword Puzzles for Chemistry Education: Learning Goals beyond Vocabulary

ERIC Educational Resources Information Center

Yuriev, Elizabeth; Capuano, Ben; Short, Jennifer L.

2016-01-01

Chemistry is a technical scientific discipline strongly underpinned by its own complex and diverse language. To be successful in the problem-solving aspects of chemistry, students must master the language of chemistry, and in particular, the definition of terms and concepts. To assist students in this challenging task, a variety of instructional…

"Triangulation": An Expression for Stimulating Metacognitive Reflection Regarding the Use of "Triplet" Representations for Chemistry Learning

ERIC Educational Resources Information Center

Thomas, Gregory P.

2017-01-01

Concerns persist regarding high school students' chemistry learning. Learning chemistry is challenging because of chemistry's innate complexity and the need for students to construct associations between different, yet related representations of matter and its changes. Students should be taught to reason about and consider chemical phenomena using…

Pi-metal complexes of tetrapyrrolic systems. A novel coordination mode in "porphyrin-like" chemistry.

PubMed

Cuesta, Luciano; Sessler, Jonathan L

2009-09-01

The coordination chemistry of porphyrins and related tetrapyrrolic ligands has traditionally centered around the ability of these systems to form pyrrole N-ligated complexes via the formation of sigma bonds, either within the N(4) core or displaced above it. In fact, such sigma-complexes are known with almost every metal cation in the periodic table. However, a growing number of pi-complexes derived from tetrapyrrolic ligands have been reported in recent years. The underlying coordination mode, while still novel in the context of "porphyrin-like" chemistry, is already being recognized for the effects it can impart over the reactivity, as well as the spectroscopic, redox, electronic, and optical properties of various oligopyrrolic macrocycles. This critical review summarizes accomplishments made in this fast-emerging field (59 references).

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

Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode

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

Dares, C. J.; Lapides, A. M.; Mincher, B. J.

A high surface area, tin-doped indium oxide electrode surface-derivatized with a terpyridine ligand has been applied to the oxidation of trivalent americium to Am(V) and Am(VI) in nitric acid. Potentials as low as 1.8 V vs. the saturated calomel electrode are used, 0.7 V lower than the 2.6 V potential for one-electron oxidation of Am(III) to Am(IV) in 1 M acid. This simple electrochemical procedure provides, for the first time, a method for accessing the higher oxidation states of Am in non-complexing media for developing the coordination chemistries of Am(V) and Am(VI) and, more importantly, for separation of americium frommore » nuclear waste streams.« less

Engineering Transition-Metal-Coated Tungsten Carbides for Efficient and Selective Electrochemical Reduction of CO2 to Methane.

PubMed

Wannakao, Sippakorn; Artrith, Nongnuch; Limtrakul, Jumras; Kolpak, Alexie M

2015-08-24

The design of catalysts for CO2 reduction is challenging because of the fundamental relationships between the binding energies of the reaction intermediates. Metal carbides have shown promise for transcending these relationships and enabling low-cost alternatives. Herein, we show that directional bonding arising from the mixed covalent/metallic character plays a critical role in governing the surface chemistry. This behavior can be described by consideration of individual d-band components. We use this model to predict efficient catalysts based on tungsten carbide with a sub-monolayer of iron adatoms. Our approach can be used to predict site-preference and binding-energy trends for complex catalyst surfaces. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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…

Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

ERIC Educational Resources Information Center

Ison, Elon A.; Ison, Ana

2012-01-01

A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

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.

Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface

PubMed Central

2016-01-01

Interfaces are ubiquitous in the environment and many atmospheric key processes, such as gas deposition, aerosol, and cloud formation are, at one stage or another, strongly impacted by physical and chemical processes occurring at interfaces. Here, the photoinduced chemistry of an air/water interface coated with nonanoic acid—a fatty acid surfactant we use as a proxy for chemically complex natural aqueous surface microlayers—was investigated as a source of volatile and semivolatile reactive organic species. The carboxylic acid coating significantly increased the propensity of photosensitizers, chosen to mimic those observed in real environmental waters, to partition to the interface and enhance reactivity there. Photochemical formation of functionalized and unsaturated compounds was systematically observed upon irradiation of these coated surfaces. The role of a coated interface appears to be critical in providing a concentrated medium allowing radical–radical reactions to occur in parallel with molecular oxygen additions. Mechanistic insights are provided from extensive analysis of products observed in both gas and aqueous phases by online switchable reagent ion-time of flight-mass spectrometry and by off-line ultraperformance liquid chromatography coupled to a Q Exactive high resolution mass spectrometer through heated electrospray ionization, respectively. PMID:27611489

Single-molecule dynamics in nanofabricated traps

NASA Astrophysics Data System (ADS)

Cohen, Adam

2009-03-01

The Anti-Brownian Electrokinetic trap (ABEL trap) provides a means to immobilize a single fluorescent molecule in solution, without surface attachment chemistry. The ABEL trap works by tracking the Brownian motion of a single molecule, and applying feedback electric fields to induce an electrokinetic motion that approximately cancels the Brownian motion. We present a new design for the ABEL trap that allows smaller molecules to be trapped and more information to be extracted from the dynamics of a single molecule than was previously possible. In particular, we present strategies for extracting dynamically fluctuating mobilities and diffusion coefficients, as a means to probe dynamic changes in molecular charge and shape. If one trapped molecule is good, many trapped molecules are better. An array of single molecules in solution, each immobilized without surface attachment chemistry, provides an ideal test-bed for single-molecule analyses of intramolecular dynamics and intermolecular interactions. We present a technology for creating such an array, using a fused silica plate with nanofabricated dimples and a removable cover for sealing single molecules within the dimples. With this device one can watch the shape fluctuations of single molecules of DNA or study cooperative interactions in weakly associating protein complexes.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

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.

Modeling the chemistry of complex petroleum mixtures.

PubMed Central

Quann, R J

1998-01-01

Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the astronomical number of molecular components. Modeling the composition and behavior of such complex mixtures in refinery processes has accordingly evolved along a simplifying concept called lumping. Lumping reduces the complexity of the problem to a manageable form by grouping the entire set of molecular components into a handful of lumps. This traditional approach does not have a molecular basis and therefore excludes important aspects of process chemistry and molecular property fundamentals from the model's formulation. A new approach called structure-oriented lumping has been developed to model the composition and chemistry of complex mixtures at a molecular level. The central concept is to represent an individual molecular or a set of closely related isomers as a mathematical construct of certain specific and repeating structural groups. A complex mixture such as petroleum can then be represented as thousands of distinct molecular components, each having a mathematical identity. This enables the automated construction of large complex reaction networks with tens of thousands of specific reactions for simulating the chemistry of complex mixtures. Further, the method provides a convenient framework for incorporating molecular physical property correlations, existing group contribution methods, molecular thermodynamic properties, and the structure--activity relationships of chemical kinetics in the development of models. PMID:9860903

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.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Multifunctional Surface Modification of Nanodiamonds Based on Dopamine Polymerization.

PubMed

Zeng, Yun; Liu, Wenyan; Wang, Zheyu; Singamaneni, Srikanth; Wang, Risheng

2018-04-03

Surface functionalization of nanodiamonds (NDs), which is of great interest in advanced material and therapeutic applications, requires the immobilization of functional species, such as nucleic acids, bioprobes, drugs, and metal nanoparticles, onto NDs' surfaces to form stable nanoconjugates. However, it is still challenging to modify the surface of NDs due to the complexity of their surface chemistry and the low density of each functional group on the surfaces of NDs. In this work, we demonstrate a general applicable surface functionalization approach for the preparation of ND-based core-shell nanoconjugates using dopamine polymerization. By taking advantage of the universal adhesion and versatile reactivity of polydopamine, we have effectively conjugated DNA and silver nanoparticles onto NDs. Moreover, the catalytic activity of ND-supported silver nanoparticle was characterized by the reduction of 4-nitrophenol, and the addressability of NDs was tested through DNA hybridization that formed satellite ND-gold nanorod conjugation. This simple and robust method we have presented may significantly improve the capability for attaching various functionalities onto NDs and open up new platforms for applications of NDs.

Surface CHEMKIN (Version 4. 0): A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface---gas-phase interface

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

Coltrin, M.E.; Kee, R.J.; Rupley, F.M.

1991-07-01

Heterogeneous reaction at the interface between a solid surface and adjacent gas is central to many chemical processes. Our purpose for developing the software package SURFACE CHEMKIN was motivated by our need to understand the complex surface chemistry in chemical vapor deposition systems involving silicon, silicon nitride, and gallium arsenide. However, we have developed the approach and implemented the software in a general setting. Thus, we expect it will find use in such diverse applications as chemical vapor deposition, chemical etching, combustion of solids, and catalytic processes, and for a wide range of chemical systems. We believe that it providesmore » a powerful capability to help model, understand, and optimize important industrial and research chemical processes. The SURFACE CHEMKIN software is designed to work in conjunction with the CHEMKIN-2 software, which handles the chemical kinetics in the gas phase. It may also be used in conjunction with the Transport Property Package, which provides information about molecular diffusion. Thus, these three packages provide a foundation on which a user can build applications software to analyze gas-phase and heterogeneous chemistry in flowing systems. These packages should not be considered programs'' in the ordinary sense. That is, they are not designed to accept input, solve a particular problem, and report the answer. Instead, they are software tools intended to help a user work efficiently with large systems of chemical reactions and develop Fortran representations of systems of equations that define a particular problem. It is up the user to solve the problem and interpret the answer. 11 refs., 15 figs., 5 tabs.« less

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

PubMed

Glatz, Brittany; Sarupria, Sapna

2018-01-23

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

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

DTIC Science & Technology

1992-05-26

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

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

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

Not Available

1987-08-01

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

Testing grain-surface chemistry in massive hot-core regions

NASA Astrophysics Data System (ADS)

Bisschop, S. E.; Jørgensen, J. K.; van Dishoeck, E. F.; de Wachter, E. B. M.

2007-04-01

Aims:We study the chemical origin of a set of complex organic molecules thought to be produced by grain surface chemistry in high mass young stellar objects (YSOs). Methods: A partial submillimeter line-survey was performed toward 7 high-mass YSOs aimed at detecting H2CO, CH3OH, CH2CO, CH3CHO, C2H5OH, HCOOH, HNCO and NH2CHO. In addition, lines of CH3CN, C2H5CN, CH3CCH, HCOOCH3, and CH3OCH3 were observed. Rotation temperatures and beam-averaged column densities are determined. To correct for beam dilution and determine abundances for hot gas, the radius and H2 column densities of gas at temperatures >100 K are computed using 850 μm dust continuum data and source luminosity. Results: Based on their rotation diagrams, molecules can be classified as either cold (<100 K) or hot (>100 K). This implies that complex organics are present in at least two distinct regions. Furthermore, the abundances of the hot oxygen-bearing species are correlated, as are those of HNCO and NH2CHO. This is suggestive of chemical relationships within, but not between, those two groups of molecules. Conclusions: .The most likely explanation for the observed correlations of the various hot molecules is that they are "first generation" species that originate from solid-state chemistry. This includes H2CO, CH3OH, C2H5OH, HCOOCH3, CH3OCH3, HNCO, NH2CHO, and possibly CH3CN, and C2H5CN. The correlations between sources implies very similar conditions during their formation or very similar doses of energetic processing. Cold species such as CH2CO, CH3CHO, and HCOOH, some of which are seen as ices along the same lines of sight, are probably formed in the solid state as well, but appear to be destroyed at higher temperatures. A low level of non-thermal desorption by cosmic rays can explain their low rotation temperatures and relatively low abundances in the gas phase compared to the solid state. The CH3CCH abundances can be fully explained by low temperature gas phase chemistry. No cold N-containing molecules are found. Appendices are only available in electronic form at http://www.aanda.org

Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

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

Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.

The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

DOE PAGES

Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.; ...

2017-06-12

The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains, Colorado and New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Bove, D.J.; Plumlee, G.S.; Runkel, R.L.

2009-01-01

Acidic, metal-rich waters produced by the oxidative weathering and resulting leaching of major and trace elements from pyritic rocks can adversely affect water quality in receiving streams and riparian ecosystems. Five study areas in the southern Rocky Mountains with naturally acidic waters associated with porphyry mineralization were studied to document variations in water chemistry and processes that control the chemical variations. Study areas include the Upper Animas River watershed, East Alpine Gulch, Mount Emmons, and Handcart Gulch in Colorado and the Red River in New Mexico. Although host-rock lithologies in all these areas range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, the mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous, ranging from ???1 to >5 vol.%. Springs and headwater streams have pH values as low as 2.6, SO4 up to 3700 mg/L and high dissolved metal concentrations (for example: Fe up to 400 mg/L; Cu up to 3.5 mg/L; and Zn up to 14.4 mg/L). Intensity of hydrothermal alteration and presence of sulfides are the primary controls of water chemistry of these naturally acidic waters. Subbasins underlain by intensely hydrothermally altered lithologies are poorly vegetated and quite susceptible to storm-induced surface runoff. Within the Red River study area, results from a storm runoff study documented downstream changes in river chemistry: pH decreased from 7.80 to 4.83, alkalinity decreased from 49.4 to <1 mg/L, SO4 increased from 162 to 314 mg/L, dissolved Fe increased from to 0.011 to 0.596 mg/L, and dissolved Zn increased from 0.056 to 0.607 mg/L. Compared to mine drainage in the same study areas, the chemistry of naturally acidic waters tends to overlap but not reach the extreme concentrations of metals and acidity as some mine waters. The chemistry of waters draining these mineralized but unmined areas can be used to estimate premining conditions at sites with similar geologic and hydrologic conditions. For example, the US Geological Survey was asked to estimate premining ground-water chemistry at the Questa Mo mine, and the proximal analog approach was used because a mineralized but unmined area was located adjacent to the mine property. By comparing and contrasting water chemistry from different porphyry mineralized areas, this study not only documents the range in concentrations of constituents of interest but also provides insight into the primary controls of water chemistry.

Let Students Derive, by Themselves, Two-Dimensional Atomic and Molecular Quantum Chemistry from Scratch

ERIC Educational Resources Information Center

Ge, Yingbin

2016-01-01

Hands-on exercises are designed for undergraduate physical chemistry students to derive two-dimensional quantum chemistry from scratch for the H atom and H[subscript 2] molecule, both in the ground state and excited states. By reducing the mathematical complexity of the traditional quantum chemistry teaching, these exercises can be completed…

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.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

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

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan

2015-11-10

Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupledmore » with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.« less

Evidence of Aerosols as a Media for Rapid Daytime HONO Production over China

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

Liu, Zhen; Wang, Yuhang; Costabile, Francesa

Current knowledge of daytime HONO sources remains incomplete. A large missing daytime HONO source has been found in many places around the world, including polluted regions in China. Conventional understanding and recent studies attributed this missing source mainly to ground surface processes or gas-phase chemistry, while assuming aerosols to be an insignificant media for HONO production. We analyze in situ observations of HONO and its precursors at an urban site in Beijing, China, and report an apparent dependence of the missing HONO source strength on aerosol surface area and solar ultraviolet radiation. Based on extensive correlation analysis and process-modeling, wemore » propose that the rapid daytime HONO production in Beijing can be explained by enhanced hydrolytic disproportionation of NO2 on aqueous aerosol surfaces due to catalysis by dicarboxylic acid anions. The combination of high abundance of NO2, aromatic hydrocarbons, and aerosols over broad regions in China likely leads to elevated HONO levels, rapid OH production, and enhanced oxidizing capacity on a regional basis. Our findings call for attention to aerosols as a media for daytime heterogeneous HONO production in polluted regions like Beijing. This study also highlights the complex and uncertain heterogeneous chemistry in China, which merits future efforts of reconciling regional modeling and laboratory experiments, in order to understand and mitigate the regional particulate and O3 pollutions over China.« less

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.

Adsorption of various types of amino acids on the graphene and boron-nitride nano-sheet, a DFT-D3 study

NASA Astrophysics Data System (ADS)

Zhiani, Rahele

2017-07-01

The binding properties of the adsorption of five different classes of amino acids, namely, alanine (Ala), arginine (Arg), asparagine (Asn), histidine (His) and cysteine (Cys) on the surface of the graphene (Gra) and the born-nitride (BN) nano-sheet structures were studied from molecular viewpoint using quantum mechanics methods. Density functional theory (DFT) and DFT-D3 calculations were carried out to investigate the electronic properties and the dispersion interaction of the amino acid/adsorbent complexes. Several parameters affecting the interactions between the amino acids and the adsorbent surfaces such as solvent effect, adsorption energy and separation distance were investigated. Findings show that Arg forms the most stable complexes with the graphene and the BN nano-sheet compare to the other amino acids used in this study. The observed frequency results which were related to the band gap energies were consistent with the above statement. Results exhibit that adsorption of the amino acids on the surface of the BN nano-sheet and the graphene accompanied with the release of the energy. Calculations show that there are no bonded interactions between the amino acids and adsorbent surfaces. The polarity of the BN nano-sheet provides the more affinity towards the amino acids. These results were proved by the quantum chemistry studies.

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.

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.

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.

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

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.

Evaluation of the new EMAC-SWIFT chemistry climate model

NASA Astrophysics Data System (ADS)

Scheffler, Janice; Langematz, Ulrike; Wohltmann, Ingo; Rex, Markus

2016-04-01

It is well known that the representation of atmospheric ozone chemistry in weather and climate models is essential for a realistic simulation of the atmospheric state. Including atmospheric ozone chemistry into climate simulations is usually done by prescribing a climatological ozone field, by including a fast linear ozone scheme into the model or by using a climate model with complex interactive chemistry. While prescribed climatological ozone fields are often not aligned with the modelled dynamics, a linear ozone scheme may not be applicable for a wide range of climatological conditions. Although interactive chemistry provides a realistic representation of atmospheric chemistry such model simulations are computationally very expensive and hence not suitable for ensemble simulations or simulations with multiple climate change scenarios. A new approach to represent atmospheric chemistry in climate models which can cope with non-linearities in ozone chemistry and is applicable to a wide range of climatic states is the Semi-empirical Weighted Iterative Fit Technique (SWIFT) that is driven by reanalysis data and has been validated against observational satellite data and runs of a full Chemistry and Transport Model. SWIFT has recently been implemented into the ECHAM/MESSy (EMAC) chemistry climate model that uses a modular approach to climate modelling where individual model components can be switched on and off. Here, we show first results of EMAC-SWIFT simulations and validate these against EMAC simulations using the complex interactive chemistry scheme MECCA, and against observations.

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.

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

PubMed

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

2012-04-07

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

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...

On the Surface Formation of NH3 and HNCO in Dark Molecular Clouds - Searching for Wöhler Synthesis in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Fedoseev, Gleb; Lamberts, Thanja; Linnartz, Harold; Ioppolo, Sergio; Zhao, Dongfeng

Despite its potential to reveal the link between the formation of simple species and more complex molecules (e.g., amino acids), the nitrogen chemistry of the interstellar medium (ISM) is still poorly understood. Ammonia (NH _{3}) is one of the few nitrogen-bearing species that have been observed in interstellar ices toward young stellar objects (YSOs) and quiescent molecular clouds. The aim of the present work is to experimentally investigate surface formation routes of NH _{3} and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant cryogenic temperatures. This study focuses on the formation of NH _{3} and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing start to become predominant. Our work confirms the surface formation of ammonia through the sequential addition of three hydrogen/deuterium atoms to a single nitrogen atom at low temperature. The H/D fractionation of the formed ammonia is also shown. Furthermore, we show the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH _{3}. Finally, we discuss the implications of HNCO in astrobiology, as a possible starting point for the formation of more complex prebiotic species.

Imaging of surface spin textures on bulk crystals by scanning electron microscopy

NASA Astrophysics Data System (ADS)

Akamine, Hiroshi; Okumura, So; Farjami, Sahar; Murakami, Yasukazu; Nishida, Minoru

2016-11-01

Direct observation of magnetic microstructures is vital for advancing spintronics and other technologies. Here we report a method for imaging surface domain structures on bulk samples by scanning electron microscopy (SEM). Complex magnetic domains, referred to as the maze state in CoPt/FePt alloys, were observed at a spatial resolution of less than 100 nm by using an in-lens annular detector. The method allows for imaging almost all the domain walls in the mazy structure, whereas the visualisation of the domain walls with the classical SEM method was limited. Our method provides a simple way to analyse surface domain structures in the bulk state that can be used in combination with SEM functions such as orientation or composition analysis. Thus, the method extends applications of SEM-based magnetic imaging, and is promising for resolving various problems at the forefront of fields including physics, magnetics, materials science, engineering, and chemistry.

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

DOE PAGES

Osborn, David L.

2017-03-15

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential andmore » well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.« less

Surface Traps in Colloidal Quantum Dots: A Combined Experimental and Theoretical Perspective

PubMed Central

2017-01-01

Surface traps are ubiquitous to nanoscopic semiconductor materials. Understanding their atomistic origin and manipulating them chemically have capital importance to design defect-free colloidal quantum dots and make a leap forward in the development of efficient optoelectronic devices. Recent advances in computing power established computational chemistry as a powerful tool to describe accurately complex chemical species and nowadays it became conceivable to model colloidal quantum dots with realistic sizes and shapes. In this Perspective, we combine the knowledge gathered in recent experimental findings with the computation of quantum dot electronic structures. We analyze three different systems: namely, CdSe, PbS, and CsPbI3 as benchmark semiconductor nanocrystals showing how different types of trap states can form at their surface. In addition, we suggest experimental healing of such traps according to their chemical origin and nanocrystal composition. PMID:28972763

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

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

Osborn, David L.

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential andmore » well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.« less

Creating Semantic Waves: Using Legitimation Code Theory as a Tool to Aid the Teaching of Chemistry

ERIC Educational Resources Information Center

Blackie, Margaret A. L.

2014-01-01

This is a conceptual paper aimed at chemistry educators. The purpose of this paper is to illustrate the use of the semantic code of Legitimation Code Theory in chemistry teaching. Chemistry is an abstract subject which many students struggle to grasp. Legitimation Code Theory provides a way of separating out abstraction from complexity both of…

Students' Learning with the Connected Chemistry (CC1) Curriculum: Navigating the Complexities of the Particulate World

ERIC Educational Resources Information Center

Levy, Sharona T.; Wilensky, Uri

2009-01-01

The focus of this study is students' learning with a Connected Chemistry unit, CC1 (denotes Connected Chemistry, chapter 1), a computer-based environment for learning the topics of gas laws and kinetic molecular theory in chemistry (Levy and Wilensky 2009). An investigation was conducted into high-school students' learning with Connected…

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.

A platform for the advanced spatial and temporal control of biomolecules

NASA Astrophysics Data System (ADS)

Hook, Andrew L.; Thissen, Helmut; Hayes, Jason P.; Voelcker, Nicolas H.

2007-01-01

Manipulating biomolecules at solid/liquid interfaces is important for the development of various biodevices including microarrays. Smart materials that enable both spatial and temporal control of biomolecules by combining switchability with patterned surface chemistry offer unprecedented levels of control of biomolecule manipulation. Such a system has been developed for the microscale spatial control over both DNA and cell growth on highly doped p-type silicon. Surface modification, involving plasma polymerisation of allylamine and poly(ethlylene glycol) grafting with subsequent laser ablation, led to the production of a patterned surface with dual biomolecule adsorption and desorption properties. On patterned surfaces, preferential electro-stimulated adsorption of DNA to the allylamine plasma polymer surface and subsequent desorption by the application of a negative bias was observed. The ability of this surface to control both DNA and cell attachment in four dimensions has been demonstrated, exemplifying its capacity to be used for complex biological studies such as gene function analysis. This system has been successfully applied to living microarray applications and is an exciting platform for any system incorporating biomolecules.

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...

From Metaphors to Models: Broadening the Lens of the Hunter Warrior Experiment with a Complex Adaptive System Tool

DTIC Science & Technology

1999-01-01

chemistry tells us why it is inevitable, pervasive, and won’t go away. Fortunately, there is the companion new science of complexity, rooted in...article. 30llachinski, Land Warfare and Complexity, Part II, 43. 32 Ilachinski, 43. Etymologically , metaphor (the Greek metafora, "carry over") means...anthropology, chemistry , economics, military and political science among others. Santa Fe Institute, http://www.santafe.edu/sfl/research. 53SAIC

Synthesis and Characterization of Europium(III) and Terbium(III) Complexes: An Advanced Undergraduate Inorganic Chemistry Experiment

ERIC Educational Resources Information Center

Swavey, Shawn

2010-01-01

Undergraduate laboratories rarely involve lanthanide coordination chemistry. This is unfortunate in light of the ease with which many of these complexes are made and the interesting and instructive photophysical properties they entail. The forbidden nature of the 4f transitions associated with the lanthanides is overcome by incorporation of…

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

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.

Hierarchically nanostructured materials for sustainable environmental applications

PubMed Central

Ren, Zheng; Guo, Yanbing; Liu, Cai-Hong; Gao, Pu-Xian

2013-01-01

This review presents a comprehensive overview of the hierarchical nanostructured materials with either geometry or composition complexity in environmental applications. The hierarchical nanostructures offer advantages of high surface area, synergistic interactions, and multiple functionalities toward water remediation, biosensing, environmental gas sensing and monitoring as well as catalytic gas treatment. Recent advances in synthetic strategies for various hierarchical morphologies such as hollow spheres and urchin-shaped architectures have been reviewed. In addition to the chemical synthesis, the physical mechanisms associated with the materials design and device fabrication have been discussed for each specific application. The development and application of hierarchical complex perovskite oxide nanostructures have also been introduced in photocatalytic water remediation, gas sensing, and catalytic converter. Hierarchical nanostructures will open up many possibilities for materials design and device fabrication in environmental chemistry and technology. PMID:24790946

Hierarchically Nanostructured Materials for Sustainable Environmental Applications

NASA Astrophysics Data System (ADS)

Ren, Zheng; Guo, Yanbing; Liu, Cai-Hong; Gao, Pu-Xian

2013-11-01

This article presents a comprehensive overview of the hierarchical nanostructured materials with either geometry or composition complexity in environmental applications. The hierarchical nanostructures offer advantages of high surface area, synergistic interactions and multiple functionalities towards water remediation, environmental gas sensing and monitoring as well as catalytic gas treatment. Recent advances in synthetic strategies for various hierarchical morphologies such as hollow spheres and urchin-shaped architectures have been reviewed. In addition to the chemical synthesis, the physical mechanisms associated with the materials design and device fabrication have been discussed for each specific application. The development and application of hierarchical complex perovskite oxide nanostructures have also been introduced in photocatalytic water remediation, gas sensing and catalytic converter. Hierarchical nanostructures will open up many possibilities for materials design and device fabrication in environmental chemistry and technology.

Combinatorial nanodiamond in pharmaceutical and biomedical applications.

PubMed

Lim, Dae Gon; Prim, Racelly Ena; Kim, Ki Hyun; Kang, Eunah; Park, Kinam; Jeong, Seong Hoon

2016-11-30

One of the newly emerging carbon materials, nanodiamond (ND), has been exploited for use in traditional electric materials and this has extended into biomedical and pharmaceutical applications. Recently, NDs have attained significant interests as a multifunctional and combinational drug delivery system. ND studies have provided insights into granting new potentials with their wide ranging surface chemistry, complex formation with biopolymers, and combination with biomolecules. The studies that have proved ND inertness, biocompatibility, and low toxicity have made NDs much more feasible for use in real in vivo applications. This review gives an understanding of NDs in biomedical engineering and pharmaceuticals, focusing on the classified introduction of ND/drug complexes. In addition, the diverse potential applications that can be obtained with chemical modification are presented. Copyright © 2016 Elsevier B.V. All rights reserved.

The birth and evolution of surface science: Child of the union of science and technology

PubMed Central

Duke, C. B.

2003-01-01

This article is an account of the birth and evolution of surface science as an interdisciplinary research area. Surface science emanated from the confluence of concepts and tools in physics and chemistry with technological innovations that made it possible to determine the structure and properties of surfaces and interfaces and the dynamics of chemical reactions at surfaces. The combination in the 1960s and 1970s of ultra-high-vacuum (i.e., P < 10−7 Pascal or 10−9 Torr) technology with the recognition that electrons in the energy range from 50 to 500 eV exhibited inelastic collision mean free paths of the order of a few angstroms fostered an explosion of activity. The results were a reformulation of the theory of electron solid scattering, the nearly universal use of electron spectroscopies for surface characterization, the rise of surface science as an independent interdisciplinary research area, and the emergence of the American Vacuum Society (AVS) as a major international scientific society. The rise of microelectronics in the 1970s and 1980s resulted in huge increases in computational power. These increases enabled more complex experiments and the utilization of density functional theory for the quantitative prediction of surface structure and dynamics. Development of scanning-probe microscopies in the 1990s led to atomic-resolution images of macroscopic surfaces and interfaces as well as videos of atoms moving about on surfaces during growth and diffusion. Scanning probes have since brought solid–liquid interfaces into the realm of atomic-level surface science, expanding its scope to more complex systems, including fragile biological materials and processes. PMID:12651946

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.

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

PubMed Central

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

2012-01-01

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

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry.

PubMed

Silber, David; Kowalski, Piotr M; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-30

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO 2 (110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO 2 (110) surface.

Preliminary Analysis of Pyrite Reactivity Under Venusian Temperature and Atmosphere

NASA Technical Reports Server (NTRS)

Radoman-Shaw, B. G.; Harvey, R. P.; Jacobson, N. S.; Costa, G. C. C.

2015-01-01

Measurements of Venus surface chemistry suggest a basaltic composition with a predominantly CO2 atmosphere. In order to understand the reactivity of certain possible mineral species on the surface, previous simulation chambers conduct experiments at 1 atmosphere with a simplified CO2 atmosphere. Following this procedure, pyrite (FeS2) samples are used to estimate the reactivity of sulfide minerals under a Venusian atmosphere and climate. Sulfurous gas species have been identified and quantified in the Venusian atmosphere, and sulfurous gas and mineral species are known to be created through volcanism, which is suggested to still occur on the surface of Venus. This experimentation is necessary to constrain reactions that could occur between the surface and atmosphere of Venus to understand terrestrial geology in a thick and hot greenhouse atmosphere. Quantifying this reaction can lead to approximations necessary for further experimentation in more complex environments such as those in the GEER chamber at Glenn Research Center that can simulate pressure along with temperature and a more inclusive and representative Venusian atmosphere.

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

NASA Astrophysics Data System (ADS)

Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-01

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

The QSAR study of flavonoid-metal complexes scavenging rad OH free radical

NASA Astrophysics Data System (ADS)

Wang, Bo-chu; Qian, Jun-zhen; Fan, Ying; Tan, Jun

2014-10-01

Flavonoid-metal complexes have antioxidant activities. However, quantitative structure-activity relationships (QSAR) of flavonoid-metal complexes and their antioxidant activities has still not been tackled. On the basis of 21 structures of flavonoid-metal complexes and their antioxidant activities for scavenging rad OH free radical, we optimised their structures using Gaussian 03 software package and we subsequently calculated and chose 18 quantum chemistry descriptors such as dipole, charge and energy. Then we chose several quantum chemistry descriptors that are very important to the IC50 of flavonoid-metal complexes for scavenging rad OH free radical through method of stepwise linear regression, Meanwhile we obtained 4 new variables through the principal component analysis. Finally, we built the QSAR models based on those important quantum chemistry descriptors and the 4 new variables as the independent variables and the IC50 as the dependent variable using an Artificial Neural Network (ANN), and we validated the two models using experimental data. These results show that the two models in this paper are reliable and predictable.

Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework

DOE PAGES

Bogart, Justin A.; Lippincott, Connor A.; Carroll, Patrick J.; ...

2015-10-27

Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Clmore » - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halide series supported by the tripodal ligand framework is also reported (see scheme).« less

Systems chemistry: All in a spin

NASA Astrophysics Data System (ADS)

Clark, Lucy; Lightfoot, Philip

2016-05-01

A fundamental challenge in systems chemistry is to engineer the emergence of complex behaviour. The collective structures of metal cyanide chains have now been interpreted in the same manner as the myriad of magnetic phases displayed by frustrated spin systems, highlighting a symbiotic approach between systems chemistry and magnetism.

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

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.

Corrosion chemistry closing comments: opportunities in corrosion science facilitated by operando experimental characterization combined with multi-scale computational modelling.

PubMed

Scully, John R

2015-01-01

Recent advances in characterization tools, computational capabilities, and theories have created opportunities for advancement in understanding of solid-fluid interfaces at the nanoscale in corroding metallic systems. The Faraday Discussion on Corrosion Chemistry in 2015 highlighted some of the current needs, gaps and opportunities in corrosion science. Themes were organized into several hierarchical categories that provide an organizational framework for corrosion. Opportunities to develop fundamental physical and chemical data which will enable further progress in thermodynamic and kinetic modelling of corrosion were discussed. These will enable new and better understanding of unit processes that govern corrosion at the nanoscale. Additional topics discussed included scales, films and oxides, fluid-surface and molecular-surface interactions, selected topics in corrosion science and engineering as well as corrosion control. Corrosion science and engineering topics included complex alloy dissolution, local corrosion, and modelling of specific corrosion processes that are made up of collections of temporally and spatially varying unit processes such as oxidation, ion transport, and competitive adsorption. Corrosion control and mitigation topics covered some new insights on coatings and inhibitors. Further advances in operando or in situ experimental characterization strategies at the nanoscale combined with computational modelling will enhance progress in the field, especially if coupling across length and time scales can be achieved incorporating the various phenomena encountered in corrosion. Readers are encouraged to not only to use this ad hoc organizational scheme to guide their immersion into the current opportunities in corrosion chemistry, but also to find value in the information presented in their own ways.

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.

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.

Effect of Molecular Structure on Modulation of Passivation Films on Copper Chemical Mechanical Planarization

NASA Astrophysics Data System (ADS)

Mlynarski, Amy

In order to optimize the chemical mechanical planarization (CMP) process, there is a need to further understand the synergistic relationship between chemical and mechanical parameters to enhance the polishing process. CMP chemistry is very complex, as it contains complexing agents, oxidizing agents, passivating agents, and abrasive particles. This variety of components ensues chaos within the system, which complicates the understanding of the direct impact each component has on the CMP process. In order for there to be efficiency in the polishing process, specifically for copper (Cu) polishing, the chemistry must create a softened passivation layer on the Cu surface that is able to be readily removed by applied mechanical abrasion. Focusing on Cu CMP, the oxidation of Cu to Cu2+ needs to be thoroughly understood in order to probe the formation of creating this ideal passivated layer, which protects recessed Cu regions. The type of film that is formed, the strength of the film, and even the efficiency of film removal will be altered depending on the chemistry of interaction at the Cu surface. This thesis focuses on understanding the working mechanism of the film formation on Cu, depending on the passivating agent added to the system. The different passivating agents used, more specifically benzotriazole (BTA), triazole (TAZ), salicylhydroxamic acid (SHA), and benzimidazole (BIA), have all been known to create a light coat of protection on the recessed metal, providing corrosion resistance. In order to study the differences in these films, many different techniques can be utilized to characterize the films, such as electrochemical scans, referred to as Tafel plots, which will be performed to compare the differences of the films. By altering the temperature within the system, the activation energy for each system can also be determined as another way to characterize the density of the passive film formed. Furthermore, the generation of *OH will be monitored since the formation of *OH is imperative for catalyzing the Cu-amino acid complexes, necessary for obtaining adequate removal rates. The amount of *OH generated from each system would have a direct correlation to the polishing performance for the different systems. Additionally, the effect of changing mechanical parameters or consumables used will alter the polish, more specifically the amount of friction generated during the polishes. This work discovered that when comparing all of the different types of inhibitors, there was a significant difference seen in the type of film formed as well as the stability of the film, strongly dependent on the concentration of the corrosion inhibitor. The calculated activation energy showed a direct correlation to the concentration of the corrosion inhibitor; more specifically, as the concentration of the inhibitor increases, so does the activation energy. By looking at the generated amount of *OH for the complexes, more specifically BTA and SHA, there is a minimal amount of *OH generated within the system compared to that of TAZ and BIA which resemble more like a system containing no inhibitor at all. This would once again show how the structure determines function of the inhibitor in regards to how the complex changes for the different molecules. The removal rates for these systems, both at 100 ppm and 500 ppm, show a strong correlation to the previously discussed activation energies. BTA shows extremely low removal rates, which seems to be diminished at even higher concentration, since the film created is so dense due to the pi-pi electron interactions. Similar trends are seen in the results from TAZ where the removal rates decrease as the concentration of the inhibitor increases. Furthermore, SHA shows significant material removal rates (MRR) at lower concentrations, but the rates are vastly different when increasing the concentration to 500 ppm. This could be because the complex that forms with the surface is a stable ring-like complex, but once enough inhibitor is added, the SHA complex covers the surface entirely, eliminating any chance of Cu-glycine interaction, which would promote removal rate. Unlike the other inhibitors, the removal rates for BIA show that as the concentration of the inhibitor increases, the removal rates significantly increase as well. Since this inhibitor forms a "weaker" complex, comparatively, the more inhibitor added would allow for more of the Cu-glycine interactions to take place.

Fifty years of oxacalix[3]arenes: A review

PubMed Central

Cottet, Kevin; Marcos, Paula M

2012-01-01

Summary Hexahomotrioxacalix[3]arenes, commonly called oxacalix[3]arenes, were first reported in 1962. Since then, their chemistry has been expanded to include numerous derivatives and complexes. This review describes the syntheses of the parent compounds, their derivatives, and their complexation behaviour towards cations. Extraction data are presented, as are crystal structures of the macrocycles and their complexes with guest species. Applications in fields as diverse as ion selective electrode modifiers, fluorescence sensors, fullerene separations and biomimetic chemistry are described. PMID:22423288

Atmospheric chemistry of hydrogen fluoride

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

Cheng, Meng -Dawn

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

Atmospheric chemistry of hydrogen fluoride

DOE PAGES

Cheng, Meng -Dawn

2017-04-11

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

Alzheimer Abeta(1-42) monomer adsorbed on the self-assembled monolayers.

PubMed

Wang, Qiuming; Zhao, Jun; Yu, Xiang; Zhao, Chao; Li, Lingyan; Zheng, Jie

2010-08-03

Amyloid-beta (Abeta) peptide aggregation on the cell membranes is a key pathological event responsible for neuron cell death in Alzheimer's disease (AD). We present a collection of molecular docking and molecular dynamics simulations to study the conformational dynamics and adsorption behavior of Abeta monomer on the self-assembled monolayer (SAM), in comparison to Abeta structure in bulk solution. Two distinct Abeta conformations (i.e., alpha-helix and beta-hairpin) are selected as initial structures to mimic different adsorption states, whereas four SAM surfaces with different end groups in hydrophobicity and charge distribution are used to examine the effect of surface chemistry on Abeta structure and adsorption. Simulation results show that alpha-helical monomer displays higher structural stability than beta-hairpin monomer on all SAMs, suggesting that the preferential conformation of Abeta monomer could be alpha-helical or random structure when bound to surfaces. Structural stability and adsorption behavior of Abeta monomer on the SAMs originates from competitive interactions between Abeta and SAM and between SAM and interfacial water, which involve the conformation of Abeta, the surface chemistry of SAM, and the structure and dynamics of interfacial waters. The relative net binding affinity of Abeta with the SAMs is in the favorable order of COOH-SAM > NH(2)-SAM > CH(3)-SAM > OH-SAM, highlighting the importance of electrostatic and hydrophobic interactions for driving Abeta adsorption at the SAMs, but both interactions contribute differently to each Abeta-SAM complex. This work provides parallel insights into the understanding of Abeta structure and aggregation on cell membrane.

Molecular Modeling and Computational Chemistry at Humboldt State University.

ERIC Educational Resources Information Center

Paselk, Richard A.; Zoellner, Robert W.

2002-01-01

Describes a molecular modeling and computational chemistry (MM&CC) facility for undergraduate instruction and research at Humboldt State University. This facility complex allows the introduction of MM&CC throughout the chemistry curriculum with tailored experiments in general, organic, and inorganic courses as well as a new molecular modeling…

Proportional Reasoning in the Learning of Chemistry: Levels of Complexity

ERIC Educational Resources Information Center

Ramful, Ajay; Narod, Fawzia Bibi

2014-01-01

This interdisciplinary study sketches the ways in which proportional reasoning is involved in the solution of chemistry problems, more specifically, problems involving quantities in chemical reactions (commonly referred to as stoichiometry problems). By building on the expertise of both mathematics and chemistry education research, the present…

Observation of a Novel Low-Lying Excited State in Zinc Complexes.

DTIC Science & Technology

1985-01-22

Illinois 61801 Washington, D.C. 20375 Dr. W. M. Jackson Dr. George E. Walrafen Department of Chemistry Department of Chemistry Howard University Howard ... University Washington, D.C. 20059 Washington, D.C. 20059 Dr. M. S. Wrighton Dr. Joe Brandelik Department of Chemistry AFWAL/AADO-1 Massachusetts

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.

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

ERIC Educational Resources Information Center

Kozma, Robert B.; Russell, Joel

1997-01-01

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

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.

X-Ray Crystallography Analysis of Complexes Synthesized with Tris(2-pyridylmethyl)amine: A Laboratory Experiment for Undergraduate Students Integrating Interdisciplinary Concepts and Techniques

ERIC Educational Resources Information Center

Bazley, Isabel J.; Erie, Ellen A.; Feiereisel, Garrett M.; LeWarne, Christopher J.; Peterson, Jack M.; Sandquist, Katherine L.; Oshin, Kayode D.; Zeller, Matthias

2018-01-01

An integrated laboratory experiment applying concepts and techniques from organic chemistry, inorganic chemistry, and instrumental analysis is presented for use in the undergraduate curriculum. This experiment highlights the synthesis, characterization, and use of tris(2-pyridylmethyl)amine (TPMA) to make complexes with different metal salts. It…

Antimicrobial coatings on polyethylene terephthalate based on curcumin/cyclodextrin complex embedded in a multilayer polyelectrolyte architecture.

PubMed

Shlar, Ilya; Droby, Samir; Rodov, Victor

2018-04-01

Bacterial contamination is a growing concern worldwide. The aim of this work was to develop an antimicrobial coating based on curcumin-cyclodextrin inclusion complex and using polyethylene terephthalate (PET) film as a support matrix. After a pre-treatment aimed to provide sufficient electric charge to the PET surface, it was electrostatically coated with repeated multilayers comprising alternately deposited positively-charged poly-l-lysine (PLL) and negatively-charged poly-l-glutamic acid (PLGA) and carboxymethyl-β-cyclodextrin (CMBCD). The coatings had an architecture (PLL-PLGA) 6 -(PLL-PLGA-PLL-CMBCD) n , with the number of repeated multilayers n varying from 5 to 20. The CMBCD molecules were either covalently cross-linked using carbodiimide crosslinker chemistry or left unbound. The surface morphology, structure and elemental composition of the coatings were analysed by scanning electron microscopy and energy dispersive x-ray spectroscopy. To impart antimicrobial properties to the coatings they were loaded with a natural phenolic compound curcumin forming inclusion complexes with β-cyclodextrin. The non-cross-linked coatings showed bactericidal activity towards Escherichia coli in the dark, and this activity was further enhanced upon illumination with white light. Curcumin was released from the non-cross-linked coatings into an aqueous medium in the form of cyclodextrin inclusion complex. After the cross-linking, the coating lost its dark antimicrobial activity but retained the photodynamic properties. Stabilized cross-linked curcumin-loaded coatings can serve a basis for developing photoactivated antimicrobial surfaces controlling bacterial contamination and spread. Copyright © 2018 Elsevier B.V. All rights reserved.

Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

NASA Astrophysics Data System (ADS)

Mykhalichko, B. M.; Temkin, Oleg N.; Mys'kiv, M. G.

2000-11-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H2O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH2OH, CH=CH2, etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Chuang, K.-J.; Ioppolo, S.; Qasim, D.; van Dishoeck, E. F.; Linnartz, H.

2017-06-01

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, I.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH2CH(OH)CH2OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH2CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.

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.

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.

Quantitatively probing water and its isotopomers: from theory to experiments; the contribution of a chemical and astrophysical European network 'Our Astrochemical History'

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent

2015-08-01

In order to retrieve actual molecular abundances from astrophysical observations of molecular spectral lines, knowledge of the rotational levels excitation schemes is essential to go beyond Local Thermodynamical Equilibrium. These rates are almost always obtained from theoretical investigations, by computing classical or quantum dynamics of the interaction of molecules with these colliders (roueff2013).Our laboratories have recently calculated a set of collision coefficients characterizing the efficiency of energy transfer between molecular hydrogen of helium and a large variety of interstellar molecules. One of the main goal has been water and its isotopomers, computingrates for H2O, HDO and D2O in collision with H2 (valiron2008,faure2012,daniel2011).We felt it necessary to have a multidisciplinary approach: theoretical on the one hand, experimental on the second. Indeed, excitation coefficient computation is a process involving many codes and approximations. Hence we compared our theoretical results to several experiments: spectroscopy of the H2O-H2 van der Waals complex (vanderavoird 2012), differential cross sections (yang 2010, 2011), pressure broadening (drouin 2012).Thanks to these precise determinations, many water abundances could be quantitatively measured, like the HDO/H2O ratio (coutens 2012).While the excitation of water is by now well understood, much remains to be done for heavier molecules, paving the way to quantitative measures of complex organic molecules . A multi disciplinary approach is necessary, that keeps in mind the necessities of actual astrophysical observations. To do so, we describe the European COST network ‘Our Astrochemical History’ (http://prague2015astrohistory.vscht.cz/) , which brings together specialists of many areas of chemistry together with astronomy, in order to address this kind of problem. It focussses on the molecular evolution towards higher complexity and aim sat delivering new schemes for physical chemistry at large, like chemistry of transient species and photochemistry, in gas or on surfaces.

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

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

PubMed

Li, Tao; Wang, Yan; Mao, Huiting; Wang, Shuxiao; Talbot, Robert W; Zhou, Ying; Wang, Zhe; Nie, Xiaoling; Qie, Guanghao

2018-05-01

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L -1 , respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( N d ) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients K ad (5.9-362.7 L g -1 ) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

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.

Surface plasmon holographic microscopy for near-field refractive index detection and thin film mapping

NASA Astrophysics Data System (ADS)

Zhao, Jianlin; Zhang, Jiwei; Dai, Siqing; Di, Jianglei; Xi, Teli

2018-02-01

Surface plasmon microscopy (SPM) is widely applied for label-free detection of changes of refractive index and concentration, as well as mapping thin films in near field. Traditionally, the SPM systems are based on the detection of light intensity or phase changes. Here, we present two kinds of surface plasmon holographic microscopy (SPHM) systems for amplitude- and phase-contrast imaging simultaneously. Through recording off-axis holograms and numerical reconstruction, the complex amplitude distributions of surface plasmon resonance (SPR) images can be obtained. According to the Fresnel's formula, in a prism/ gold/ dielectric structure, the reflection phase shift is uniquely decided by refractive index of the dielectric. By measuring the phase shift difference of the reflected light exploiting prism-coupling SPHM system based on common-path interference configuration, monitoring tiny refractive index variation and imaging biological tissue are performed. Furthermore, to characterize the thin film thickness in near field, we employ a four-layer SPR model in which the third film layer is within the evanescent field. The complex reflection coefficient, including the reflectivity and reflection phase shift, is uniquely decided by the film thickness. By measuring the complex amplitude distributions of the SPR images exploiting objective-coupling SPHM system based on common-path interference configuration, the thickness distributions of thin films are mapped with sub-nanometer resolution theoretically. Owing to its high temporal stability, the recommended SPHMs show great potentials for monitoring tiny refractive index variations, imaging biological tissues and mapping thin films in near field with dynamic, nondestructive and full-field measurement capabilities in chemistry, biomedicine field, etc.

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.

Synthesis and colloidal properties of anisotropic hydrothermal barium titanate

NASA Astrophysics Data System (ADS)

Yosenick, Timothy James

2005-11-01

Nanoparticles of high dielectric constant materials, especially BaTiO3, are required to achieve decreased layer thickness in multilayer ceramic capacitors (MLCCs). Tabular metal nanoparticles can produce thin metal layers with low surface roughness via electrophoretic deposition (EPD). To achieve similar results with dielectric layers requires the synthesis and dispersion of tabular BaTiO3 nanoparticles. The goal of this study was to investigate the deposition of thin BaTiO3 layers using a colloidal process. The synthesis, interfacial chemistry and colloidal properties of hydrothermal BaTiO3 a model particle system, was investigated. After characterization of the material system particulates were deposited to form thin layers using EPD. In the current study, the synthesis of BaTiO3 has been investigated using a hydrothermal route. TEM and AFM analyses show that the synthesized particles are single crystal with a majority of the particle having a <111> zone axis and {111} large face. The particles have a median thickness of 5.8 +/- 3.1 nm and face diameter of 27.1 +/- 12.3 nm. Particle growth was likely controlled by the formation of {111} twins and the synthesis pH which stabilizes the {111} face during growth. With limited growth in the <111> direction, the particles developed a plate-like morphology. Physical property characterization shows the powder was suitable for further processing with high purity, low hydrothermal defect concentration, and controlled stoichiometry. TEM observations of thermally treated powders indicate that the particles begin to loose the plate-like morphology by 900 °C. The aqueous passivation, dispersion, and doping of nanoscale BaTiO 3 powders was investigated. Passivation BaTiO3 was achieved through the addition of oxalic acid. The oxalic acid selectively adsorbs onto the particle surface and forms a chemically stable 2-3 nm layer of barium oxalate. The negative surface charge of the oxalate effectively passivated the BaTiO3 providing a surface suitable for the use of a cationic dispersant, polyethylenimine (PEI). Rheological properties indicate the presence of an oxalate-PEI interaction which can be detrimental to dispersion. With a better understanding of the aqueous surface chemistry of BaTiO3 the surface chemistry was manipulated to control the adsorption of aqueous soluble complexes of Co, Nb, and Bi, three common dopants in the processing of BaTiO3 Surface charge, TEM, and EDS analysis showed that while in suspension the dopants selectively absorbed onto the particle surface forming an engineered coating. (Abstract shortened by UMI.)

Sensitivity of ocean acidification and oxygen to the uncertainty in climate change

NASA Astrophysics Data System (ADS)

Cao, Long; Wang, Shuangjing; Zheng, Meidi; Zhang, Han

2014-05-01

Due to increasing atmospheric CO2 concentrations and associated climate change, the global ocean is undergoing substantial physical and biogeochemical changes. Among these, changes in ocean oxygen and carbonate chemistry have great implication for marine biota. There is considerable uncertainty in the projections of future climate change, and it is unclear how the uncertainty in climate change would also affect the projection of oxygen and carbonate chemistry. To investigate this issue, we use an Earth system model of intermediate complexity to perform a set of simulations, including that which involves no radiative effect of atmospheric CO2 and those which involve CO2-induced climate change with climate sensitivity varying from 0.5 °C to 4.5 °C. Atmospheric CO2 concentration is prescribed to follow RCP 8.5 pathway and its extensions. Climate change affects carbonate chemistry and oxygen mainly through its impact on ocean temperature, ocean ventilation, and concentration of dissolved inorganic carbon and alkalinity. It is found that climate change mitigates the decrease of carbonate ions at the ocean surface but has negligible effect on surface ocean pH. Averaged over the whole ocean, climate change acts to decrease oxygen concentration but mitigates the CO2-induced reduction of carbonate ion and pH. In our simulations, by year 2500, every degree increase of climate sensitivity warms the ocean by 0.8 °C and reduces ocean-mean dissolved oxygen concentration by 5.0%. Meanwhile, every degree increase of climate sensitivity buffers CO2-induced reduction in ocean-mean carbonate ion concentration and pH by 3.4% and 0.02 units, respectively. Our study demonstrates different sensitivities of ocean temperature, carbonate chemistry, and oxygen, in terms of both the sign and magnitude to the amount of climate change, which have great implications for understanding the response of ocean biota to climate change.

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.

Mechanised nanoparticles for drug delivery

NASA Astrophysics Data System (ADS)

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

2009-09-01

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

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

Single-Molecule Interfacial Electron Transfer

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

Lu, H. Peter

This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static andmore » dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO 2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO 2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO 2 nanoparticle surfaces by using ultrafast single-molecule spectroscopy and electrochemical AFM metal tip scanning microscopy, focusing on understanding the interfacial electron transfer dynamics at specific nanoscale electron transfer sites with high-spatially and temporally resolved topographic-and-spectroscopic characterization at individual molecule basis, characterizing single-molecule rate processes, reaction driving force, and molecule-substrate electronic coupling. One of the most significant characteristics of our new approach is that we are able to interrogate the complex interfacial electron transfer dynamics by actively pin-point energetic manipulation of the surface interaction and electronic couplings, beyond the conventional excitation and observation.« less

Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

NASA Technical Reports Server (NTRS)

Stiegman, Albert E.; Tyler, David R.

1986-01-01

A guideline to the reactivity of 17- and 19-valence electron species in organometallic chemistry is proposed which the authors believe will supersede all others. The thesis holds that the reactions of 17-electron metal radicals are associatively activated with reactions proceeding through a 19-valence electron species. The disparate reaction chemistry of the 17-electron metal radicals are unified in terms of this associative reaction pathway, and the intermediacy of 19-valence electron complexes in producing the observed products is discussed. It is suggested that related associatively activated pathways need to be considered in some reactions that are thought to occur by more conventional routes involving 16- and 18-electron intermediates. The basic reaction chemistry and electronic structures of these species are briefly discussed.

Chemical modification of poly(ethylene terephthalate) and immobilization of the selected enzymes on the modified film

NASA Astrophysics Data System (ADS)

Irena, Gancarz; Jolanta, Bryjak; Karolina, Zynek

2009-07-01

Poly(ethylene terephthalate) (PET) film was modified by reaction with hydrazine (HD), ethylenediamine (EDA), 1,2-diaminopropane (1,2-DAP) and 1,3-diaminopropane (1,3-DAP). The maximal amount of amine functionalities introduced in the chosen conditions on the surface was found as 0.07, 3.35, 0.76 and 1.99 nmol cm -2 for HD, EDA, 1,2-DAP and 1,3-DAP respectively. During the modification process etching of the sample and an increase of stiffness takes place. FTIR-ATR spectra prove that the surface chemistry after modification in amine solution is very complex. The lack of clear correlation between the surface tension and surface concentration of amine functionalities seems to confirm that. For immobilization purpose invertase, laccase and tyrosinase were used. The amount of covalently attached proteins at first increases with the increase of surface concentration of amine groups but after reaching a certain level of amine groups, decrease of the immobilization level was observed. All enzymes tested showed highest activity for a moderate level of aminolysis and this activity had the highest values for EDA-modified PET.

Fiber optic-based biosensor

NASA Technical Reports Server (NTRS)

Ligler, Frances S.

1991-01-01

The NRL fiber optic biosensor is a device which measures the formation of a fluorescent complex at the surface of an optical fiber. Antibodies and DNA binding proteins provide the mechanism for recognizing an analyze and immobilizing a fluorescent complex on the fiber surface. The fiber optic biosensor is fast, sensitive, and permits analysis of hazardous materials remote from the instrumentation. The fiber optic biosensor is described in terms of the device configuration, chemistry for protein immobilization, and assay development. A lab version is being used for assay development and performance characterization while a portable device is under development. Antibodies coated on the fiber are stable for up to two years of storage prior to use. The fiber optic biosensor was used to measure concentration of toxins in the parts per billion (ng/ml) range in under a minute. Immunoassays for small molecules and whole bacteria are under development. Assays using DNA probes as the detection element can also be used with the fiber optic sensor, which is currently being developed to detect biological warfare agents, explosives, pathogens, and toxic materials which pollute the environment.

Analysis of leaf surfaces using scanning ion conductance microscopy.

PubMed

Walker, Shaun C; Allen, Stephanie; Bell, Gordon; Roberts, Clive J

2015-05-01

Leaf surfaces are highly complex functional systems with well defined chemistry and structure dictating the barrier and transport properties of the leaf cuticle. It is a significant imaging challenge to analyse the very thin and often complex wax-like leaf cuticle morphology in their natural state. Scanning electron microscopy (SEM) and to a lesser extent Atomic force microscopy are techniques that have been used to study the leaf surface but their remains information that is difficult to obtain via these approaches. SEM is able to produce highly detailed and high-resolution images needed to study leaf structures at the submicron level. It typically operates in a vacuum or low pressure environment and as a consequence is generally unable to deal with the in situ analysis of dynamic surface events at submicron scales. Atomic force microscopy also possess the high-resolution imaging required and can follow dynamic events in ambient and liquid environments, but can over exaggerate small features and cannot image most leaf surfaces due to their inherent roughness at the micron scale. Scanning ion conductance microscopy (SICM), which operates in a liquid environment, provides a potential complementary analytical approach able to address these issues and which is yet to be explored for studying leaf surfaces. Here we illustrate the potential of SICM on various leaf surfaces and compare the data to SEM and atomic force microscopy images on the same samples. In achieving successful imaging we also show that SICM can be used to study the wetting of hydrophobic surfaces in situ. This has potentially wider implications than the study of leaves alone as surface wetting phenomena are important in a range of fundamental and applied studies. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

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

Facile Method for the Site-Specific, Covalent Attachment of full-length IgG onto Nanoparticles

PubMed Central

Hui, James Zhe; Al Zaki, Ajlan; Cheng, Zhiliang; Popik, Vladimir; Zhang, Hongtao; Luning Prak, Eline T.

2014-01-01

Antibodies, most commonly IgGs, have been widely used as targeting ligands in research and therapeutic applications due to their wide array of targets, high specificity and proven efficacy. Many of these applications require antibodies to be conjugated onto surfaces (e.g. nanoparticles and microplates); however, most conventional bioconjugation techniques exhibit low crosslinking efficiencies, reduced functionality due to non-site-specific labeling and random surface orientation, and/or require protein engineering (e.g. cysteine handles), which can be technically challenging. To overcome these limitations, we have recombinantly expressed Protein Z, which binds the Fc region of IgG, with an UV active non-natural amino acid benzoylphenyalanine (BPA) within its binding domain. Upon exposure to long wavelength UV light, the BPA is activated and forms a covalent link between the Protein Z and the bound Fc region of IgG. This technology was combined with expressed protein ligation (EPL), which allowed for the introduction of a fluorophore and click chemistry-compatible azide group onto the C-terminus of Protein Z during the recombinant protein purification step. This enabled crosslinked-Protein Z-IgG complexes to be efficiently and site-specifically attached to aza-dibenzycyclooctyne-modified nanoparticles, via copper-free click chemistry. PMID:24729432

Facile method for the site-specific, covalent attachment of full-length IgG onto nanoparticles.

PubMed

Hui, James Zhe; Al Zaki, Ajlan; Cheng, Zhiliang; Popik, Vladimir; Zhang, Hongtao; Luning Prak, Eline T; Tsourkas, Andrew

2014-08-27

Antibodies, most commonly IgGs, have been widely used as targeting ligands in research and therapeutic applications due to their wide array of targets, high specificity and proven efficacy. Many of these applications require antibodies to be conjugated onto surfaces (e.g. nanoparticles and microplates); however, most conventional bioconjugation techniques exhibit low crosslinking efficiencies, reduced functionality due to non-site-specific labeling and random surface orientation, and/or require protein engineering (e.g. cysteine handles), which can be technically challenging. To overcome these limitations, we have recombinantly expressed Protein Z, which binds the Fc region of IgG, with an UV active non-natural amino acid benzoylphenyalanine (BPA) within its binding domain. Upon exposure to long wavelength UV light, the BPA is activated and forms a covalent link between the Protein Z and the bound Fc region of IgG. This technology was combined with expressed protein ligation (EPL), which allowed for the introduction of a fluorophore and click chemistry-compatible azide group onto the C-terminus of Protein Z during the recombinant protein purification step. This enabled the crosslinked-Protein Z-IgG complexes to be efficiently and site-specifically attached to aza-dibenzocyclooctyne-modified nanoparticles, via copper-free click chemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE PAGES

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.; ...

2018-05-11

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

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

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

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%.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

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.

Dialysis, Albumin Binding, and Competitive Binding: A Laboratory Lesson Relating Three Chemical Concepts to Healthcare

ERIC Educational Resources Information Center

Domingo, Jennifer P.; Abualia, Mohammed; Barragan, Diana; Schroeder, Lianne; Wink, Donald J.; King, Maripat; Clark, Ginevra A.

2017-01-01

Introductory Chemistry laboratories must go beyond "cookbook" methods to illustrate how chemistry concepts apply to complex, real-world problems. In our case, we are preparing students to use their chemistry knowledge in the healthcare profession. The experiment described here explicitly models three important chemical concepts: dialysis…

Stratospheric chemistry and transport

NASA Technical Reports Server (NTRS)

Prather, Michael; Garcia, Maria M.

1990-01-01

A Chemical Tracer Model (CTM) that can use wind field data generated by the General Circulation Model (GCM) is developed to implement chemistry in the three dimensional GCM of the middle atmosphere. Initially, chemical tracers with simple first order losses such as N2O are used. Successive models are to incorporate more complex ozone chemistry.

Crocodile Chemistry. [CD-ROM].

ERIC Educational Resources Information Center

1999

This high school chemistry resource is an on-screen chemistry lab. In the program, students can experiment with a huge range of chemicals, choosing the form, quantity and concentrations. Dangerous or difficult experiments can be investigated safely and easily. A vast range of equipment can be set up, and complex simulations can be put together and…

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…

Practicing What We Preach: Assessing "Critical Thinking" in Organic Chemistry

ERIC Educational Resources Information Center

Stowe, Ryan L.; Cooper, Melanie M.

2017-01-01

Organic chemistry is often promoted as a course designed to cultivate skill in scientific "ways of thinking." Expert organic chemists perceive their field as one in which plausible answers to complex questions are arrived at through analytical thought processes. They draw analogy between problem solving in organic chemistry and diagnosis…

Synthesis and Characterization of Calixarene Tetraethers: An Exercise in Supramolecular Chemistry for the Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

Debbert, Stefan L.; Hoh, Bradley D.; Dulak, David J.

2016-01-01

In this experiment for an introductory undergraduate organic chemistry lab, students tetraalkylate tertbutylcalix[4]arene, a bowl-shaped macrocyclic oligophenol, and examine the supramolecular chemistry of the tetraether product by proton nuclear magnetic resonance (NMR) spectroscopy. Complexation with a sodium ion reduces the conformational…

Investigating Pre-Service Chemistry Teachers' Problem Solving Strategies: Towards Developing a Framework in Teaching Stoichiometry

ERIC Educational Resources Information Center

Espinosa, Allen A.; Nueva España, Rebecca C.; Marasigan, Arlyne C.

2016-01-01

The present study investigated pre-service chemistry teachers' problem solving strategies and alternative conceptions in solving stoichiometric problems and later on formulate a teaching framework based from the result of the study. The pre-service chemistry teachers were given four stoichiometric problems with increasing complexity and they need…

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.

Effects of Thermo-Mechanical Treatments on Deformation Behavior and IGSCC Susceptibility of Stainless Steels in Pwr Primary Water Chemistry

NASA Astrophysics Data System (ADS)

Nouraei, S.; Tice, D. R.; Mottershead, K. J.; Wright, D. M.

Field experience of 300 series stainless steels in the primary circuit of PWR plant has been good. Stress Corrosion Cracking of components has been infrequent and mainly associated with contamination by impurities/oxygen in occluded locations. However, some instances of failures have been observed which cannot necessarily be attributed to deviations in the water chemistry. These failures appear to be associated with the presence of cold-work produced by surface finishing and/or by welding-induced shrinkage. Recent data indicate that some heats of SS show an increased susceptibility to SCC; relatively high crack growth rates were observed even when the crack growth direction is orthogonal to the cold-work direction. SCC of cold-worked SS in PWR coolant is therefore determined by a complex interaction of material composition, microstructure, prior cold-work and heat treatment. This paper will focus on the interactions between these parameters on crack propagation in simulated PWR conditions.

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.

Microscale Synthesis, Reactions, and (Super 1)H NMR Spectroscopic Investigations of Square Planar Macrocyclic, Tetramido-N Co(III) Complexes Relevant to Green Chemistry

ERIC Educational Resources Information Center

Watson, Tanya T.; Uffelman, Erich S.; Lee, Daniel W., III; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen, R.

2004-01-01

The microscale preparation, characterization, and reactivity of a square planar Co(III) complex that has grown out of a program to introduce experiments of relevance to green chemistry into the undergraduate curriculum is presented. The given experiments illustrate the remarkable redox and aqueous acid-base stability that make the macrocycles very…