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.

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

PubMed

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

2012-01-01

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

Controlling the Surface Chemistry of Graphite by Engineered Self-Assembled Peptides

PubMed Central

Khatayevich, Dmitriy; So, Christopher R.; Hayamizu, Yuhei; Gresswell, Carolyn; Sarikaya, Mehmet

2012-01-01

The systematic control over surface chemistry is a long-standing challenge in biomedical and nanotechnological applications for graphitic materials. As a novel approach, we utilize graphite-binding dodecapeptides that self-assemble into dense domains to form monolayer thick long-range ordered films on graphite. Specifically, the peptides are rationally designed through their amino acid sequences to predictably display hydrophilic and hydrophobic characteristics while maintaining their self-assembly capabilities on the solid substrate. The peptides are observed to maintain a high tolerance for sequence modification, allowing the control over surface chemistry via their amino acid sequence. Furthermore, through a single step co-assembly of two different designed peptides, we predictably and precisely tune the wettability of the resulting functionalized graphite surfaces from 44 to 83 degrees. The modular molecular structures and predictable behavior of short peptides demonstrated here give rise to a novel platform for functionalizing graphitic materials that offers numerous advantages, including non-invasive modification of the substrate, bio-compatible processing in an aqueous environment, and simple fusion with other functional biological molecules. PMID:22428620

Surface chemistry from wettability and charge for the control of mesenchymal stem cell fate through self-assembled monolayers.

PubMed

Hao, Lijing; Fu, Xiaoling; Li, Tianjie; Zhao, Naru; Shi, Xuetao; Cui, Fuzhai; Du, Chang; Wang, Yingjun

2016-12-01

Self-assembled monolayers (SAMs) of alkanethiols on gold are highly controllable model substrates and have been employed to mimic the extracellular matrix for cell-related studies. This study aims to systematically explore how surface chemistry influences the adhesion, morphology, proliferation and osteogenic differentiation of mouse mesenchymal stem cells (mMSCs) using various functional groups (-OEG, -CH 3 , -PO 3 H 2 , -OH, -NH 2 and -COOH). Surface analysis demonstrated that these functional groups produced a wide range of wettability and charge: -OEG (hydrophilic and moderate iso-electric point (IEP)), -CH 3 (strongly hydrophobic and low IEP), -PO 3 H 2 (moderate wettability and low IEP), -OH (hydrophilic and moderate IEP), -NH 2 (moderate wettability and high IEP) and -COOH (hydrophilic and low IEP). In terms of cell responses, the effect of wettability may be more influential than charge for these groups. Moreover, compared to -OEG and -CH 3 groups, -PO 3 H 2 , -OH, -NH 2 and -COOH functionalities tended to promote not only cell adhesion, proliferation and osteogenic differentiation but also the expression of α v and β 1 integrins. This finding indicates that the surface chemistry may guide mMSC activities through α v and β 1 integrin signaling pathways. Model surfaces with controllable chemistry may provide insight into biological responses to substrate surfaces that would be useful for the design of biomaterial surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Surface analysis of gold nanoparticles functionalized with thiol-modified glucose SAMs for biosensor applications.

NASA Astrophysics Data System (ADS)

Spampinato, Valentina; Parracino, Mariaantonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-02-01

In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behaviour of the glucose-modified particles in presence of the maltose binding protein.

Surface Analysis of Gold Nanoparticles Functionalized with Thiol-Modified Glucose SAMs for Biosensor Applications

PubMed Central

Spampinato, Valentina; Parracino, Maria Antonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-01-01

In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behavior of the glucose-modified particles in the presence of the maltose binding protein. PMID:26973830

Effect of Native Oxide Film on Commercial Magnesium Alloys Substrates and Carbonate Conversion Coating Growth and Corrosion Resistance

PubMed Central

Feliu, Sebastián; Samaniego, Alejandro; Bermudez, Elkin Alejandro; El-Hadad, Amir Abdelsami; Llorente, Irene; Galván, Juan Carlos

2014-01-01

Possible relations between the native oxide film formed spontaneously on the AZ31 and AZ61 magnesium alloy substrates with different surface finish, the chemistry of the outer surface of the conversion coatings that grows after their subsequent immersion on saturated aqueous NaHCO3 solution treatment and the enhancement of corrosion resistance have been studied. The significant increase in the amount of aluminum and carbonate compounds on the surface of the conversion coating formed on the AZ61 substrate in polished condition seems to improve the corrosion resistance in low chloride ion concentration solutions. In contrast, the conversion coatings formed on the AZ31 substrates in polished condition has little effect on their protective properties compared to the respective as-received surface. PMID:28788582

Effect of Native Oxide Film on Commercial Magnesium Alloys Substrates and Carbonate Conversion Coating Growth and Corrosion Resistance.

PubMed

Feliu, Sebastián; Samaniego, Alejandro; Bermudez, Elkin Alejandro; El-Hadad, Amir Abdelsami; Llorente, Irene; Galván, Juan Carlos

2014-03-28

Possible relations between the native oxide film formed spontaneously on the AZ31 and AZ61 magnesium alloy substrates with different surface finish, the chemistry of the outer surface of the conversion coatings that grows after their subsequent immersion on saturated aqueous NaHCO₃ solution treatment and the enhancement of corrosion resistance have been studied. The significant increase in the amount of aluminum and carbonate compounds on the surface of the conversion coating formed on the AZ61 substrate in polished condition seems to improve the corrosion resistance in low chloride ion concentration solutions. In contrast, the conversion coatings formed on the AZ31 substrates in polished condition has little effect on their protective properties compared to the respective as-received surface.

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.

Controlling Film Morphology in Conjugated Polymer

PubMed Central

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

2009-01-01

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

Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

NASA Astrophysics Data System (ADS)

Hoang, Michelle V.; Chung, Hyun-Joong; Elias, Anastasia L.

2016-10-01

Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm-1) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ~0.2 N mm-1 (method 1) and  >0.3 N mm-1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Submicron Surface-Patterned Fibers and Textiles

DTIC Science & Technology

2016-11-04

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

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

PubMed

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

2012-10-23

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

Structural Chemistry of Human RNA Methyltransferases.

PubMed

Schapira, Matthieu

2016-03-18

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

The tunable wettability in multistimuli-responsive smart graphene surfaces

NASA Astrophysics Data System (ADS)

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

2013-01-01

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

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.

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.

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

Stable Carboxylate-Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyl Tin Compound.

PubMed

Ortiz, Mayreli; Mehdi, Ahmed; Methivier, Christophe; Thorimbert, Serge; Hasenknopf, Bernold; O'Sullivan, Ciara K

2018-05-21

Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol-gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. In the work reported here, we demonstrate that a carboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques was used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long term stability studies over the period of one year, demonstrating thermostability up to 90 oC and storage stability for at least 12 months when stored at 4 oC protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications including molecular techniques such as solid-phase amplification and solid-phase melting curve analysis that require elevated temperature stability, as well as biosensors, which require long-term storage stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of Viscous Dissipative Processes on the Wetting of Textured Surfaces

PubMed Central

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Determining the orientation of a chiral substrate using full-hemisphere angle-resolved photoelectron spectroscopy.

PubMed

Tadich, A; Riley, J; Thomsen, L; Cowie, B C C; Gladys, M J

2011-10-21

Chiral interfaces and substrates are of increasing importance in the field of enantioselective chemistry. To fully understand the enantiospecific interactions between chiral adsorbate molecules and the chiral substrate, it is vital that the chiral orientation of the substrate is known. In this Letter we demonstrate that full-hemisphere angle-resolved photoemission permits straightforward identification of the orientation of a chiral surface. The technique can be applied to any solid state system for which photoemission measurements are possible. © 2011 American Physical Society

Recycling microcavity optical biosensors.

PubMed

Hunt, Heather K; Armani, Andrea M

2011-04-01

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

Continuous fabrication of nanostructure arrays for flexible surface enhanced Raman scattering substrate

PubMed Central

Zhang, Chengpeng; Yi, Peiyun; Peng, Linfa; Lai, Xinmin; Chen, Jie; Huang, Meizhen; Ni, Jun

2017-01-01

Surface-enhanced Raman spectroscopy (SERS) has been a powerful tool for applications including single molecule detection, analytical chemistry, electrochemistry, medical diagnostics and bio-sensing. Especially, flexible SERS substrates are highly desirable for daily-life applications, such as real-time and in situ Raman detection of chemical and biological targets, which can be used onto irregular surfaces. However, it is still a major challenge to fabricate the flexible SERS substrate on large-area substrates using a facile and cost-effective technique. The roll-to-roll ultraviolet nanoimprint lithography (R2R UV-NIL) technique provides a solution for the continuous fabrication of flexible SERS substrate due to its high-speed, large-area, high-resolution and high-throughput. In this paper, we presented a facile and cost-effective method to fabricate flexible SERS substrate including the fabrication of polymer nanostructure arrays and the metallization of the polymer nanostructure arrays. The polymer nanostructure arrays were obtained by using R2R UV-NIL technique and anodic aluminum oxide (AAO) mold. The functional SERS substrates were then obtained with Au sputtering on the surface of the polymer nanostructure arrays. The obtained SERS substrates exhibit excellent SERS and flexibility performance. This research can provide a beneficial direction for the continuous production of the flexible SERS substrates. PMID:28051175

Modification of heterogeneous chemistry by complex substrate morphology

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

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

1998-12-31

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

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

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

Vapor bridges between solid substrates in the presence of the contact line pinning effect: Stability and capillary force

NASA Astrophysics Data System (ADS)

Liu, Yawei; Zhang, Xianren

2016-12-01

In this work, we focus on investigating how nanobubbles mediate long-range interaction between neighboring solid substrates in the presence of the contact line pinning effect caused by surface heterogeneities. Using the constrained lattice density functional theory (LDFT), we prove that the nanobubbles, which take the form of vapor bridges here, are stabilized by the pinning effect if the separation between two substrates is less than a critical distance. The critical distance strongly depends on the chemical potential (i.e., the degree of saturation) and could become extremely long at a special chemical potential. Moreover, under the pinning effect, the substrate chemistry only determines the stability of the vapor bridges and the range of the capillary force, but has less influences on the magnitude of the capillary force, indicating that the substrate chemistry or the apparent contact angle for droplets or bubbles on the substrates is no longer a direct parameter to determine the magnitude of capillary force. A qualitative analysis for the two dimensional vapor bridges by considering the feedback mechanism can explain the results from the LDFT calculations.

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

PubMed

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

2018-06-05

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

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

NASA Astrophysics Data System (ADS)

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

2008-10-01

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

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

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

PubMed Central

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

2011-01-01

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

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

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

PubMed

Gu, Junsi; Fahrenkrug, Eli; Maldonado, Stephen

2014-09-02

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

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).

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

NASA Technical Reports Server (NTRS)

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

1974-01-01

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

In situ oligonucleotide synthesis on poly(dimethylsiloxane): a flexible substrate for microarray fabrication

PubMed Central

Moorcroft, Matthew J.; Meuleman, Wouter R. A.; Latham, Steven G.; Nicholls, Thomas J.; Egeland, Ryan D.; Southern, Edwin M.

2005-01-01

In this paper, we demonstrate in situ synthesis of oligonucleotide probes on poly(dimethylsiloxane) (PDMS) microchannels through use of conventional phosphoramidite chemistry. PDMS polymer was moulded into a series of microchannels using standard soft lithography (micro-moulding), with dimensions <100 μm. The surface of the PDMS was derivatized by exposure to ultraviolet/ozone followed by vapour phase deposition of glycidoxypropyltrimethoxysilane and reaction with poly(ethylene glycol) spacer, resulting in a reactive surface for oligonucleotide coupling. High, reproducible yields were achieved for both 6mer and 21mer probes as assessed by hybridization to fluorescent oligonucleotides. Oligonucleotide surface density was comparable with that obtained on glass substrates. These results suggest PDMS as a stable and flexible alternative to glass as a suitable substrate in the fabrication and synthesis of DNA microarrays. PMID:15870385

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

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

Dong, Ban Xuan; Strzalka, Joseph; Jiang, Zhang

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show thatmore » MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. Furthermore, the evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.« less

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

DOE PAGES

Dong, Ban Xuan; Strzalka, Joseph; Jiang, Zhang; ...

2017-11-23

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show thatmore » MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. Furthermore, the evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.« less

Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.

PubMed

Greenwood, John; Phan, Thanh Hai; Fujita, Yasuhiko; Li, Zhi; Ivasenko, Oleksandr; Vanderlinden, Willem; Van Gorp, Hans; Frederickx, Wout; Lu, Gang; Tahara, Kazukuni; Tobe, Yoshito; Uji-I, Hiroshi; Mertens, Stijn F L; De Feyter, Steven

2015-05-26

We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.

Modification of Silicone Elastomer Surfaces with Zwitterionic Polymers: Short-Term Fouling Resistance and Triggered Biofouling Release.

PubMed

Shivapooja, Phanindhar; Yu, Qian; Orihuela, Beatriz; Mays, Robin; Rittschof, Daniel; Genzer, Jan; López, Gabriel P

2015-11-25

We present a method for dual-mode-management of biofouling by modifying surface of silicone elastomers with zwitterionic polymeric grafts. Poly(sulfobetaine methacrylate) was grafted from poly(vinylmethylsiloxane) elastomer substrates using thiol-ene click chemistry and surface-initiated, controlled radical polymerization. These surfaces exhibited both fouling resistance and triggered fouling-release functionality. The zwitterionic polymers exhibited fouling resistance over short-term (∼hours) exposure to bacteria and barnacle cyprids. The biofilms that eventually accumulated over prolonged-exposure (∼days) were easily detached by applying mechanical strain to the elastomer substrate. Such dual-functional surfaces may be useful in developing environmentally and biologically friendly coatings for biofouling management on marine, industrial, and biomedical equipment because they can obviate the use of toxic compounds.

Measuring shear force transmission across a biomimetic glycocalyx

NASA Astrophysics Data System (ADS)

Bray, Isabel; Young, Dylan; Scrimgeour, Jan

Human blood vessels are lined with a low-density polymer brush known as the glycocalyx. This brush plays an active role in defining the mechanical and biochemical environment of the endothelial cell in the blood vessel wall. In addition, it is involved in the detection of mechanical stimuli, such as the shear stress from blood flowing in the vessel. In this work, we construct a biomimetic version of the glycocalyx on top of a soft deformable substrate in order to measure its ability to modulate the effects of shear stress at the endothelial cell surface. The soft substrate is stamped on to a glass substrate and then enclosed inside a microfluidic device that generates a controlled flow over the substrate. The hydrogel chemistry has been optimized so that it reliably stamps into a defined shape and has consistent mechanical properties. Fluorescent microbeads embedded in the gel allow measurement of the surface deformation, and subsequently, calculation of the shear force at the surface of the soft substrate. We investigate the effect of the major structural elements of the glycocalyx, hyaluronic acid and charged proteoglycans, on the magnitude of the shear force transmitted to the surface of the hydrogel.

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.

Biofunctionalization of a “Clickable” Organic Layer Photochemically Grafted on Titanium Substrates

PubMed Central

Li, Yan; Zhao, Meirong; Wang, Jun; Liu, Kai; Cai, Chengzhi

2011-01-01

We have developed a general method combining photochemical grafting and copper-catalyzed click chemistry for biofunctionalization of titanium substrates. The UV-activated grafting of an α,ω-alkenyne onto TiO2/Ti substrates provided a “clickable” thin film platform. The selective attachment of the vinyl end of the molecule to the surface was achieved by masking the alkynyl end with a trimethylgermanyl (TMG) protecting group. Subsequently, various oligo(ethylene glycol) (OEG) derivatives terminated with an azido group were attached to the TMG-alkynyl modified titanium surface via a one-pot deprotection/click reaction. The films were characterized by X-ray photoelectron spectroscopy (XPS), contact angle goniometry, ellipsometry, and atomic force microscopy (AFM). We showed that the titanium surface presenting click-immobilized OEG substantially suppressed the nonspecific attachment of protein and cells as compared to the unmodified titanium substrate. Furthermore, glycine-arginine-glycine-aspartate (GRGD), a cell adhesion peptide, was coimmobilized with OEG on the platform. We demonstrated that the resultant GRGD-presenting thin film on Ti substrates can promote the specific adhesion and spreading of AsPC-1 cells. PMID:21417429

Influence of the surface chemistry on TiO2 - TiO2 nanocontact forces as measured by an UHV-AFM

NASA Astrophysics Data System (ADS)

Kunze, Christian; Giner, Ignacio; Torun, Boray; Grundmeier, Guido

2014-03-01

Particle-wall contact forces between a TiO2 film coated AFM tip and TiO2(1 1 0) single crystal surfaces were analyzed by means of UHV-AFM. As a reference system an octadecylphosphonic acid monolayer covered TiO2(1 1 0) surface was studied. The defect chemistry of the TiO2 substrate was modified by Ar ion bombardment, water dosing at 3 × 10-6 Pa and an annealing step at 473 K which resulted in a varying density of Ti(III) states. The observed contact forces are correlated to the surface defect density and are discussed in terms of the change in the electronic structure and its influence on the Hamaker constant.

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.

Zwitterionic modification of polyurethane membranes for enhancing the anti-fouling property.

PubMed

Liu, Peiming; Huang, Tao; Liu, Pingsheng; Shi, Shufeng; Chen, Qiang; Li, Li; Shen, Jian

2016-10-15

Polyurethane (PU) is a biopolymer that has been commonly used for biomedical applications. However, the biofouling phenomenon on the hydrophobic PU surface is one of the crucial issues that embarrassing its applications. Here, we report a facile & efficient approach to improve the anti-biofouling ability of the PU substrates. Active residues were firstly generated on the PU surface by using the low temperature air-plasma treatment, promoting the immobilization of the atom transfer radical polymerization (ATRP) initiators on the surface. Then, three types of zwitterionic polymer brushes, as well as PEG brushes, have been fabricated on the PU substrates through surface-initiated ATRP (SI-ATRP). Robust surface characterizations that capable of revealing the surface chemistry (including X-ray photoelectron spectroscopy (XPS) and wettability tests), and antifouling evaluations of the PU substrates (protein adsorption, platelet adhesion, and cell adhesion measurements) were performed. Results showed that three types of zwitterionic brushes have been successful grafted on the PU surface, respectively. And the three types of zwitterionic brushes, in general, significantly inhibited the protein adsorption, the platelet adhesion, and the cell adhesion on the PU surface, endowing a significantly improved anti-fouling ability to the PU substrates. Furthermore, we found that this facial zwitterionic surface modification did not compromise the mechanical property of the PU substrates. This strategy could be easily exploited to PU-based biomaterials to improve their performance in many applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Superhydrophobicity enhancement through substrate flexibility

NASA Astrophysics Data System (ADS)

Vasileiou, Thomas; Gerber, Julia; Prautzsch, Jana; Schutzius, Thomas; Poulikakos, Dimos

2017-11-01

Inspired by manifestations in nature, micro/nanoengineering superhydrophobic surfaces has been the focus of much work. Generally, hydrophobicity is increased through the combined effects of surface texturing and chemistry; being durable, rigid substrate materials are the norm. However, many natural and technical materials are flexible, and the resulting effect on hydrophobicity has been largely unexplored. Here, we show that the rational tuning of flexibility can work collaboratively with the surface micro/nanotexture to enhance liquid repellency performance, defined by impalement and breakup resistance, contact time reduction, and restitution coefficient increase. Reduction in substrate stiffness and areal density imparts immediate acceleration and intrinsic responsiveness to impacting droplets, mitigating the collision and lowering the impalement probability by 60 % without the need for active actuation. We demonstrate the above discoveries with materials ranging from thin steel or polymer sheets to butterfly wings. Partial support of the Swiss National Science Foundation under Grant 162565 and the European Research Council under Advanced Grant 669908 (INTICE) is acknowledged.

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

NASA Astrophysics Data System (ADS)

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

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

Preparing Al-Mg Substrate for Thermal Spraying: Evaluation of Surface State After Different Pretreatments

NASA Astrophysics Data System (ADS)

Lukauskaitė, R.; Valiulis, A. V.; Černašėjus, O.; Škamat, J.; Rębiś, J. A.

2016-08-01

The article deals with the pretreatment technique for preparing the surface of aluminum alloy EN AW 5754 before thermal spray. The surface after different pretreatments, including degreasing with acetone, chemical etching with acidic and alkali solutions, grit-blasting, cathodic cleaning, and some combinations of these techniques, has been studied. The investigation of pre-treated surfaces covered the topographical study (using scanning electron microscopy, atomic force microscopy, and 3D profilometry), the chemical analysis by x-ray photoelectron spectroscopy, the evaluation of surface wettability (sessile drop method), and the assessment of surface free energy. Compared with all the techniques used in present work, the cathodic cleaning and its combination with grit-blasting provide the most preferable chemistry of the surface. Due to the absence of hydroxides at the surface and, possible, due to the diffusion of magnesium to the surface of substrate, the surface wettability and the surface free energy have been significantly improved. No direct correlation between the surface topography and the surface wettability has been established.

Rapid Covalent Modification of Silicon Oxide Surfaces through Microwave-Assisted Reactions with Alcohols.

PubMed

Lee, Austin W H; Gates, Byron D

2016-07-26

We demonstrate the method of a rapid covalent modification of silicon oxide surfaces with alcohol-containing compounds with assistance by microwave reactions. Alcohol-containing compounds are prevalent reagents in the laboratory, which are also relatively easy to handle because of their stability against exposure to atmospheric moisture. The condensation of these alcohols with the surfaces of silicon oxides is often hindered by slow reaction kinetics. Microwave radiation effectively accelerates this condensation reaction by heating the substrates and/or solvents. A variety of substrates were modified in this demonstration, such as silicon oxide films of various thicknesses, glass substrates such as microscope slides (soda lime), and quartz. The monolayers prepared through this strategy demonstrated the successful formation of covalent surface modifications of silicon oxides with water contact angles of up to 110° and typical hysteresis values of 2° or less. An evaluation of the hydrolytic stability of these monolayers demonstrated their excellent stability under acidic conditions. The techniques introduced in this article were successfully applied to tune the surface chemistry of silicon oxides to achieve hydrophobic, oleophobic, and/or charged surfaces.

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.

Conformal dip-coating of patterned surfaces for capillary die-to-substrate self-assembly

NASA Astrophysics Data System (ADS)

Mastrangeli, M.; Ruythooren, W.; Van Hoof, C.; Celis, J.-P.

2009-04-01

Capillarity-driven self-assembly of small chips onto planar target substrates is a promising alternative to robotic pick-and-place assembly. It critically relies on the selective deposition of thin fluid films on patterned binding sites, which is anyway normally non-conformal. We found that the addition of a thin wetting sidewall, surrounding the entire site perimeter, enables the conformal fluid coverage of arbitrarily shaped sites through dip-coating, significantly improves the reproducibility of the coating process and strongly reduces its sensitivity to surface defects. In this paper we support the feasibility and potential of this method by demonstrating the conformal dip-coating of square and triangular sites conditioned with combinations of different hydrophobic and hydrophilic surface chemistries. We present both experimental and simulative evidence of the advantages brought by the introduction of the wetting boundary on film coverage accuracy. Application of our surface preparation method to capillary self-assembly could result in higher precision in die-to-substrate registration and larger freedom in site shape design.

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.

Surface design for controlled crystallization: the role of surface chemistry and nanoscale pores in heterogeneous nucleation.

PubMed

Diao, Ying; Myerson, Allan S; Hatton, T Alan; Trout, Bernhardt L

2011-05-03

Current industrial practice for control of primary nucleation (nucleation from a system without pre-existing crystalline matter) during crystallization from solution involves control of supersaturation generation, impurity levels, and solvent composition. Nucleation behavior remains largely unpredictable, however, due to the presence of container surfaces, dust, dirt, and other impurities that can provide heterogeneous nucleation sites, thus making the control and scale-up of processes that depend on primary nucleation difficult. To develop a basis for the rational design of surfaces to control nucleation during crystallization from solution, we studied the role of surface chemistry and morphology of various polymeric substrates on heterogeneous nucleation using aspirin as a model compound. Nucleation induction time statistics were utilized to investigate and quantify systematically the effectiveness of polymer substrates in inducing nucleation. The nucleation induction time study revealed that poly(4-acryloylmorpholine) and poly(2-carboxyethyl acrylate), each cross-linked by divinylbenzene, significantly lowered the nucleation induction time of aspirin while the other polymers were essentially inactive. In addition, we found the presence of nanoscopic pores on certain polymer surfaces led to order-of-magnitude faster aspirin nucleation rates when compared with surfaces without pores. We studied the preferred orientation of aspirin crystals on polymer films and found the nucleation-active polymer surfaces preferentially nucleated the polar facets of aspirin, guided by hydrogen bonds. A model based on interfacial free energies was also developed which predicted the same trend of polymer surface nucleation activities as indicated by the nucleation induction times.

Direct write with microelectronic circuit fabrication

DOEpatents

Drummond, T.; Ginley, D.

1988-05-31

In a process for deposition of material onto a substrate, for example, the deposition of metals for dielectrics onto a semiconductor laser, the material is deposited by providing a colloidal suspension of the material and directly writing the suspension onto the substrate surface by ink jet printing techniques. This procedure minimizes the handling requirements of the substrate during the deposition process and also minimizes the exchange of energy between the material to be deposited and the substrate at the interface. The deposited material is then resolved into a desired pattern, preferably by subjecting the deposit to a laser annealing step. The laser annealing step provides high resolution of the resultant pattern while minimizing the overall thermal load of the substrate and permitting precise control of interface chemistry and interdiffusion between the substrate and the deposit. 3 figs.

Direct write with microelectronic circuit fabrication

DOEpatents

Drummond, Timothy; Ginley, David

1992-01-01

In a process for deposition of material onto a substrate, for example, the deposition of metals or dielectrics onto a semiconductor laser, the material is deposited by providing a colloidal suspension of the material and directly writing the suspension onto the substrate surface by ink jet printing techniques. This procedure minimizes the handling requirements of the substrate during the deposition process and also minimizes the exchange of energy between the material to be deposited and the substrate at the interface. The deposited material is then resolved into a desired pattern, preferably by subjecting the deposit to a laser annealing step. The laser annealing step provides high resolution of the resultant pattern while minimizing the overall thermal load of the substrate and permitting precise control of interface chemistry and interdiffusion between the substrate and the deposit.

Mechanical Characterization of Polydopamine-Assisted Silver Deposition on Polymer Substrates

NASA Astrophysics Data System (ADS)

Cordes, Amanda Laurence

Inspired by the adhesive proteins in marine mussels, polydopamine has become a popular adhesive ad-layer for surface functionalization of a variety of substrates. Based on the chemistry of the dopamine monomer, amine and thiol functional groups are hypothesized to increase adhesion between polymer substrates and polydopamine thin films. This hypothesis was the central motivation for development of a tailorable thiol-ene system in order to study the effects of substrate chemistry on polydopamine adhesion. While polydopamine-adhered silver has been studied on a variety of substrates, no in depth mechanical characterization has been performed and to date, no research has been published on thiol-enes coated in polydopamine-adhered silver. The purpose of this study was to characterize the mechanical durability and adhesion properties of a polydopamine-adhered silver film on commercial substrates and a tailorable thiol-ene system. Polydopamine and silver coatings were deposited on a variety of polymer substrates through a simple dip-coat process. The polydopamine forms a thin uniform adhesive layer and the silver deposits in a discontinuous manner with a nanoparticle sized base layer covering the full surface and micron-sized clusters adhered sporadically on top. Mechanical tensile testing was performed to characterize the durability of the silver coating on commercial polymers. Coated nylon and HDPE showed no signs of degradation or delamination of the polydopamine-adhered silver coating up to 30% strain although both substrates showed large plastic deformation. Peel tests were performed on both commercial polymers as well as a tailorable thiol-ene system. Results support the hypothesis that polydopamine adhesion is increased with the presence of functional groups. Parts of the HDPE sample were cleanly peeled, but silver patches were left sporadically across the surface pointing to weaker adhesion between polyethylene and polydopamine. A high adhesive strength tape was used on nylon and the thiol-ene polymers and removed some of the large clusters but was ineffective at removing the particle base layer. The silver base layer remained firmly attached on the surface after multiple rounds of peel testing. With the addition of functional groups in the polymer makeup, the adhesion strength of polydopamine-adhered silver coatings can be increased to create a mechanically durable and adhesively robust silver coating.

Polymer Brushes Containing Sulfonated Sugar Repeat Units: Synthesis, Characterization and In Vitro Testing of Blood Coagulation Activation

PubMed Central

Ayres, N.; Holt, D. J.; Jones, C.F.; Corum, L. E.; Grainger, D. W.

2009-01-01

A new polymer brush chemistry containing sulfonated carbohydrate repeat units has been synthesized from silicon substrates using ATRP methods and characterized both in bulk and using surface analysis. The polymer brush was designed to act as a mimic for the naturally occurring sulfonated glycosaminoglycan, heparin, commonly used for modifying blood-contacting surfaces both in vitro and in vivo. Surface analysis showed conversion of brush saccharide precursor chemistry to the desired sulfonated polymer product. The sulfonated polymer brush surface was further analyzed using three conventional in vitro tests for blood compatibility -- plasma recalcification times, complement activation, and thrombin generation. The sulfonated polymer brush films on silicon oxide wafers exhibited better assay performance in these blood component assays than the unsulfonated sugar functionalized polymer brush in all tests performed. PMID:19859552

Influence of chemistry on wetting dynamics of nanotextured hydrophobic surfaces.

PubMed

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

2010-04-06

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

The physics and chemistry of graphene-on-surfaces.

PubMed

Zhao, Guoke; Li, Xinming; Huang, Meirong; Zhen, Zhen; Zhong, Yujia; Chen, Qiao; Zhao, Xuanliang; He, Yijia; Hu, Ruirui; Yang, Tingting; Zhang, Rujing; Li, Changli; Kong, Jing; Xu, Jian-Bin; Ruoff, Rodney S; Zhu, Hongwei

2017-07-31

Graphene has demonstrated great potential in next-generation electronics due to its unique two-dimensional structure and properties including a zero-gap band structure, high electron mobility, and high electrical and thermal conductivity. The integration of atom-thick graphene into a device always involves its interaction with a supporting substrate by van der Waals forces and other intermolecular forces or even covalent bonding, and this is critical to its real applications. Graphene films on different surfaces are expected to exhibit significant differences in their properties, which lead to changes in their morphology, electronic structure, surface chemistry/physics, and surface/interface states. Therefore, a thorough understanding of the surface/interface properties is of great importance. In this review, we describe the major "graphene-on-surface" structures and examine the roles of their properties and related phenomena in governing the overall performance for specific applications including optoelectronics, surface catalysis, anti-friction and superlubricity, and coatings and composites. Finally, perspectives on the opportunities and challenges of graphene-on-surface systems are discussed.

Time-Dependent Migratory Behaviors in the Long-Term Studies of Fibroblast Durotaxis on a Hydrogel Substrate Fabricated with a Soft Band

PubMed Central

2015-01-01

Durotaxis, biased cell movement up a stiffness gradient on culture substrates, is one of the useful taxis behaviors for manipulating cell migration on engineered biomaterial surfaces. In this study, long-term durotaxis was investigated on gelatinous substrates containing a soft band of 20, 50, and 150 μm in width fabricated using photolithographic elasticity patterning; sharp elasticity boundaries with a gradient strength of 300 kPa/50 μm were achieved. Time-dependent migratory behaviors of 3T3 fibroblast cells were observed during a time period of 3 days. During the first day, most of the cells were strongly repelled by the soft band independent of bandwidth, exhibiting the typical durotaxis behavior. However, the repellency by the soft band diminished, and more cells crossed the soft band or exhibited other mixed migratory behaviors during the course of the observation. It was found that durotaxis strength is weakened on the substrate with the narrowest soft band and that adherent affinity-induced entrapment becomes apparent on the widest soft band with time. Factors, such as changes in surface topography, elasticity, and/or chemistry, likely contributing to the apparent diminishing durotaxis during the extended culture were examined. Immunofluorescence analysis indicated preferential collagen deposition onto the soft band, which is derived from secretion by fibroblast cells, resulting in the increasing contribution of haptotaxis toward the soft band over time. The deposited collagen did not affect surface topography or surface elasticity but did change surface chemistry, especially on the soft band. The observed time-dependent durotaxis behaviors are the result of the mixed mechanical and chemical cues. In the studies and applications of cell migratory behavior under a controlled stimulus, it is important to thoroughly examine other (hidden) compounding stimuli in order to be able to accurately interpret data and to design suitable biomaterials to manipulate cell migration. PMID:24851722

Quantitative Comparison of Protein Adsorption and Conformational Changes on Dielectric-Coated Nanoplasmonic Sensing Arrays.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Sut, Tun Naw; Cho, Nam-Joon

2018-04-22

Nanoplasmonic sensors are a popular, surface-sensitive measurement tool to investigate biomacromolecular interactions at solid-liquid interfaces, opening the door to a wide range of applications. In addition to high surface sensitivity, nanoplasmonic sensors have versatile surface chemistry options as plasmonic metal nanoparticles can be coated with thin dielectric layers. Within this scope, nanoplasmonic sensors have demonstrated promise for tracking protein adsorption and substrate-induced conformational changes on oxide film-coated arrays, although existing studies have been limited to single substrates. Herein, we investigated human serum albumin (HSA) adsorption onto silica- and titania-coated arrays of plasmonic gold nanodisks by localized surface plasmon resonance (LSPR) measurements and established an analytical framework to compare responses across multiple substrates with different sensitivities. While similar responses were recorded on the two substrates for HSA adsorption under physiologically-relevant ionic strength conditions, distinct substrate-specific behavior was observed at lower ionic strength conditions. With decreasing ionic strength, larger measurement responses occurred for HSA adsorption onto silica surfaces, whereas HSA adsorption onto titania surfaces occurred independently of ionic strength condition. Complementary quartz crystal microbalance-dissipation (QCM-D) measurements were also performed, and the trend in adsorption behavior was similar. Of note, the magnitudes of the ionic strength-dependent LSPR and QCM-D measurement responses varied, and are discussed with respect to the measurement principle and surface sensitivity of each technique. Taken together, our findings demonstrate how the high surface sensitivity of nanoplasmonic sensors can be applied to quantitatively characterize protein adsorption across multiple surfaces, and outline broadly-applicable measurement strategies for biointerfacial science applications.

Reduction of structural defects in thick 4H-SiC epitaxial layers grown on 4° off-axis substrates

NASA Astrophysics Data System (ADS)

Yazdanfar, M.; Ivanov, I. G.; Pedersen, H.; Kordina, O.; Janzén, E.

2013-06-01

By carefully controlling the surface chemistry of the chemical vapor deposition process for silicon carbide (SiC), 100 μm thick epitaxial layers with excellent morphology were grown on 4° off-axis SiC substrates at growth rates exceeding 100 μm/h. In order to reduce the formation of step bunching and structural defects, mainly triangular defects, the effect of varying parameters such as growth temperature, C/Si ratio, Cl/Si ratio, Si/H2 ratio, and in situ pre-growth surface etching time are studied. It was found that an in-situ pre growth etch at growth temperature and pressure using 0.6% HCl in hydrogen for 12 min reduced the structural defects by etching preferentially on surface damages of the substrate surface. By then applying a slightly lower growth temperature of 1575 °C, a C/Si ratio of 0.8, and a Cl/Si ratio of 5, 100 μm thick, step-bunch free epitaxial layer with a minimum triangular defect density and excellent morphology could be grown, thus enabling SiC power device structures to be grown on 4° off axis SiC substrates.

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

Biomaterial adherent macrophage apoptosis is increased by hydrophilic and anionic substrates in vivo

NASA Astrophysics Data System (ADS)

Brodbeck, William G.; Patel, Jasmine; Voskerician, Gabriela; Christenson, Elizabeth; Shive, Matthew S.; Nakayama, Yasuhide; Matsuda, Takehisa; Ziats, Nicholas P.; Anderson, James M.

2002-08-01

An in vivo rat cage implant system was used to identify potential surface chemistries that prevent failure of implanted biomedical devices and prostheses by limiting monocyte adhesion and macrophage fusion into foreign-body giant cells while inducing adherent-macrophage apoptosis. Hydrophobic, hydrophilic, anionic, and cationic surfaces were used for implantation. Analysis of the exudate surrounding the materials revealed no differences between surfaces in the types or levels of cells present. Conversely, the proportion of adherent cells undergoing apoptosis was increased significantly on anionic and hydrophilic surfaces (46 ± 3.7 and 57 ± 5.0%, respectively) when compared with the polyethylene terephthalate base surface. Additionally, hydrophilic and anionic substrates provided decreased rates of monocyte/macrophage adhesion and fusion. These studies demonstrate that biomaterial-adherent cells undergo material-dependent apoptosis in vivo, rendering potentially harmful macrophages nonfunctional while the surrounding environment of the implant remains unaffected.

The effect of steel chemistry on the formation of Fe-Zn intermetallic compounds of galvanneal-coated steel sheets

NASA Astrophysics Data System (ADS)

Lin, C. S.; Meshii, M.

1994-10-01

The effects of steel chemistry on the formation of Fe-Zn intermetallic compounds in the galvanneal coatings have been investigated by examining the microstructure of galvanneal coat-ings on extra-low-carbon (ELC) steel, interstitial-free (IF) steel, and interstitial-free rephos-phorized (IFP) steel. The layer structure of the coatings was revealed by chemical etching. Phases present in each layer were then identified using electron diffraction in transmission elec-tron microscopy (TEM). A two-layer structure, one consisting of the δ phase with a small fraction of the ζ, phase dispersed on the surface and Γ phases and another consisting of the δ and Γ1 phases, was observed in the ELC sample and the IFP sample, respectively. A three-layer structure consisting of the δ, Γ1 + δ, and Γ phases was observed in the IF sample. The presence of C in the steel substrate retarded the alloying between Fe and Zn; while P in the steel favored the formation of the Γ1, phase over the Γ phase by its surface segregation in the steel substrate. The orientation relationship between coating and substrate was also studied by electron diffraction. Three α-Fe/Γ orientation relationships were frequently observed.

Smooth perfluorinated surfaces with different chemical and physical natures: their unusual dynamic dewetting behavior toward polar and nonpolar liquids.

PubMed

Cheng, Dalton F; Masheder, Benjamin; Urata, Chihiro; Hozumi, Atsushi

2013-09-10

The effects of surface chemistry and the mobility of surface-tethered functional groups of various perfluorinated surfaces on their dewetting behavior toward polar (water) and nonpolar (n-hexadecane, n-dodecane, and n-decane) liquids were investigated. In this study, three types of common smooth perfluorinated surfaces, that is, a perfluoroalkylsilane (heptadecafluoro-1,1,2,2-tetrahydrooctyl-dimethylchlorosilane, FAS17) monomeric layer, an amorphous fluoropolymer film (Teflon AF 1600), and a perfluorinated polyether (PFPE)-terminated polymer brush film (Optool DSX), were prepared and their static/dynamic dewetting characteristics were compared. Although the apparent static contact angles (CAs) of these surfaces with all probe liquids were almost identical to each other, the ease of movement of liquid drops critically depended on the physical (solidlike or liquidlike) natures of the substrate surface. CA hysteresis and substrate tilt angles (TAs) of all probe liquids on the Optool DSX surface were found to be much lower than those of Teflon AF1600 and FAS17 surfaces due to its physical polymer chain mobility at room temperature and the resulting liquidlike nature. Only 6.0° of substrate incline was required to initiate movement for a small drop (5 μL) of n-decane, which was comparable to the reported substrate TA value (5.3°) for a superoleophobic surface (θ(S) > 160°, textured perfluorinated surface). Such unusual dynamic dewetting behavior of the Optool DSX surface was also markedly enhanced due to the significant increase in the chain mobility of PFPE by moderate heating (70 °C) of the surface, with substrate TA reducing to 3.0°. CA hysteresis and substrate TAs rather than static CAs were therefore determined to be of greater consequence for the estimation of the actual dynamic dewetting behavior of alkane probe liquids on these smooth perfluorinated surfaces. Their dynamic dewettability toward alkane liquids is in the order of Optool DSX > Teflon AF1600 ≈ FAS17.

Developing the Surface Chemistry of Transparent Butyl Rubber for Impermeable Stretchable Electronics.

PubMed

Vohra, Akhil; Carmichael, R Stephen; Carmichael, Tricia Breen

2016-10-11

Transparent butyl rubber is a new elastomer that has the potential to revolutionize stretchable electronics due to its intrinsically low gas permeability. Encapsulating organic electronic materials and devices with transparent butyl rubber protects them from problematic degradation due to oxygen and moisture, preventing premature device failure and enabling the fabrication of stretchable organic electronic devices with practical lifetimes. Here, we report a methodology to alter the surface chemistry of transparent butyl rubber to advance this material from acting as a simple device encapsulant to functioning as a substrate primed for direct device fabrication on its surface. We demonstrate a combination of plasma and chemical treatment to deposit a hydrophilic silicate layer on the transparent butyl rubber surface to create a new layered composite that combines Si-OH surface chemistry with the favorable gas-barrier properties of bulk transparent butyl rubber. We demonstrate that these surface Si-OH groups react with organosilanes to form self-assembled monolayers necessary for the deposition of electronic materials, and furthermore demonstrate the fabrication of stretchable gold wires using nanotransfer printing of gold films onto transparent butyl rubber modified with a thiol-terminated self-assembled monolayer. The surface modification of transparent butyl rubber establishes this material as an important new elastomer for stretchable electronics and opens the way to robust, stretchable devices.

The Effect of Molybdenum Substrate Oxidation on Molybdenum Splat Formation

NASA Astrophysics Data System (ADS)

Wang, Jun; Li, Chang-Jiu

2018-01-01

Disk splats are usually observed when the deposition temperature exceeds the transition temperature, whereas thick oxide layer will reduce the adhesion resulting from high deposition temperature. In present study, single molybdenum splats were deposited onto polished molybdenum substrates with different preheating processes to clarify the effect of surface oxidation on the splat formation. Three substrate samples experienced three different preheating processes in an argon atmosphere. Two samples were preheated to 350 and 550 °C, and another sample was cooled to 350 °C after it was preheated to 550 °C. The chemistry and compositions of substrate surface were examined by XPS. The cross sections of splats were prepared by focus ion beam (FIB) and then characterized by SEM. Nearly disk-shaped splat with small fingers in the periphery was observed on the sample preheated to 350 °C. A perfect disk-shape splat was deposited at 550 °C. With the sample on the substrate preheated to 350 °C (cooling down from 550 °C), flower-shaped splat exhibited a central core and discrete periphery detached by some voids. The results of peeling off splats by carbon tape and the morphology of FIB sampled cross sections indicated that no effective bonding formed at the splat-substrate interface for the substrate ever heated to 550 °C, due to the increasing content of MoO3 on the preheated molybdenum surface.

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.

Monolayer graphene on nanostructured Ag for enhancement of surface-enhanced Raman scattering stable platform

NASA Astrophysics Data System (ADS)

Dai, Zhigao; Mei, Fei; Xiao, Xiangheng; Liao, Lei; Wu, Wei; Zhang, Yupeng; Ying, Jianjian; Wang, Lingbo; Ren, Feng; Jiang, Changzhong

2015-03-01

We have reported that the Ag nanostructure-based substrate is particularly suitable for surface-enhanced Raman scattering when it is coated with monolayer graphene, an optically transparent and chemistry-inertness material in the visible range. Ag bowtie nanoantenna arrays and Ag nanogrids were fabricated using plasma-assisted nanosphere lithography. Our measurements show that atmospheric sulfur containing compounds are powerless to break in the monolayer graphene to vulcanize the surfaces of the Ag bowtie nanoantenna arrays and Ag nanogrids by various means, including scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). Furthermore, the Ag nanostructure substrate coated with the monolayer graphene film shows a larger enhancement of Raman activity and the electromagnetic field than the uncoated substrate. Compared with those of bare Ag nanostructures, the averaged EFs of graphene-film-coated Ag nanostructures were estimated to be about 21 and 5 for Ag bowtie nanoantenna arrays and nanogrids after one month later in air, respectively. These observations are further supported by theoretical calculations.

Picosecond laser micro/nano surface texturing of nickel for superhydrophobicity

NASA Astrophysics Data System (ADS)

Wang, X. C.; Wang, B.; Xie, H.; Zheng, H. Y.; Lam, Y. C.

2018-03-01

A single step direct picosecond laser texturing process was demonstrated to be able to obtain a superhydrophobic surface on a nickel substrate, a key material for mold fabrication in the manufacture of various devices, including polymeric microfluidic devices. A two-scale hierarchical surface structure of regular 2D array micro-bumps with nano-ripples was produced on a nickel surface. The laser textured surface initially showed superhydrophilicity with almost complete wetting of the structured surface just after laser treatment, then quickly changed to nearly superhydrophobic with a water contact angle (WCA) of 140° in less than 1 d, and finally became superhydrophobic with a WCA of more than 150° and a contact angle hysteresis (CAH) of less than 5°. The mechanism involved in the process is discussed in terms of surface morphology and surface chemistry. The ultra-fast laser induced NiO catalytic effect was thought to play a key role in modifying the surface chemistry so as to lower the surface energy. The developed process has the potential to improve the performance of nickel mold in the fabrication of microfluidic devices.

Key advances in the chemical modification of nanocelluloses.

PubMed

Habibi, Youssef

2014-03-07

Nanocelluloses, including nanocrystalline cellulose, nanofibrillated cellulose and bacterial cellulose nanofibers, have become fascinating building blocks for the design of new biomaterials. Derived from the must abundant and renewable biopolymer, they are drawing a tremendous level of attention, which certainly will continue to grow in the future driven by the sustainability trend. This growing interest is related to their unsurpassed quintessential physical and chemical properties. Yet, owing to their hydrophilic nature, their utilization is restricted to applications involving hydrophilic or polar media, which limits their exploitation. With the presence of a large number of chemical functionalities within their structure, these building blocks provide a unique platform for significant surface modification through various chemistries. These chemical modifications are prerequisite, sometimes unavoidable, to adapt the interfacial properties of nanocellulose substrates or adjust their hydrophilic-hydrophobic balance. Therefore, various chemistries have been developed aiming to surface-modify these nano-sized substrates in order to confer to them specific properties, extending therefore their use to highly sophisticated applications. This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.

High-content profiling of cell responsiveness to graded substrates based on combinyatorially variant polymers.

PubMed

Liu, Er; Treiser, Matthew D; Patel, Hiral; Sung, Hak-Joon; Roskov, Kristen E; Kohn, Joachim; Becker, Matthew L; Moghe, Prabhas V

2009-08-01

We have developed a novel approach combining high information and high throughput analysis to characterize cell adhesive responses to biomaterial substrates possessing gradients in surface topography. These gradients were fabricated by subjecting thin film blends of tyrosine-derived polycarbonates, i.e. poly(DTE carbonate) and poly(DTO carbonate) to a gradient temperature annealing protocol. Saos-2 cells engineered with a green fluorescent protein (GFP) reporter for farnesylation (GFP-f) were cultured on the gradient substrates to assess the effects of nanoscale surface topology and roughness that arise during the phase separation process on cell attachment and adhesion strength. The high throughput imaging approach allowed us to rapidly identify the "global" and "high content" structure-property relationships between cell adhesion and biomaterial properties such as polymer chemistry and topography. This study found that cell attachment and spreading increased monotonically with DTE content and were significantly elevated at the position with intermediate regions corresponding to the highest "gradient" of surface roughness, while GFP-f farnesylation intensity descriptors were sensitively altered by surface roughness, even in cells with comparable levels of spreading.

Characterizations of the Formation of Polydopamine-Coated Halloysite Nanotubes in Various pH Environments.

PubMed

Feng, Junran; Fan, Hailong; Zha, Dao-An; Wang, Le; Jin, Zhaoxia

2016-10-11

Recent studies demonstrated that polydopamine (PDA) coating is universal to nearly all substrates, and it endows substrates with biocompatibility, postfunctionality, and other useful properties. Surface chemistry of PDA coating is important for its postmodifications and applications. However, there is less understanding of the formation mechanism and surface functional groups of PDA layers generated in different conditions. Halloysite is a kind of clay mineral with tubular nanostructure. Water-swellable halloysite has unique reactivity. In this study, we have investigated the reaction of dopamine in the presence of water-swellable halloysite. We have tracked the reaction progresses in different pH environments by using UV-vis spectroscopy and surface-enhanced Raman spectroscopy (SERS). The surface properties of PDA on halloysite were clarified by X-ray photoelectron spectroscopy (XPS), SERS, Fourier transform infrared (FTIR) characterizations, zeta potential, surface wettability, and morphological characterizations. We noticed that the interaction between halloysite surface and dopamine strongly influences the surface functionality of coated PDA. In addition, pH condition further modulates surface functional groups, resulting in less content of secondary/aromatic amine in PDA generated in weak acidic environment. This study demonstrates that the formation mechanism of polydopamine becomes complex in the presence of inorganic nanomaterials. Substrate property and reaction condition dominate the functionality of obtained PDA together.

Orthogonal functionalization of nanoporous substrates: control of 3D surface functionality.

PubMed

Lazzara, Thomas D; Kliesch, Torben-Tobias; Janshoff, Andreas; Steinem, Claudia

2011-04-01

Anodic aluminum oxide (AAO) membranes with aligned, cylindrical, nonintersecting pores were selectively functionalized in order to create dual-functionality substrates with different pore-rim and pore-interior surface functionalities, using silane chemistry. We used a two-step process involving an evaporated thin gold film to protect the underlying surface functionality of the pore rims. Subsequent treatment with oxygen plasma of the modified AAO membrane removed the unprotected organic functional groups, i.e., the pore-interior surface. After gold removal, the substrate became optically transparent, and displayed two distinct surface functionalities, one at the pore-rim surface and another at the pore-interior surface. We achieved a selective hydrophobic functionalization with dodecyl-trichlorosilane of either the pore rims or the pore interiors. The deposition of planar lipid membranes on the functionalized areas by addition of small unilamellar vesicles occurred in a predetermined fashion. Small unilamellar vesicles only ruptured upon contact with the hydrophobic substrate regions forming solid supported hybrid bilayers. In addition, pore-rim functionalization with dodecyl-trichlorosilane allowed the formation of pore-spanning hybrid lipid membranes as a result of giant unilamellar vesicle rupture. Confocal laser scanning microscopy was employed to identify the selective spatial localization of the adsorbed fluorescently labeled lipids. The corresponding increase in the AAO refractive index due to lipid adsorption on the hydrophobic regions was monitored by optical waveguide spectroscopy. This simple orthogonal functionalization route is a promising method to control the three-dimensional surface functionality of nanoporous films. © 2011 American Chemical Society

Inkjet Printed Surface Enhanced Raman Spectroscopy Array on Cellulose Paper

PubMed Central

Yu, Wei W.; White, Ian M.

2011-01-01

A novel, ultra low-cost surface enhanced Raman spectroscopy (SERS) substrate has been developed by modifying the surface chemistry of cellulose paper and patterning nanoparticle arrays, all with a consumer inkjet printer. Micro/nanofabrication of SERS substrates for on-chip chemical and biomolecular analysis has been under intense investigation. However, the high cost of producing these substrates and the limited shelf life severely limit their use, especially for routine laboratory analysis and for point-of-sample analysis in the field. Paper-based microfluidic biosensing systems have shown great potential as low-cost disposable analysis tools. In this work, this concept is extended to SERS-based detection. Using an inexpensive consumer inkjet printer, cellulose paper substrates are modified to be hydrophobic in the sensing regions. Synthesized silver nanoparticles are printed onto this hydrophobic paper substrate with microscale precision to form sensing arrays. The hydrophobic surface prevents the aqueous sample from spreading throughout the paper and thus concentrates the analyte within the sensing region. A SERS fingerprint signal for Rhodamine 6G dye was observed for samples with as low as 10 femtomoles of analyte in a total sample volume of 1 μL. This extraordinarily simple technique can be used to construct SERS microarrays immediately before sample analysis, enabling ultra low-cost chemical and biomolecular detection in the lab as well as in the field at the point of sample collection. PMID:21058689

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.

Toward a mechanistic understanding of patterns in biomineralization and new insights for old dogmas in geological settings (Invited)

NASA Astrophysics Data System (ADS)

Dove, P. M.; Hamm, L.; Giuffre, A. J.; Han, N.; De Yoreo, J. J.

2013-12-01

The ability of organisms to mineralize tissues into skeletons and other functional structures is a remarkable achievement of biology. Yet, the physical basis for how macromolecules regulate the placement and onset of mineral formation is not well established. Efforts to understand nucleation onto organic substrates have produced two, seemingly contradictory, lines of thought: The biomineralization community widely assumes the organic matrix promotes nucleation through stereochemical matching to guide the organization of solute ions, while materials synthesis groups use simple binding assays to correlate high binding strength with good promoters of nucleation. This study reconciles the two views and provides a mechanistic explanation for template-directed nucleation by correlating heterogeneous nucleation barriers with crystal-substrate binding free energies. Using surface assembled monolayers (SAM) as simple model systems, we first measure the kinetics of calcite nucleation onto model substrates that present different functional group chemistries (carboxyl, thiol, phosphate, hydroxyl) and conformations (C11, C16 chain lengths). We find rates are substrate-specific and obey predictions of classical nucleation theory at supersaturations that extend above the solubility of amorphous calcium carbonate (ACC). Analysis of the kinetic data shows the thermodynamic barrier to nucleation is reduced by minimizing the interfacial free energy of the system, γ. We then use dynamic force spectroscopy to independently measure calcite-substrate binding free energies, ΔGb. Moreover, we show that within the classical theory of nucleation, γ and ΔGb should be linearly related. The results bear out this prediction and demonstrate that low energy barriers to nucleation correlate with strong crystal-substrate binding. This relationship is general to all functional group chemistries and conformations. These findings reconcile the long-standing concept of templated nucleation through stereochemical matching with the conventional wisdom that ';good binders are good nucleators'. Alternative perspectives become internally consistent when viewed through the lens of crystal-substrate binding and provide a physical basis for how organic chemistry can direct temporal and spatial patterns of carbonate nucleation.

Growth kinetics of disk-shaped copper islands in electrochemical deposition.

PubMed

Guo, Lian; Zhang, Shouliang; Searson, Peter

2009-05-01

The ability to independently dictate the shape and crystal orientation of islands in electrocrystallization remains a significant challenge. The main reason for this is that the complex interplay between the substrate, nucleation, and surface chemistry is not fully understood. Here we report on the kinetics of island growth for copper on ruthenium oxide. The small nucleation overpotential leads to enhanced lateral growth and the formation of hexagonal disk-shaped islands. The amorphous substrate allows the nuclei to achieve the thermodynamically favorable orientation, i.e., a 111 surface normal. Island growth follows power law kinetics in both lateral and vertical directions. At shorter times, the two growth exponents are equal to 1/2 whereas at longer times lateral growth slows down while vertical growth speeds up. We propose a growth mechanism, wherein the lateral growth of disk-shaped islands is initiated by attachment of Cu adatoms on the ruthenium oxide surface onto the island periphery while vertical growth is initiated by two-dimensional nucleation on the top terrace and followed by lateral step propagation. These results indicate three criteria for enhanced lateral growth in electrodeposition: (i) a substrate that leads to a small nucleation overpotential, (ii) fast adatom surface diffusion on substrate to promote lateral growth, and (iii) preferential anion adsorption to stabilize the basal plane.

The adsorption of alkyl-dimethyl-benzyl-ammonium chloride onto cotton nonwoven hydroentangled substrates at the solid-liquid interface is minimized by additive chemistries

USDA-ARS?s Scientific Manuscript database

Quaternary ammonium compounds, commonly referred to as quats, are cationic surfactants widely used as the active biocide ingredient for disposable disinfecting wipes. The cationic nature of quats results in a strong ionic interaction and adsorption onto wipes materials that have an anionic surface ...

Characterization of ion beam modified ceramic wear surfaces using Auger electron spectroscopy

NASA Technical Reports Server (NTRS)

Wei, W.; Lankford, J.

1987-01-01

An investigation of the surface chemistry and morphology of the wear surfaces of ceramic material surfaces modified by ion beam mixing has been conducted using Auger electron spectroscopy and secondary electron microscopy. Studies have been conducted on ceramic/ceramic friction and wear couples made up of TiC and NiMo-bonded TiC cermet pins run against Si3N4 and partially stabilized zirconia disc surfaces modified by the ion beam mixing of titanium and nickel, as well as ummodified ceramic/ceramic couples in order to determine the types of surface changes leading to the improved friction and wear behavior of the surface modified ceramics in simulated diesel environments. The results of the surface analyses indicate that the formation of a lubricating oxide layer of titanium and nickel, is responsible for the improvement in ceramic friction and wear behavior. The beneficial effect of this oxide layer depends on several factors, including the adherence of the surface modified layer or subsequently formed oxide layer to the disc substrate, the substrate materials, the conditions of ion beam mixing, and the environmental conditions.

Generation and Evaluation of Lunar Dust Adhesion Mitigating Materials

NASA Technical Reports Server (NTRS)

Wohl, Christopher J.; Connell, John W.; Lin, Yi; Belcher, Marcus A.; Palmieri, Frank L.

2011-01-01

Particulate contamination is of concern in a variety of environments. This issue is especially important in confined spaces with highly controlled atmospheres such as space exploration vehicles involved in extraterrestrial surface missions. Lunar dust was a significant challenge for the Apollo astronauts and will be of greater concern for longer duration, future missions. Passive mitigation strategies, those not requiring external energy, may decrease some of these concerns, and have been investigated in this work. A myriad of approaches to modify the surface chemistry and topography of a variety of substrates was investigated. These involved generation of novel materials, photolithographic techniques, and other template approaches. Additionally, single particle and multiple particle methods to quantitatively evaluate the particle-substrate adhesion interactions were developed.

Covalent Coupling of Nanoparticles with Low-Density Functional Ligands to Surfaces via Click Chemistry

PubMed Central

Rianasari, Ina; de Jong, Michel P.; Huskens, Jurriaan; van der Wiel, Wilfred G.

2013-01-01

We demonstrate the application of the 1,3-dipolar cycloaddition (“click” reaction) to couple gold nanoparticles (Au NPs) functionalized with low densities of functional ligands. The ligand coverage on the citrate-stabilized Au NPs was adjusted by the ligand:Au surface atom ratio, while maintaining the colloidal stability of the Au NPs in aqueous solution. A procedure was developed to determine the driving forces governing the selectivity and reactivity of citrate-stabilized and ligand-functionalized Au NPs on patterned self-assembled monolayers. We observed selective and remarkably stable chemical bonding of the Au NPs to the complimentarily functionalized substrate areas, even when estimating that only 1–2 chemical bonds are formed between the particles and the substrate. PMID:23434666

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

The influence of titanium adhesion layer oxygen stoichiometry on thermal boundary conductance at gold contacts

NASA Astrophysics Data System (ADS)

Olson, David H.; Freedy, Keren M.; McDonnell, Stephen J.; Hopkins, Patrick E.

2018-04-01

We experimentally demonstrate the role of oxygen stoichiometry on the thermal boundary conductance across Au/TiOx/substrate interfaces. By evaporating two different sets of Au/TiOx/substrate samples under both high vacuum and ultrahigh vacuum conditions, we vary the oxygen composition in the TiOx layer from 0 ≤ x ≤ 2.85. We measure the thermal boundary conductance across the Au/TiOx/substrate interfaces with time-domain thermoreflectance and characterize the interfacial chemistry with x-ray photoemission spectroscopy. Under high vacuum conditions, we speculate that the environment provides a sufficient flux of oxidizing species to the sample surface such that one essentially co-deposits Ti and these oxidizing species. We show that slower deposition rates correspond to a higher oxygen content in the TiOx layer, which results in a lower thermal boundary conductance across the Au/TiOx/substrate interfacial region. Under the ultrahigh vacuum evaporation conditions, pure metallic Ti is deposited on the substrate surface. In the case of quartz substrates, the metallic Ti reacts with the substrate and getters oxygen, leading to a TiOx layer. Our results suggest that Ti layers with relatively low oxygen compositions are best suited to maximize the thermal boundary conductance.

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

PubMed

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

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.

Synthesis and patterning of polymers for biomedical applications

NASA Astrophysics Data System (ADS)

He, Wei

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

Biofunctionalization on alkylated silicon substrate surfaces via "click" chemistry.

PubMed

Qin, Guoting; Santos, Catherine; Zhang, Wen; Li, Yan; Kumar, Amit; Erasquin, Uriel J; Liu, Kai; Muradov, Pavel; Trautner, Barbara Wells; Cai, Chengzhi

2010-11-24

Biofunctionalization of silicon substrates is important to the development of silicon-based biosensors and devices. Compared to conventional organosiloxane films on silicon oxide intermediate layers, organic monolayers directly bound to the nonoxidized silicon substrates via Si-C bonds enhance the sensitivity of detection and the stability against hydrolytic cleavage. Such monolayers presenting a high density of terminal alkynyl groups for bioconjugation via copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC, a "click" reaction) were reported. However, yields of the CuAAC reactions on these monolayer platforms were low. Also, the nonspecific adsorption of proteins on the resultant surfaces remained a major obstacle for many potential biological applications. Herein, we report a new type of "clickable" monolayers grown by selective, photoactivated surface hydrosilylation of α,ω-alkenynes, where the alkynyl terminal is protected with a trimethylgermanyl (TMG) group, on hydrogen-terminated silicon substrates. The TMG groups on the film are readily removed in aqueous solutions in the presence of Cu(I). Significantly, the degermanylation and the subsequent CuAAC reaction with various azides could be combined into a single step in good yields. Thus, oligo(ethylene glycol) (OEG) with an azido tag was attached to the TMG-alkyne surfaces, leading to OEG-terminated surfaces that reduced the nonspecific adsorption of protein (fibrinogen) by >98%. The CuAAC reaction could be performed in microarray format to generate arrays of mannose and biotin with varied densities on the protein-resistant OEG background. We also demonstrated that the monolayer platform could be functionalized with mannose for highly specific capturing of living targets (Escherichia coli expressing fimbriae) onto the silicon substrates.

Antibacterial Performance of Alginic Acid Coating on Polyethylene Film

PubMed Central

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

2014-01-01

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

Superhydrophobicity enhancement through substrate flexibility.

PubMed

Vasileiou, Thomas; Gerber, Julia; Prautzsch, Jana; Schutzius, Thomas M; Poulikakos, Dimos

2016-11-22

Inspired by manifestations in nature, microengineering and nanoengineering of synthetic materials to achieve superhydrophobicity has been the focus of much work. Generally, hydrophobicity is enhanced through the combined effects of surface texturing and chemistry; being durable, rigid materials are the norm. However, many natural and technical surfaces are flexible, and the resulting effect on hydrophobicity has been largely ignored. Here, we show that the rational tuning of flexibility can work synergistically with the surface microtexture or nanotexture to enhance liquid repellency performance, characterized by impalement and breakup resistance, contact time reduction, and restitution coefficient increase. Reduction in substrate areal density and stiffness imparts immediate acceleration and intrinsic responsiveness to impacting droplets (∼350 × g), mitigating the collision and lowering the impalement probability by ∼60% without the need for active actuation. Furthermore, we exemplify the above discoveries with materials ranging from man-made (thin steel or polymer sheets) to nature-made (butterfly wings).

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

NASA Technical Reports Server (NTRS)

Avni, R.; Spalvins, T.

1984-01-01

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

Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

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

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N., E-mail: gnp@ncsu.edu

2016-01-15

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less

Selective PEGylation of Parylene-C/SiO2 Substrates for Improved Astrocyte Cell Patterning.

PubMed

Raos, B J; Doyle, C S; Simpson, M C; Graham, E S; Unsworth, C P

2018-02-09

Controlling the spatial distribution of glia and neurons in in vitro culture offers the opportunity to study how cellular interactions contribute to large scale network behaviour. A recently developed approach to cell-patterning uses differential adsorption of animal-serum protein on parylene-C and SiO 2 surfaces to enable patterning of neurons and glia. Serum, however, is typically poorly defined and generates reproducibility challenges. Alternative activation methods are highly desirable to enable patterning without relying on animal serum. We take advantage of the innate contrasting surface chemistries of parylene-C and SiO 2 to enable selective bonding of polyethylene glycol SiO 2 surfaces, i.e. PEGylation, rendering them almost completely repulsive to cell adhesion. As the reagents used in the PEGylation protocol are chemically defined, the reproducibility and batch-to-batch variability complications associated with the used of animal serum are avoided. We report that PEGylated parylene-C/SiO 2 substrates achieve a contrast in astrocyte density of 65:1 whereas the standard serum-immersion protocol results in a contrast of 5.6:1. Furthermore, single-cell isolation was significantly improved on PEGylated substrates when astrocytes were grown on close-proximity parylene-C nodes, whereas isolation was limited on serum-activated substrates due tolerance for cell adhesion on serum-adsorbed SiO 2 surfaces.

Atomic Layer Deposition in Bio-Nanotechnology: A Brief Overview.

PubMed

Bishal, Arghya K; Butt, Arman; Selvaraj, Sathees K; Joshi, Bela; Patel, Sweetu B; Huang, Su; Yang, Bin; Shukohfar, Tolou; Sukotjo, Cortino; Takoudis, Christos G

2015-01-01

Atomic layer deposition (ALD) is a technique increasingly used in nanotechnology and ultrathin film deposition; it is ideal for films in the nanometer and Angstrom length scales. ALD can effectively be used to modify the surface chemistry and functionalization of engineering-related and biologically important surfaces. It can also be used to alter the mechanical, electrical, chemical, and other properties of materials that are increasingly used in biomedical engineering and biological sciences. ALD is a relatively new technique for optimizing materials for use in bio-nanotechnology. Here, after a brief review of the more widely used modes of ALD and a few of its applications in biotechnology, selected results that show the potential of ALD in bio-nanotechnology are presented. ALD seems to be a promising means for tuning the hydrophilicity/hydrophobicity characteristics of biomedical surfaces, forming conformal ultrathin coatings with desirable properties on biomedical substrates with a high aspect ratio, tuning the antibacterial properties of substrate surfaces of interest, and yielding multifunctional biomaterials for medical implants and other devices.

Rupture and Spreading Dynamics of Lipid Membranes on a Solid Surface

NASA Astrophysics Data System (ADS)

Perazzo, Antonio; Shin, Sangwoo; Colosqui, Carlos; Young, Yuan-Nan; Stone, Howard A.

2017-11-01

The spreading of lipid membranes on solid surfaces is a dynamic phenomenon relevant to drug delivery, endocytosis, biofouling, and the synthesis of supported lipid bilayers. Current technological developments are limited by an incomplete understanding of the spreading and adhesion dynamics of a lipid bilayer under different physicochemical conditions. Here, we present recent experimental and theoretical results for the spreading of giant unilamellar vesicles (GUVs), where the vesicle shell consists of a lipid bilayer. In particular, we study the effect of different background ion concentrations, osmolarity mismatches between the interior and the exterior of the vesicles, and different surface chemistries of the glass substrate. In all of the studied cases, we observe a delay time before a GUV in contact with the solid surface eventually ruptures. The rupture kinetics and subsequent spreading dynamics is controlled by the ionic screening within the thin film of liquid between the vesicle and the surface. Different rupture mechanisms, mobilities of the spreading vesicle, and degrees of substrate coverage are observed by varying the electrolyte concentration, solid surface charge, and osmolarity mismatch.

Influence of FeEDDS, FeEDTA, FeDTPA, FeEDDHA, and FeSO4 on Marigold Growth and Nutrition, and Substrate and Runoff Chemistry

USDA-ARS?s Scientific Manuscript database

Objectives of the study were to determine effects of Fe source on plant growth, plant nutrition, substrate chemistry and runoff chemistry. Iron source (FS) treatments consisted of Fe-aminopolycarboxylic acid (APCA) complexones iron ethylenediaminetetraacetic acid (FeEDTA), iron [S, S']-ethylenediam...

Effects of surface chemistry on hot corrosion life

NASA Technical Reports Server (NTRS)

Fryxell, R. E.

1985-01-01

Burner rig tests were conducted under the following conditions: 900 C, hourly thermal cycling, 0.5 ppm sodium as MaCl in the gas stream, velocity 0.3 Mach. The alloys are Udiment 700, Rene 80, uncoated and with RT21, Codep, or NiCoCrAlY coatings. These tests were completed for specimens in the as-processed condition and after aging at 1100 C in oxidizing or inert evnivronments for time up to 600 hours. Coil inductance changes used for periodic nondestructive inspection of specimens were useful in following the course of corrosion. Typical sulfidation was observed in all cases, structurally similar to that observed for service-run turbine components. Aging at cuased a severe decrease in hot corrosion life of RT21 and Codep coatings and a significant but less decrease in the life of the NiCoCrAlY coating. The extent of these decreases was much greater for all three coatings on U700 substrates than on Rene 80 substrates. Coating/substrate interdiffusion rather than by surface oxidation.

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

Metzler, Dominik; Li, Chen; Engelmann, Sebastian

With the increasing interest in establishing directional etching methods capable of atomic scale resolution for fabricating highly scaled electronic devices, the need for development and characterization of atomic layer etching (ALE) processes, or generally etch processes with atomic layer precision, is growing. In this work, a flux-controlled cyclic plasma process is used for etching of SiO 2 and Si at the Angstrom-level. This is based on steady-state Ar plasma, with periodic, precise injection of a fluorocarbon (FC) precursor (C 4F 8 and CHF 3), and synchronized, plasma-based Ar+ ion bombardment [D. Metzler et al., J Vac Sci Technol A 32,more » 020603 (2014), and D. Metzler et al., J Vac Sci Technol A 34, 01B101 (2016)]. For low energy Ar+ ion bombardment conditions, physical sputter rates are minimized, whereas material can be etched when FC reactants are present at the surface. This cyclic approach offers a large parameter space for process optimization. Etch depth per cycle, removal rates, and self-limitation of removal, along with material dependence of these aspects, were examined as a function of FC surface coverage, ion energy, and etch step length using in situ real time ellipsometry. The deposited FC thickness per cycle is found to have a strong impact on etch depth per cycle of SiO 2 and Si, but is limited with regard to control over material etching selectivity. Ion energy over the 20 to 30 eV range strongly impacts material selectivity. The choice of precursor can have a significant impact on the surface chemistry and chemically enhanced etching. CHF 3 has a lower FC deposition yield for both SiO 2 and Si, and also exhibits a strong substrate dependence of FC deposition yield, in contrast to C4F 8. The thickness of deposited FC layers using CHF 3 is found to be greater for Si than for SiO 2. X-ray photoelectron spectroscopy was used to study surface chemistry. When thicker FC films of 11 Å are employed, strong changes of FC film chemistry during a cycle are seen whereas the chemical state of the substrate varies much less. On the other hand, for FC film deposition of 5 Å for each cycle, strong substrate surface chemical changes are seen during an etching cycle. The nature of this cyclic etching with periodic deposition of thin FC films differs significantly from conventional etching with steady-state FC layers since surface conditions change strongly throughout each cycle.« less

Characterizing fluorocarbon assisted atomic layer etching of Si using cyclic Ar/C4F8 and Ar/CHF3 plasma

NASA Astrophysics Data System (ADS)

Metzler, Dominik; Li, Chen; Engelmann, Sebastian; Bruce, Robert L.; Joseph, Eric A.; Oehrlein, Gottlieb S.

2017-02-01

With the increasing interest in establishing directional etching methods capable of atomic scale resolution for fabricating highly scaled electronic devices, the need for development and characterization of atomic layer etching processes, or generally etch processes with atomic layer precision, is growing. In this work, a flux-controlled cyclic plasma process is used for etching of SiO2 and Si at the Angstrom-level. This is based on steady-state Ar plasma, with periodic, precise injection of a fluorocarbon (FC) precursor (C4F8 and CHF3) and synchronized, plasma-based Ar+ ion bombardment [D. Metzler et al., J. Vac. Sci. Technol., A 32, 020603 (2014) and D. Metzler et al., J. Vac. Sci. Technol., A 34, 01B101 (2016)]. For low energy Ar+ ion bombardment conditions, physical sputter rates are minimized, whereas material can be etched when FC reactants are present at the surface. This cyclic approach offers a large parameter space for process optimization. Etch depth per cycle, removal rates, and self-limitation of removal, along with material dependence of these aspects, were examined as a function of FC surface coverage, ion energy, and etch step length using in situ real time ellipsometry. The deposited FC thickness per cycle is found to have a strong impact on etch depth per cycle of SiO2 and Si but is limited with regard to control over material etching selectivity. Ion energy over the 20-30 eV range strongly impacts material selectivity. The choice of precursor can have a significant impact on the surface chemistry and chemically enhanced etching. CHF3 has a lower FC deposition yield for both SiO2 and Si and also exhibits a strong substrate dependence of FC deposition yield, in contrast to C4F8. The thickness of deposited FC layers using CHF3 is found to be greater for Si than for SiO2. X-ray photoelectron spectroscopy was used to study surface chemistry. When thicker FC films of 11 Å are employed, strong changes of FC film chemistry during a cycle are seen whereas the chemical state of the substrate varies much less. On the other hand, for FC film deposition of 5 Å for each cycle, strong substrate surface chemical changes are seen during an etching cycle. The nature of this cyclic etching with periodic deposition of thin FC films differs significantly from conventional etching with steady-state FC layers since surface conditions change strongly throughout each cycle.

Regenerative biomaterials that "click": simple, aqueous-based protocols for hydrogel synthesis, surface immobilization, and 3D patterning.

PubMed

Nimmo, Chelsea M; Shoichet, Molly S

2011-11-16

The click chemistry era has generated a library of versatile "spring-loaded" reactions that offer high yields, regio- and stereospecificity, and outstanding functional group tolerance. These powerful transformations are particularly advantageous for the design of sophisticated biomaterials that require high levels of precision and control, namely, materials that promote tissue regeneration such as hydrogels, 2D functionalized substrates, and 3D biomimetic scaffolds. In this review, the synthesis and application of regenerative biomaterials via click chemistry are summarized. Particular emphasis is placed on the copper(I)-catalyzed alkyne-azide cycloaddition, Diels-Alder cycloadditions, and thiol-click coupling.

Symposium on Biosensors

DTIC Science & Technology

1989-11-01

cherists because a new parameter; the refractive index of materials is an important in design as the chemistry of the absorbing or reacting layer ...redox electrode surfaces (the Sharp electrodes); use of enzymes in reactive layers to generate from neutral charge substrate species that can be...and natural and synthetic ionophores in monovalent and divalent ion sensors since 1965); use of selective layers to extract or partition species into

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

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

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

2014-03-15

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

Adjusting the surface areal density of click-reactive azide groups by kinetic control of the azide substitution reaction on bromine-functional SAMs.

PubMed

Zhang, Shuo; Maidenberg, Yanir; Luo, Kai; Koberstein, Jeffrey T

2014-06-03

Azide-alkyne click chemistry has emerged as an important and versatile means for tethering a wide variety of guest molecules to virtually any substrate. In many of these applications, it is important to exercise control over the areal density of surface functional groups to achieve a desired areal density of the tethered guest molecule of interest. We demonstrate herein that the areal density of surface azide groups on flat germanium surfaces and nanoparticle substrates (silica and iron oxide) can be controlled kinetically by appropriately timed quenching of the S(N)2 substitution reaction of bromo-alkane-silane monolayers induced by the addition of sodium azide. The kinetics of the azide substitution reaction on monolayers formed on flat Ge substrates, determined by attenuated total reflection infrared spectroscopy (ATR-IR), are found to be identical to those for monolayers formed on both silica and iron oxide nanoparticles, the latter determined by transmission infrared spectroscopy. To validate the method, the percentages of surface bromine groups converted to azide groups after various reaction times were measured by quenching the S(N)2 reaction followed by analysis with ATR-IR (for Ge) and thermogravimetric analysis (after a subsequent click reaction with an alkyne-terminal polymer) for the nanoparticle substrates. The conversions found after quenching agree well with those expected from the standard kinetic curves. The latter result suggests that the kinetic method for the control of azide group areal density is a versatile means for functionalizing substrates with a prescribed areal density of azide groups for subsequent click reactions, and that the method is universal for any substrate, flat or nanoparticle, that can be modified with bromo-alkane-silane monolayers. Regardless of the surface geometry, we find that the azide substitution reaction is complete within 2-3 h, in sharp contrast to previous reports that indicate times of 48-60 h required for completion of the reaction.

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

PubMed

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

2018-01-15

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

Ecosystem and physiological controls over methane production in northern wetlands

NASA Technical Reports Server (NTRS)

Valentine, David W.; Holland, Elisabeth A.; Schimel, David S.

1994-01-01

Peat chemistry appears to exert primary control over methane production rates in the Canadian Northern Wetlands Study (NOWES) area. We determined laboratory methane production rate potentials in anaerobic slurries of samples collected from a transect of sites through the NOWES study area. We related methane production rates to indicators of resistance to microbial decay (peat C: N and lignin: N ratios) and experimentally manipulated substrate availability for methanogenesis using ethanol (EtOH) and plant litter. We also determined responses of methane production to pH and temperature. Methane production potentials declined along the gradient of sites from high rates in the coastal fens to low rates in the interior bogs and were generally highest in surface layers. Strong relationships between CH4 production potentials and peat chemistry suggested that methanogenesis was limited by fermentation rates. Methane production at ambient pH responded strongly to substrate additions in the circumneutral fens with narrow lignin: N and C: N ratios (delta CH4/delta EtOH = 0.9-2.3 mg/g) and weakly in the acidic bogs with wide C: N and lignin: N ratios (delta CH4/delta EtOH = -0.04-0.02 mg/g). Observed Q(sub 10) values ranged from 1.7 to 4.7 and generally increased with increasing substrate availability, suggesting that fermentation rates were limiting. Titration experiments generally demonstrated inhibition of methanogenesis by low pH. Our results suggest that the low rates of methane emission observed in interior bogs during NOWES likely resulted from pH and substrate quality limitation of the fermentation step in methane production and thus reflect intrinsically low methane production potentials. Low methane emission rates observed during NOWES will likely be observed in other northern wetland regions with similar vegetation chemistry.

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

PubMed

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

2017-01-27

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Wrinkling and Folding on Patched Elastic Surfaces: Modulation of the Chemistry and Pattern Size of Microwrinkled Surfaces.

PubMed

Nogales, Aurora; Del Campo, Adolfo; Ezquerra, Tiberio A; Rodriguez-Hernández, Juan

2017-06-14

An unconventional strategy is proposed that takes advantage of localized high-deformation areas, referred to as folded wrinkles, to produce microstructured elastic surfaces with precisely controlled pattern dimensions and chemical distribution. For that purpose, elastic PDMS substrates were prestretched to a different extent and oxidized in particular areas using a mask. When the stretching was removed, the PDMS substrate exhibited out-of-plane deformations that largely depend on the applied prestretching. Prestretchings below 100% lead to affine deformations in which the treated areas are buckled. On the contrary, prestretchings above ε >100% prior to surface treatment induce the formation of folded wrinkles on those micrometer-size ultraviolet-ozone (UVO) treated areas upon relaxation. As a result, dual periodic wrinkles were formed due to the alternation of highly deformed (folded) and low deformed (buckled) areas. Our strategy is based on the surface treatment at precise positions upon prestretching of the elastic substrate (PDMS). Additionally, this approach can be used to template the formation of wrinkled surfaces by alternating lines of folded wrinkles (valleys) and low-deformed areas (hills). This effect allowed us to precisely tune the shape and distribution of the UVO exposed areas by varying the prestretching direction. Moreover, the wrinkle characteristics, including period and amplitude, exhibit a direct relation to the dimensions of the patterns present in the mask.

Thumbnail Sketches: The Chemistry of Printed Circuit Substrates: Some of the Latest Developments.

ERIC Educational Resources Information Center

Freeman, James H.

1984-01-01

Discusses some of the latest developments in the chemistry of printed circuit substrates. Topics considered include soldering, dicy (a catalyst), Kevlar (an aramid polymer fiber), maleimide copolymers, and flexible circuits. (JN)

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.

Temperature and substrate chemistry as major drivers of interregional variability of leaf microbial decomposition and cellulolytic activity in headwater streams.

PubMed

Fenoy, Encarnación; Casas, J Jesús; Díaz-López, Manuel; Rubio, Juan; Guil-Guerrero, J Luís; Moyano-López, Francisco J

2016-11-01

Abiotic factors, substrate chemistry and decomposers community composition are primary drivers of leaf litter decomposition. In soil, much of the variation in litter decomposition is explained by climate and substrate chemistry, but with a significant contribution of the specialisation of decomposer communities to degrade specific substrates (home-field advantage, HFA). In streams, however, HFA effects on litter decomposition have not been explicitly tested. We evaluated responses of microbial decomposition and β-glucosidase activity to abiotic factors, substrate and decomposer assemblages, using a reciprocal litter transplant experiment: 'ecosystem type' (mountain vs lowland streams) × 'litter chemistry' (alder vs reed). Temperature, pH and ionic concentration were higher in lowland streams. Decomposition for both species was faster in lowland streams. Decomposition of reed was more accelerated in lowland compared with mountain streams than that of alder, suggesting higher temperature sensitivity of decomposition in reed. Q10 (5°C-15°C) values of β-glucosidase activity were over 2. The alkaline pH and high ionic concentration of lowland streams depleted enzyme activity. We found similar relationships of decomposition or enzyme activity with abiotic factors for both species, suggesting limited support to the HFA hypothesis. Overall, our results suggest a prime role of temperature interacting with substrate chemistry on litter decomposition. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Ultra-thin Polyethylene glycol Coatings for Stem Cell Culture

NASA Astrophysics Data System (ADS)

Schmitt, Samantha K.

Human mesenchymal stem cells (hMSCs) are a widely accessible and a clinically relevant cell type that are having a transformative impact on regenerative medicine. However, current clinical expansion methods can lead to selective changes in hMSC phenotype resulting from relatively undefined cell culture surfaces. Chemically defined synthetic surfaces can aid in understanding stem cell behavior. In particular we have developed chemically defined ultra-thin coatings that are stable over timeframes relevant to differentiation of hMSCs (several weeks). The approach employs synthesis of a copolymer with distinct chemistry in solution before application to a substrate. This provides wide compositional flexibility and allows for characterization of the orthogonal crosslinking and peptide binding groups. Characterization is done in solution by proton NMR and after crosslinking by X-ray photoelectron spectroscopy (XPS). The solubility of the copolymer in ethanol and low temperature crosslinking, expands its applicability to plastic substrates, in addition to silicon, glass, and gold. Cell adhesive peptides, namely Arg-Gly-Asp (RGD) fragments, are coupled to coating via different chemistries resulting in the urethane, amide or the thioester polymer-peptide bonds. Development of azlactone-based chemistry allowed for coupling in water at low peptide concentrations and resulted in either an amide or thioester bonds, depending on reactants. Characterization of the peptide functionalized coating by XPS, infrared spectroscopy and cell culture assays, showed that the amide linkages can present peptides for multiple weeks, while shorter-term presentation of a few days is possible using the more labile thioester bond. Regardless, coatings promoted initial adhesion and spreading of hMSCs in a peptide density dependent manner. These coatings address the following challenges in chemically defined cell culture simultaneously: (i) substrate adaptability, (ii) scalability over large areas, (ii) quantification of peptides, (iv) chemically defined passage of hMSCs, (v) stability of peptide-polymer bonds, and (vi) long-term coating stability. These coating platforms can potentially elucidate cell-material interactions in vitro and have far-reaching effects on stem cell culture methods.

Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

PubMed

Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

2018-04-11

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

Modifying surface resistivity and liquid moisture management property of keratin fibers through thiol-ene click reactions.

PubMed

Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

2014-01-22

This paper reports on a new method for improving the antistatic and liquid moisture management properties of keratinous materials. The method involves the generation of thiols by controlled reduction of cystine disulfide bonds in keratin with tris(2-carboxyethyl) phosphine hydrochloride and subsequent grafting of hydrophilic groups onto the reduced keratin by reaction with an acrylate sulfonate or acrylamide sulfonate through thiol-ene click chemistry. The modified substrates were characterized with Raman spectroscopy and scanning electron microscopy and evaluated for their performance changes in liquid moisture management, surface resistivity, and wet burst strength. The results have revealed that the thiol-acrylate reaction is more efficient than the thiol-acrylamide reaction, and the keratinous substrate modified with an acrylate sulfonate salt exhibits significantly improved antistatic and liquid moisture management properties.

Pulsed laser deposition of plasmonic nanostructured gold on flexible transparent polymers at atmospheric pressure

NASA Astrophysics Data System (ADS)

McCann, Ronán; Hughes, Cian; Bagga, Komal; Stalcup, Apryll; Vázquez, Mercedes; Brabazon, Dermot

2017-06-01

In this paper, we outline a novel technique for the deposition of nanostructured thin films utilizing a modified form of pulsed laser deposition (PLD). We demonstrate confined atmospheric PLD (CAP) for the deposition of gold on cyclic olefin polymer substrates. The deposition process is a simplified form of conventional PLD, with deposition conducted under atmospheric conditions and the substrate and target in close proximity. It was found that this confinement results in the deposition of nanostructured thin films on the substrate. Infrared spectroscopy showed no significant change of polymer surface chemistry as a result of the deposition process, and optical spectroscopy revealed plasmonic behavior of the resulting thin film. The effect of laser fluence on the deposition process was also examined with more uniform films deposited at higher fluences.

Effect of Surface Curvature and Chemistry on Protein Stability, Adsorption and Aggregation

NASA Astrophysics Data System (ADS)

Radhakrishna, Mithun

Enzyme immobilization has been of great industrial importance because of its use in various applications like bio-fuel cells, bio-sensors, drug delivery and bio-catalytic films. Although research on enzyme immobilization dates back to the 1970's, it has been only in the past decade that scientists have started to address the problems involved systematically. Most of the previous works on enzyme immobilization have been retrospective in nature i.e enzymes were immobilized on widely used substrates without a compatibility study between the enzyme and the substrate. Consequently, most of the enzymes lost their activity upon immobilization onto these substrates due to many governing factors like protein-surface and inter-protein interactions. These interactions also play a major role biologically in cell signaling, cell adhesion and inter-protein interactions specifically is believed to be the major cause for neurodegenerative diseases like Alzheimer's and Parkinson's disease. Therefore understanding the role of these forces on proteins is the need of the hour. In my current research, I have mainly focused on two factors a) Surface Curvature b) Surface Chemistry as both of these play a pivotal role in influencing the activity of the enzymes upon immobilization. I study the effect of these factors computationally using a stochastic method known as Monte Carlo simulations. My research work carried out in the frame work of a Hydrophobic-Polar (HP) lattice model for the protein shows that immobilizing enzymes inside moderately hydrophilic or hydrophobic pores results in an enhancement of the enzymatic activity compared to that in the bulk. Our results also indicate that there is an optimal value of surface curvature and hydrophobicity/hydrophilicity where this enhancement of enzymatic activity is highest. Further, our results also show that immobilization of enzymes inside hydrophobic pores of optimal sizes are most effective in mitigating protein-aggregation. These results provide us a rationale to understand the role of chaperonins in protein folding and disaggregation. Our results indicate that strong protein-surface interactions and confinement inducement stability inside pores makes it best suitable for enzyme immobilization.

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.

High-Performance, Large Format Surfaces for Surface-Enhanced Raman Spectroscopy: Increasing the Accessibility of an Analytical Platform

NASA Astrophysics Data System (ADS)

Kanipe, Katherine Nicole

Although surface-enhanced Raman spectroscopy (SERS) is a spectroscopic technique with unusually high sensitivity and molecular specificity, few practical analytical applications have been implemented that take advantage of its power. Based on what is understood about SERS from the experimental and theoretical research of the past forty years, we developed a few well-defined design principles on the basis of which a reliable and reproducibly manufacturable SERS-active substrate could be fabricated that is highly enhancing, highly uniform, stable, and based on a broad range of metals so that various chemical processes could be probed. Finally, we restricted ourselves to using only readily scalable fabrication techniques. The resulting SERS-active device was a metal over silica, two-dimensional nano-grating that was shown to produce enhancements of ˜107 when compared to a smooth surface of the same metal. This SERS substrate also shows unprecedented signal uniformity over square centimeters, and is fabricated using commonly-available foundry-based approaches exclusively. Initially, we explored the properties of a gold-coated substrates in which a first-order grating resonance due to long-range symmetry is augmented by a local resonance due to the individual core-shell grating elements. The SERS properties of such grating systems were systematically studied as a function of various structural parameters such as the grating pitch, the inter-element gap and the thickness of the metal layer. The most enhancing substrates were found to have a grating parameter with a radiative, rather than evanescent, first-order resonance; a sufficiently small gap between nearest neighbor grating elements to produce near-field interactions; and a gold layer whose thickness was larger than the electronic mean-free-path of the conduction electrons, so as to ensure a high conductivity for the metal layer to sustain strong surface plasmons. We applied these same architectural principles to metals other than gold, and concluded that every workable metal (and virtually any material with sufficiently high electrical conductivity) when appropriately nanostructured, has the potential to be an efficient SERS substrate. The use of materials for SERS beyond silver and gold, has significant advantages, most importantly, allowing SERS to be used to study the surface chemistry and catalysis taking place on metals with more interesting chemistries than those of Au and Ag. Additionally, SERS substrates can be fabricated from high natural abundance, low cost materials. This was illustrated by producing SERS substrates using copper, aluminum, and nickel in addition to silver and gold which were used as benchmarks. All five metals were found to yield high SERS intensities. The variation of the SERS enhancement among them is ascribed mainly to local field effects, with the (larger) grating-based enhancement making an approximately equivalent contribution to the SERS enhancement of the five metals. This conclusion is supported by local electric field simulations. The utility of these new grating-based SERS substrates was demonstrated by implementing them in chemical analysis in both aqueous and gas phases for which, for example, we were able to readily detect opioids such as fentanyl and morphine at concentrations as low as less than one part per billion. Additionally, we have made good progress toward integration of this substrate architecture into a microfluidic channel for a higher degree of sample workup and control.

Metal-dielectric interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Superficial physicochemical properties of polyurethane biomaterials as osteogenic regulators in human mesenchymal stem cells fates.

PubMed

Shahrousvand, Mohsen; Sadeghi, Gity Mir Mohamad; Shahrousvand, Ehsan; Ghollasi, Marzieh; Salimi, Ali

2017-08-01

All of the cells' interactions are done through their surfaces. Evaluation of surface physicochemical scaffolds along with other factors is important and determines the fate of stem cells. In this work, biodegradable and biocompatible polyester/polyether based polyurethanes (PUs) were synthesized by polycaprolactone diol (PCL) and poly (tetra methylene ether) glycol (PTMEG) as the soft segment. To assess better the impact of surface parameters such as stiffness and roughness effects on osteogenic differentiation of the human mesenchymal stem cell (hMSC), the dimension effect of substrates was eliminated and two-dimensional membranes were produced by synthesized polyurethane. Surface and bulk properties of prepared 2D membranes such as surface chemistry, roughness, stiffness and tensile behavior were evaluated by Attenuated total reflectance Fourier transform infrared (ATR-FTIR), atomic force microscopy (AFM) and tensile behavior. The prepared 2D PU films had suitable hydrophilicity, biodegradability, water absorption, surface roughness and bulk strength. The hMSCs showed greater osteogenesis expression in PU substrates with more roughness and stiffness than others. The results demonstrated that surface parameters along with other differentiation cues have a synergistic effect on stem cells fates. Copyright © 2017 Elsevier B.V. All rights reserved.

Polarity Control of Heteroepitaxial GaN Nanowires on Diamond.

PubMed

Hetzl, Martin; Kraut, Max; Hoffmann, Theresa; Stutzmann, Martin

2017-06-14

Group III-nitride materials such as GaN nanowires are characterized by a spontaneous polarization within the crystal. The sign of the resulting sheet charge at the top and bottom facet of a GaN nanowire is determined by the orientation of the wurtzite bilayer of the different atomic species, called N and Ga polarity. We investigate the polarity distribution of heteroepitaxial GaN nanowires on different substrates and demonstrate polarity control of GaN nanowires on diamond. Kelvin Probe Force Microscopy is used to determine the polarity of individual selective area-grown and self-assembled nanowires over a large scale. At standard growth conditions, mixed polarity occurs for selective GaN nanowires on various substrates, namely on silicon, on sapphire and on diamond. To obtain control over the growth orientation on diamond, the substrate surface is modified by nitrogen and oxygen plasma exposure prior to growth, and the growth parameters are adjusted simultaneously. We find that the surface chemistry and the substrate temperature are the decisive factors for obtaining control of up to 93% for both polarity types, whereas the growth mode, namely selective area or self-assembled growth, does not influence the polarity distribution significantly. The experimental results are discussed by a model based on the interfacial bonds between the GaN nanowires, the termination layer, and the substrate.

Temperature dependent droplet impact dynamics on flat and textured surfaces

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

Azar Alizadeh; Vaibhav Bahadur; Sheng Zhong

Droplet impact dynamics determines the performance of surfaces used in many applications such as anti-icing, condensation, boiling and heat transfer. We study impact dynamics of water droplets on surfaces with chemistry/texture ranging from hydrophilic to superhydrophobic and across a temperature range spanning below freezing to near boiling conditions. Droplet retraction shows very strong temperature dependence especially for hydrophilic surfaces; it is seen that lower substrate temperatures lead to lesser retraction. Physics-based analyses show that the increased viscosity associated with lower temperatures can explain the decreased retraction. The present findings serve to guide further studies of dynamic fluid-structure interaction at variousmore » temperatures.« less

Hierarchical roughness of sticky and non-sticky superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Raza, Muhammad Akram; Kooij, Stefan; van Silfhout, Arend; Zandvliet, Harold; Poelsema, Bene; Physics Of Interfaces; Nanomaterials Team

2011-03-01

The importance of superhydrophobic substrates (contact angle > 150 r withslidingangle 10 r) inmoderntechnologyisundeniable . Wepresentasimplecolloidalroutetomanufacturesuperstructuredarrayswithsingle - andmulti - length - scaledroughnesstoobtainstickyandnon - stickysuperhydrophobicsurfaces . Thelargestlengthscaleisprovidedby (multi -) layersofsilicaspheres (1 μ m, 500nm and 150nm diameter). Decoration with gold nanoparticles (14nm, 26nm and 47nm) gives rise to a second length scale. To lower the surface energy, gold nanoparticles are functionalized with dodecanethiol and the silica spheres by perfluorooctyltriethoxysilane. The morphology was examined by helium ion microscopy (HIM), while wettability measurements were performed by using the sessile drop method. We conclude that wettability can be controlled by changing the surface chemistry and/or length scales of the structures. To achieve truly non-sticky superhydrophobic surfaces, hierarchical roughness plays a vital role.

Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography

NASA Astrophysics Data System (ADS)

Wang, Qing Hua; Jin, Zhong; Kim, Ki Kang; Hilmer, Andrew J.; Paulus, Geraldine L. C.; Shih, Chih-Jen; Ham, Moon-Ho; Sanchez-Yamagishi, Javier D.; Watanabe, Kenji; Taniguchi, Takashi; Kong, Jing; Jarillo-Herrero, Pablo; Strano, Michael S.

2012-09-01

Graphene has exceptional electronic, optical, mechanical and thermal properties, which provide it with great potential for use in electronic, optoelectronic and sensing applications. The chemical functionalization of graphene has been investigated with a view to controlling its electronic properties and interactions with other materials. Covalent modification of graphene by organic diazonium salts has been used to achieve these goals, but because graphene comprises only a single atomic layer, it is strongly influenced by the underlying substrate. Here, we show a stark difference in the rate of electron-transfer reactions with organic diazonium salts for monolayer graphene supported on a variety of substrates. Reactions proceed rapidly for graphene supported on SiO2 and Al2O3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces, as shown by Raman spectroscopy. We also develop a model of reactivity based on substrate-induced electron-hole puddles in graphene, and achieve spatial patterning of chemical reactions in graphene by patterning the substrate.

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

DOE PAGES

Huang, Lu; Tian, Mengkun; Wu, Dong; ...

2017-11-24

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Surface Mechanoengineering of a Zr-based Bulk Metallic Glass via Ar-Nanobubble Doping to Probe Cell Sensitivity to Rigid Materials

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

Huang, Lu; Tian, Mengkun; Wu, Dong

In this paper, a new materials platform, utilizing the amorphous microstructure of bulk metallic glasses (BMGs) and the versatility of ion implantation, was developed for the fundamental investigation of cell responses to substrate-rigidity variations in the gigapascal modulus range, which was previously unattainable with polymeric materials. The surface rigidity of a Zr-Al- Ni-Cu-Y BMG was modulated with low-energy Ar-ion implantation owing to the impartment of Ar nanobubbles into the amorphous matrix. Surface softening was achieved due to the formation of nanobubble-doped transitional zones in the Zrbased BMG substrate. Bone-forming cell studies on this newly designed platform demonstrated that mechanical cues,more » accompanied with the potential effects of other surface properties (i.e. roughness, morphology, and chemistry), contributed to modulating cell behaviors. Cell adhesion and actin filaments were found to be less established on less stiff surfaces, especially on the surface with an elastic modulus of 51 GPa. Cell growth appeared to be affected by surface mechanical properties. A lower stiffness was generally related to a higher growth rate. Findings in this study broadened our fundamental understanding concerning the mechanosensing of bone cells on stiff substrates. It also suggests that surface mechano-engineering of metallic materials could be a potential strategy to promote osseointegration of such materials for bone-implant applications. Further investigations are proposed to fine tune the ion implantation variables in order to further distinguish the surface-mechanical effect on bone-forming cell activities from the contributions of other surface properties.« less

Ferroelectric based catalysis: Switchable surface chemistry

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2015-03-01

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

Plasma Amino Acid Coatings for a Conformal Growth of Titania Nanoparticles

DTIC Science & Technology

2010-04-01

of dry nitrogen. Periodic porous polymer SU8 templates fabricated using multi-beam IL according to published procedures have been supplied by Thomas...3D periodic polymer structures via plasma enhanced chemical vapor deposition. We demonstrate the efficient utilization of this functional amino acid...nanoparticles were grown directly on histidine-functionalized planar and 3D polymer substrates by a wet-chemistry method that showed uniform surface

Plasma Processing of Metallic and Semiconductor Thin Films in the Fisk Plasma Source

NASA Technical Reports Server (NTRS)

Lampkin, Gregory; Thomas, Edward, Jr.; Watson, Michael; Wallace, Kent; Chen, Henry; Burger, Arnold

1998-01-01

The use of plasmas to process materials has become widespread throughout the semiconductor industry. Plasmas are used to modify the morphology and chemistry of surfaces. We report on initial plasma processing experiments using the Fisk Plasma Source. Metallic and semiconductor thin films deposited on a silicon substrate have been exposed to argon plasmas. Results of microscopy and chemical analyses of processed materials are presented.

Chemical Evolution of Interstellar Methanol Ice Analogs upon Ultraviolet Irradiation: The Role of the Substrate

NASA Astrophysics Data System (ADS)

Ciaravella, A.; Jiménez-Escobar, A.; Cosentino, G.; Cecchi-Pestellini, C.; Peres, G.; Candia, R.; Collura, A.; Barbera, M.; Di Cicca, G.; Varisco, S.; Venezia, A. M.

2018-05-01

An important issue in the chemistry of interstellar ices is the role of dust materials. In this work, we study the effect of an amorphous water-rich magnesium silicate deposited onto ZnSe windows on the chemical evolution of ultraviolet-irradiated methanol ices. For comparison, we also irradiate similar ices deposited onto bare ZnSe windows. Silicates are produced at relatively low temperatures exploiting a sol–gel technique. The chemical composition of the synthesized material reflects the forsterite stoichiometry. Si–OH groups and magnesium carbonates are incorporated during the process. The results show that the substrate material does affect the chemical evolution of the ice. In particular, the CO2/CO ratio within the ice is larger for methanol ices deposited onto the silicate substrate as a result of concurrent effects: the photolysis of carbonates present in the adopted substrate as a source of CO2, CO, and carbon and oxygen atoms; reactions of water molecules and hydroxyl radicals released from the substrate with the CO formed in the ice by the photolysis of the methanol ice; and changes in the structure and energy of the silicate surface by ultraviolet irradiation, leading to more favorable conditions for chemical reactions or catalysis at the grain surface. The results of our experiments allow such chemical effects contributed by the various substrate material components to be disentangled.

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

PubMed Central

Yáñez-Sedeño, Paloma

2018-01-01

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

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

PubMed

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

2018-02-24

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

Water at surfaces with tunable surface chemistries

NASA Astrophysics Data System (ADS)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Design of Microstructured Conducting Polymer Films for Enhanced Trace Explosives Detection

NASA Astrophysics Data System (ADS)

Laster, Jennifer S.

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

Hydrophobic fluorescent probes introduce artifacts into single molecule tracking experiments due to non-specific binding.

PubMed

Zanetti-Domingues, Laura C; Tynan, Christopher J; Rolfe, Daniel J; Clarke, David T; Martin-Fernandez, Marisa

2013-01-01

Single-molecule techniques are powerful tools to investigate the structure and dynamics of macromolecular complexes; however, data quality can suffer because of weak specific signal, background noise and dye bleaching and blinking. It is less well-known, but equally important, that non-specific binding of probe to substrates results in a large number of immobile fluorescent molecules, introducing significant artifacts in live cell experiments. Following from our previous work in which we investigated glass coating substrates and demonstrated that the main contribution to this non-specific probe adhesion comes from the dye, we carried out a systematic investigation of how different dye chemistries influence the behaviour of spectrally similar fluorescent probes. Single-molecule brightness, bleaching and probe mobility on the surface of live breast cancer cells cultured on a non-adhesive substrate were assessed for anti-EGFR affibody conjugates with 14 different dyes from 5 different manufacturers, belonging to 3 spectrally homogeneous bands (491 nm, 561 nm and 638 nm laser lines excitation). Our results indicate that, as well as influencing their photophysical properties, dye chemistry has a strong influence on the propensity of dye-protein conjugates to adhere non-specifically to the substrate. In particular, hydrophobicity has a strong influence on interactions with the substrate, with hydrophobic dyes showing much greater levels of binding. Crucially, high levels of non-specific substrate binding result in calculated diffusion coefficients significantly lower than the true values. We conclude that the physic-chemical properties of the dyes should be considered carefully when planning single-molecule experiments. Favourable dye characteristics such as photostability and brightness can be offset by the propensity of a conjugate for non-specific adhesion.

Hydrophobic Fluorescent Probes Introduce Artifacts into Single Molecule Tracking Experiments Due to Non-Specific Binding

PubMed Central

Rolfe, Daniel J.; Clarke, David T.; Martin-Fernandez, Marisa

2013-01-01

Single-molecule techniques are powerful tools to investigate the structure and dynamics of macromolecular complexes; however, data quality can suffer because of weak specific signal, background noise and dye bleaching and blinking. It is less well-known, but equally important, that non-specific binding of probe to substrates results in a large number of immobile fluorescent molecules, introducing significant artifacts in live cell experiments. Following from our previous work in which we investigated glass coating substrates and demonstrated that the main contribution to this non-specific probe adhesion comes from the dye, we carried out a systematic investigation of how different dye chemistries influence the behaviour of spectrally similar fluorescent probes. Single-molecule brightness, bleaching and probe mobility on the surface of live breast cancer cells cultured on a non-adhesive substrate were assessed for anti-EGFR affibody conjugates with 14 different dyes from 5 different manufacturers, belonging to 3 spectrally homogeneous bands (491 nm, 561 nm and 638 nm laser lines excitation). Our results indicate that, as well as influencing their photophysical properties, dye chemistry has a strong influence on the propensity of dye-protein conjugates to adhere non-specifically to the substrate. In particular, hydrophobicity has a strong influence on interactions with the substrate, with hydrophobic dyes showing much greater levels of binding. Crucially, high levels of non-specific substrate binding result in calculated diffusion coefficients significantly lower than the true values. We conclude that the physic-chemical properties of the dyes should be considered carefully when planning single-molecule experiments. Favourable dye characteristics such as photostability and brightness can be offset by the propensity of a conjugate for non-specific adhesion. PMID:24066121

Effect of Surface Chemistry on the Fluorescence of Detonation Nanodiamonds.

PubMed

Reineck, Philipp; Lau, Desmond W M; Wilson, Emma R; Fox, Kate; Field, Matthew R; Deeleepojananan, Cholaphan; Mochalin, Vadym N; Gibson, Brant C

2017-11-28

Detonation nanodiamonds (DNDs) have unique physical and chemical properties that make them invaluable in many applications. However, DNDs are generally assumed to show weak fluorescence, if any, unless chemically modified with organic molecules. We demonstrate that detonation nanodiamonds exhibit significant and excitation-wavelength-dependent fluorescence from the visible to the near-infrared spectral region above 800 nm, even without the engraftment of organic molecules to their surfaces. We show that this fluorescence depends on the surface functionality of the DND particles. The investigated functionalized DNDs, produced from the same purified DND as well as the as-received polyfunctional starting material, are hydrogen, hydroxyl, carboxyl, ethylenediamine, and octadecylamine-terminated. All DNDs are investigated in solution and on a silicon wafer substrate and compared to fluorescent high-pressure high-temperature nanodiamonds. The brightest fluorescence is observed from octadecylamine-functionalized particles and is more than 100 times brighter than the least fluorescent particles, carboxylated DNDs. The majority of photons emitted by all particle types likely originates from non-diamond carbon. However, we locally find bright and photostable fluorescence from nitrogen-vacancy centers in diamond in hydrogenated, hydroxylated, and carboxylated detonation nanodiamonds. Our results contribute to understanding the effects of surface chemistry on the fluorescence of DNDs and enable the exploration of the fluorescent properties of DNDs for applications in theranostics as nontoxic fluorescent labels, sensors, nanoscale tracers, and many others where chemically stable and brightly fluorescent nanoparticles with tailorable surface chemistry are needed.

Surface chemistry of liquid metals

NASA Technical Reports Server (NTRS)

Mann, J. Adin, Jr.; Peebles, Henry; Peebles, Diamond; Rye, Robert; Yost, Fred

1993-01-01

The fundamental surface chemistry of the behavior of liquid metals spreading on a solid substrate is not at all well understood. Each of these questions involves knowing the details of the structure of interfaces and their dynamics. For example the structure of a monolayer of tin oxide on pure liquid tin is unknown. This is in contrast to the relatively large amount of data available on the structure of copper oxide monolayers on solid, pure copper. However, since liquid tin has a vapor pressure below 10(exp -10)torr for a reasonable temperature range above its melting point, it is possible to use the techniques of surface science to study the geometric, electronic and vibrational structures of these monolayers. In addition, certain techniques developed by surface chemists for the study of liquid systems can be applied to the ultra-high vacuum environment. In particular we have shown that light scattering spectroscopy can be used to study the surface tension tensor of these interfaces. The tin oxide layer in particular is very interesting in that the monolayer is rigid but admits of bending. Ellipsometric microscopy allows the visualization of monolayer thick films and show whether island formation occurs at various levels of dosing.

Direct monolithic integration of vertical single crystalline octahedral molecular sieve nanowires on silicon

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

Carretero-Genevrier, Adrian; Oro-Sole, Judith; Gazquez, Jaume

2013-12-13

We developed an original strategy to produce vertical epitaxial single crystalline manganese oxide octahedral molecular sieve (OMS) nanowires with tunable pore sizes and compositions on silicon substrates by using a chemical solution deposition approach. The nanowire growth mechanism involves the use of track-etched nanoporous polymer templates combined with the controlled growth of quartz thin films at the silicon surface, which allowed OMS nanowires to stabilize and crystallize. α-quartz thin films were obtained after thermal activated crystallization of the native amorphous silica surface layer assisted by Sr 2+- or Ba 2+-mediated heterogeneous catalysis in the air at 800 °C. These α-quartzmore » thin films work as a selective template for the epitaxial growth of randomly oriented vertical OMS nanowires. Furthermore, the combination of soft chemistry and epitaxial growth opens new opportunities for the effective integration of novel technological functional tunneled complex oxides nanomaterials on Si substrates.« less

Performance evaluations of oxidation-resistant carbon-carbon composites in simulated hypersonic vehicle environments

NASA Technical Reports Server (NTRS)

Barrett, D. M.; Maahs, H. G.; Ohlhorst, C. W.; Vaughn, W. L.; Martin, R. H.

1989-01-01

An evaluation is made of the oxidation-protection requirements of carbon-carbon composite (CCC) structural components in a hypersonic vehicle aerothermodynamic environment, where maximum test temperatures in air are of the order of 2800 F, and pressures range from 0.03 to 1.0 atm. The specimens were exposed to high humidity between tests. Attention was given to the effects of coating composition and thickness, and of substrate architecture and surface preparation, on the oxidation resistance of CCCs. Both surface preparation and coating chemistry have a profound effect on coating adherence and longevity.

Characterizing Fluorocarbon Assisted Atomic Layer Etching of Si Using Cyclic Ar/C 4F 8 and Ar/CHF 3 Plasma

DOE PAGES

Metzler, Dominik; Li, Chen; Engelmann, Sebastian; ...

2016-09-08

With the increasing interest in establishing directional etching methods capable of atomic scale resolution for fabricating highly scaled electronic devices, the need for development and characterization of atomic layer etching (ALE) processes, or generally etch processes with atomic layer precision, is growing. In this work, a flux-controlled cyclic plasma process is used for etching of SiO 2 and Si at the Angstrom-level. This is based on steady-state Ar plasma, with periodic, precise injection of a fluorocarbon (FC) precursor (C 4F 8 and CHF 3), and synchronized, plasma-based Ar+ ion bombardment [D. Metzler et al., J Vac Sci Technol A 32,more » 020603 (2014), and D. Metzler et al., J Vac Sci Technol A 34, 01B101 (2016)]. For low energy Ar+ ion bombardment conditions, physical sputter rates are minimized, whereas material can be etched when FC reactants are present at the surface. This cyclic approach offers a large parameter space for process optimization. Etch depth per cycle, removal rates, and self-limitation of removal, along with material dependence of these aspects, were examined as a function of FC surface coverage, ion energy, and etch step length using in situ real time ellipsometry. The deposited FC thickness per cycle is found to have a strong impact on etch depth per cycle of SiO 2 and Si, but is limited with regard to control over material etching selectivity. Ion energy over the 20 to 30 eV range strongly impacts material selectivity. The choice of precursor can have a significant impact on the surface chemistry and chemically enhanced etching. CHF 3 has a lower FC deposition yield for both SiO 2 and Si, and also exhibits a strong substrate dependence of FC deposition yield, in contrast to C4F 8. The thickness of deposited FC layers using CHF 3 is found to be greater for Si than for SiO 2. X-ray photoelectron spectroscopy was used to study surface chemistry. When thicker FC films of 11 Å are employed, strong changes of FC film chemistry during a cycle are seen whereas the chemical state of the substrate varies much less. On the other hand, for FC film deposition of 5 Å for each cycle, strong substrate surface chemical changes are seen during an etching cycle. The nature of this cyclic etching with periodic deposition of thin FC films differs significantly from conventional etching with steady-state FC layers since surface conditions change strongly throughout each cycle.« less

Scalable transfer of vertical graphene nanosheets for flexible supercapacitor applications

NASA Astrophysics Data System (ADS)

Sahoo, Gopinath; Ghosh, Subrata; Polaki, S. R.; Mathews, Tom; Kamruddin, M.

2017-10-01

Vertical graphene nanosheets (VGN) are the material of choice for application in next-generation electronic devices. The growing demand for VGN-based flexible devices for the electronics industry brings in restriction on VGN growth temperature. The difficulty associated with the direct growth of VGN on flexible substrates can be overcome by adopting an effective strategy of transferring the well-grown VGN onto arbitrary flexible substrates through a soft chemistry route. In the present study, we report an inexpensive and scalable technique for the polymer-free transfer of VGN onto arbitrary substrates without disrupting its morphology, structure, and properties. After transfer, the morphology, chemical structure, and electrical properties are analyzed by scanning electron microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, and four-probe resistive methods, respectively. The wetting properties are studied from the water contact angle measurements. The observed results indicate the retention of morphology, surface chemistry, structure, and electronic properties. Furthermore, the storage capacity of the transferred VGN-based binder-free and current collector-free flexible symmetric supercapacitor device is studied. A very low sheet resistance of 670 Ω/□ and excellent supercapacitance of 158 μF cm-2 with 86% retention after 10 000 cycles show the prospect of the damage-free VGN transfer approach for the fabrication of flexible nanoelectronic devices.

Long-lasting antifog plasma modification of transparent plastics.

PubMed

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

2014-10-08

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

Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

NASA Astrophysics Data System (ADS)

Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

2018-05-01

Ionic liquids (ILs) are considered as attractive electrolyte solvents in modern battery concepts such as Li-ion batteries. Here we present a comprehensive review of the results of previous model studies on the interaction of the battery relevant IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) with a series of structurally and chemically well-defined model electrode surfaces, which are increasingly complex and relevant for battery applications [Ag(111), Au(111), Cu(111), pristine and lithiated highly oriented pyrolytic graphite (HOPG), and rutile TiO2(110)]. Combining surface science techniques such as high resolution scanning tunneling microscopy and X-ray photoelectron spectroscopy for characterizing surface structure and chemical composition in deposited (sub-)monolayer adlayers with dispersion corrected density functional theory based calculations, this work aims at a molecular scale understanding of the fundamental processes at the electrode | electrolyte interface, which are crucial for the development of the so-called solid electrolyte interphase (SEI) layer in batteries. Performed under idealized conditions, in an ultrahigh vacuum environment, these model studies provide detailed insights on the structure formation in the adlayer, the substrate-adsorbate and adsorbate-adsorbate interactions responsible for this, and the tendency for chemically induced decomposition of the IL. To mimic the situation in an electrolyte, we also investigated the interaction of adsorbed IL (sub-)monolayers with coadsorbed lithium. Even at 80 K, postdeposited Li is found to react with the IL, leading to decomposition products such as LiF, Li3N, Li2S, LixSOy, and Li2O. In the absence of a [BMP]+[TFSI]- adlayer, it tends to adsorb, dissolve, or intercalate into the substrate (metals, HOPG) or to react with the substrate (TiO2) above a critical temperature, forming LiOx and Ti3+ species in the latter case. Finally, the formation of stable decomposition products was found to sensitively change the equilibrium between surface Li and Li+ intercalated in the bulk, leading to a deintercalation from lithiated HOPG in the presence of an adsorbed IL adlayer at >230 K. Overall, these results provide detailed insights into the surface chemistry at the solid | electrolyte interface and the initial stages of SEI formation at electrode surfaces in the absence of an applied potential, which is essential for the further improvement of future Li-ion batteries.

Modification of porous silicon rugate filters through thiol-yne photochemistry

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

Soeriyadi, Alexander H., E-mail: alexander.soeriyadi@unsw.edu.au; Zhu, Ying, E-mail: alexander.soeriyadi@unsw.edu.au; Gooding, J. Justin, E-mail: justin.gooding@unsw.edu.au

2014-02-24

Porous silicon (PSi) has a considerable potential as biosensor platform. In particular, the ability to modify the surface chemistry of porous silicon is of interest. Here we present a generic method to modify the surface of porous silicon through thiol-yne photochemistry initiated by a radical initiator. Firstly, a freshly etched porous silicon substrate is modified through thermal hydrosilylation with 1,8-nonadiyne to passivate the surface and introduce alkyne functionalities. The alkyne functional surface could then be further reacted with thiol species in the presence of a radical initiator and UV light. Functionalization of the PSi rugate filter is followed with opticalmore » reflectivity measurements as well as high resolution X-ray photoelectron spectroscopy (XPS)« less

Covalent Functionalization of NiTi Surfaces with Bioactive Peptide Amphiphile Nanofibers

PubMed Central

Sargeant, Timothy D.; Rao, Mukti S.; Koh, Chung-Yan

2009-01-01

Surface modification enables the creation of bioactive implants using traditional material substrates without altering the mechanical properties of the bulk material. For applications such as bone plates and stents, it is desirable to modify the surface of metal alloy substrates to facilitate cellular attachment, proliferation, and possibly differentiation. In this work we present a general strategy for altering the surface chemistry of nickel-titanium shape memory alloy (NiTi) in order to covalently attach self-assembled peptide amphiphile (PA) nanofibers with bioactive functions. Bioactivity in the systems studied here includes biological adhesion and proliferation of osteoblast and endothelial cell types. The optimized surface treatment creates a uniform TiO2 layer with low levels of Ni on the NiTi surface, which is subsequently covered with an aminopropylsilane coating using a novel, lower temperature vapor deposition method. This method produces an aminated surface suitable for covalent attachment of PA molecules containing terminal carboxylic acid groups. The functionalized NiTi surfaces have been characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). These techniques offer evidence that the treated metal surfaces consist primarily of TiO2 with very little Ni, and also confirm the presence of the aminopropylsilane overlayer. Self-assembled PA nanofibers presenting the biological peptide adhesion sequence Arg-Gly-Asp-Ser are capable of covalently anchoring to the treated substrate, as demonstrated by spectrofluorimetry and AFM. Cell culture and scanning electron microscopy (SEM) demonstrate cellular adhesion, spreading, and proliferation on these functionalized metal surfaces. Furthermore, these experiments demonstrate that covalent attachment is crucial for creating robust PA nanofiber coatings, leading to confluent cell monolayers. PMID:18083225

Solvophilic and solvophobic surfaces and non-Coulombic surface interactions in charge regulating electric double layers

NASA Astrophysics Data System (ADS)

Vangara, R.; van Swol, F.; Petsev, D. N.

2018-01-01

The properties of electric double layers are governed by the interface between the substrate and the adjacent electrolyte solution. This interface is involved in chemical, Coulombic, and non-Coulombic (e.g., van der Waals or Lennard-Jones) interactions with all components of the fluid phase. We present a detailed study of these interactions using a classical density functional approach. A particular focus is placed on the non-Coulombic interactions and their effect on the surface chemistry and charge regulation. The solution structure near the charged interface is also analyzed and used to offer a thorough interpretation of established concepts such as the Stern and diffuse ionic layers.

High Throughput Atomic Layer Deposition Processes: High Pressure Operations, New Reactor Designs, and Novel Metal Processing

NASA Astrophysics Data System (ADS)

Mousa, MoatazBellah Mahmoud

Atomic Layer Deposition (ALD) is a vapor phase nano-coating process that deposits very uniform and conformal thin film materials with sub-angstrom level thickness control on various substrates. These unique properties made ALD a platform technology for numerous products and applications. However, most of these applications are limited to the lab scale due to the low process throughput relative to the other deposition techniques, which hinders its industrial adoption. In addition to the low throughput, the process development for certain applications usually faces other obstacles, such as: a required new processing mode (e.g., batch vs continuous) or process conditions (e.g., low temperature), absence of an appropriate reactor design for a specific substrate and sometimes the lack of a suitable chemistry. This dissertation studies different aspects of ALD process development for prospect applications in the semiconductor, textiles, and battery industries, as well as novel organic-inorganic hybrid materials. The investigation of a high pressure, low temperature ALD process for metal oxides deposition using multiple process chemistry revealed the vital importance of the gas velocity over the substrate to achieve fast depositions at these challenging processing conditions. Also in this work, two unique high throughput ALD reactor designs are reported. The first is a continuous roll-to-roll ALD reactor for ultra-fast coatings on porous, flexible substrates with very high surface area. While the second reactor is an ALD delivery head that allows for in loco ALD coatings that can be executed under ambient conditions (even outdoors) on large surfaces while still maintaining very high deposition rates. As a proof of concept, part of a parked automobile window was coated using the ALD delivery head. Another process development shown herein is the improvement achieved in the selective synthesis of organic-inorganic materials using an ALD based process called sequential vapor infiltration. Finally, the development of a new ALD chemistry for novel metal deposition is discussed and was used to deposit thin films of tin metal for the first time in literature using an ALD process. The various challenges addressed in this work for the development of different ALD processes help move ALD closer to widespread use and industrial integration.

Microstructure and mechanical properties of diamond films on titanium-aluminum-vanadium alloy

NASA Astrophysics Data System (ADS)

Catledge, Shane Aaron

The primary focus of this dissertation is the investigation of the processing-structure-property relationships of diamond films deposited on Ti-6Al-4V alloy by microwave plasma chemical vapor deposition (MPCVD). By depositing a well-adhered protective layer of diamond on an alloy component, its hardness, wear-resistance, performance, and overall lifetime could be significantly increased. However, due to the large thermal expansion mismatch between the diamond film and metal (and the corresponding residual stress induced in the film), film adhesion is typically unsatisfactory and often results in immediate delamination after processing. Therefore, it is a major goal of this research to improve adhesion of the diamond film to the alloy substrate. Through the use of innovative processing techniques involving MPCVD deposition conditions and methane (CH4), nitrogen (N2), and hydrogen (H2) chemistry, we have achieved diamond films which consistently adhere to the alloy substrate. In addition, we have discovered that, with the appropriate choice of deposition conditions, the film structure can be tailored to range from highly crystalline, well-faceted diamond to nanocrystalline diamond with extremely low surface roughness (as low as 27 nm). The relationship between processing and structure was studied using in-situ optical emission spectroscopy, micro-Raman spectroscopy, surface profilometry, glancing-angle x-ray diffraction, and scanning electron microscopy. We observe that when nitrogen is added to the H2/CH4 feedgas mixture, a carbon-nitrogen (CN) emission band arises and its relative abundance to the carbon dimer (C2) gas species is shown to have a pronounced influence on the diamond film structure. By appropriate choice of deposition chemistry and conditions, we can tailor the diamond film structure and its corresponding properties. The mechanical properties of interest in this thesis are those relating to the integrity of the film/substrate interface, as well as the hardness, wear resistance, residual stress, and elastic modulus of the film. The mechanical properties of the diamond coatings were characterized by indentation and wear testing instruments. Finally, we developed a model based on fundamental thermodynamic and optical principles for extracting the time dependence of film thickness and surface roughness using optical pyrometry for the case of an absorbing substrate. This model provides a convenient way to determine film thickness during growth in CVD systems as well as a reliable estimate of surface roughness.

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

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

Harnisch, Jennifer Anne

2001-01-01

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performancemore » both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.« less

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Gold cleaning methods for preparation of cell culture surfaces for self-assembled monolayers of zwitterionic oligopeptides.

PubMed

Enomoto, Junko; Kageyama, Tatsuto; Myasnikova, Dina; Onishi, Kisaki; Kobayashi, Yuka; Taruno, Yoko; Kanai, Takahiro; Fukuda, Junji

2018-05-01

Self-assembled monolayers (SAMs) have been used to elucidate interactions between cells and material surface chemistry. Gold surfaces modified with oligopeptide SAMs exhibit several unique characteristics, such as cell-repulsive surfaces, micropatterns of cell adhesion and non-adhesion regions for control over cell microenvironments, and dynamic release of cells upon external stimuli under culture conditions. However, basic procedures for the preparation of oligopeptide SAMs, including appropriate cleaning methods of the gold surface before modification, have not been fully established. Because gold surfaces are readily contaminated with organic compounds in the air, cleaning methods may be critical for SAM formation. In this study, we examined the effects of four gold cleaning methods: dilute aqua regia, an ozone water, atmospheric plasma, and UV irradiation. Among the methods, UV irradiation most significantly improved the formation of oligopeptide SAMs in terms of repulsion of cells on the surfaces. We fabricated an apparatus with a UV light source, a rotation table, and HEPA filter, to treat a number of gold substrates simultaneously. Furthermore, UV-cleaned gold substrates were capable of detaching cell sheets without serious cell injury. This may potentially provide a stable and robust approach to oligopeptide SAM-based experiments for biomedical studies. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

DOE PAGES

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou; ...

2017-03-18

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

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

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Designing a Binding Interface for Control of Cancer Cell Adhesion via 3D Topography and Metabolic Oligosaccharide Engineering

PubMed Central

Du, Jian; Che, Pao-Lin; Wang, Zhi-Yun; Aich, Udayanath; Yarema, Kevin J.

2011-01-01

This study combines metabolic oligosaccharide engineering (MOE), a technology where the glycocalyx of living cells is endowed with chemical features not normally found in sugars, with custom-designed three dimensional biomaterial substrates to enhance the adhesion of cancer cells and control their morphology and gene expression. Specifically, Ac5ManNTGc, a thiol-bearing analogue of N-acetyl-d-mannosamine (ManNAc) was used to introduce thiolated sialic acids into the glycocalyx of human Jurkat T-lymphoma derived cells. In parallel 2D films and 3D electrospun nanofibrous scaffolds were prepared from polyethersulfone (PES) and (as controls) left unmodified or aminated. Alternately, the materials were malemided or gold-coated to provide bioorthogonal binding partners for the thiol groups newly expressed on the cell surface. Cell attachment was modulated by both the topography of the substrate surface and by the chemical compatibility of the binding interface between the cell and the substrate; a substantial increase in binding for normally non-adhesive Jurkat line for 3D scaffold compared to 2D surfaces with an added degree of adhesion resulting from chemoselective binding to malemidede-derivatived or gold-coated surfaces. In addition, the morphology of the cells attached to the 3D scaffolds via MOE-mediated adhesion was dramatically altered and the expression of genes involved in cell adhesion changed in a time-dependent manner. This study showed that cell adhesion could be enhanced, gene expression modulated, and cell fate controlled by introducing the 3D topograhical cues into the growth substrate and by creating a glycoengineered binding interface where the chemistry of both the cell surface and biomaterials scaffold was controlled to facilitate a new mode of carbohydrate-mediated adhesion. PMID:21549424

Atmospheric-pressure plasma-enhanced chemical vapor deposition of a-SiCN:H films: Role of precursors on the film growth and properties

DOE PAGES

Guruvenket, Srinivasan; Andrie, Steven; Simon, Mark; ...

2012-09-14

Atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using Surfx Atomflow TM 250D APPJ was utilized to synthesize amorphous silicon carbonitride coatings using tetramethyldisilizane (TMDZ) and hexamethyldisilizane (HMDZ) as the single source precursors. The effect of precursor chemistry and the substrate temperature (T s) on the properties of a-SiCN:H films were evaluated, while nitrogen was used as the reactive gas. Surface morphology of the films was evaluated using atomic force microscopy (AFM); chemical properties were determined using Fourier transform infrared spectroscopy (FTIR); thickness and optical properties were determined using spectroscopic ellipsometry and mechanical properties were determined using nano-indentation. In generalmore » films deposited at substrate temperature (T s) <200 °C contained organic moieties, while the films deposited at T s >200 oC depicted strong Si-N and Si-CN absorption. Refractive indices (n) of the thin films showed values between 1.5 -2.0 depending on the deposition parameters. Mechanical properties of the films determined using nano-indentation revealed that these films have hardness between 0.5 GPa to 15 GPa depending on the Ts. AFM evaluation of the films showed high roughness (R a) values of 2-3 nm for the films grown at low T s (< 250 °C), while the films grown at T s ≥ 300 °C exhibited atomically smooth surface with R a of ~ 0.5 nm. Furthermore, based on the gas phase (plasma) chemistry, precursor chemistry and the other experimental observations, a possible growth model that prevails in the AP-PECVD of a-SiCN:H thin films is proposed.« less

Atmospheric-pressure plasma-enhanced chemical vapor deposition of a-SiCN:H films: role of precursors on the film growth and properties.

PubMed

Guruvenket, Srinivasan; Andrie, Steven; Simon, Mark; Johnson, Kyle W; Sailer, Robert A

2012-10-24

Atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using Surfx Atomflow(TM) 250D APPJ was utilized to synthesize amorphous silicon carbonitride coatings using tetramethyldisilizane (TMDZ) and hexamethyldisilizane (HMDZ) as the single source precursors. The effect of precursor chemistry and substrate temperature (T(s)) on the properties of a-SiCN:H films were evaluated, while nitrogen was used as the reactive gas. Surface morphology of the films was evaluated using atomic force microscopy (AFM); chemical properties were determined using Fourier transform infrared spectroscopy (FTIR); thickness and optical properties were determined using spectroscopic ellipsometry and mechanical properties were determined using nanoindentation. In general, films deposited at substrate temperature (T(s)) < 200 °C contained organic moieties, while the films deposited at T(s) > 200 °C depicted strong Si-N and Si-CN absorption. Refractive indices (n) of the thin films showed values between 1.5 and 2.0, depending on the deposition parameters. Mechanical properties of the films determined using nanoindentation revealed that these films have hardness between 0.5 GPa and 15 GPa, depending on the T(s) value. AFM evaluation of the films showed high roughness (R(a)) values of 2-3 nm for the films grown at low T(s) (<250 °C) while the films grown at T(s) ≥ 300 °C exhibited atomically smooth surface with R(a) of ~0.5 nm. Based on the gas-phase (plasma) chemistry, precursor chemistry and the other experimental observations, a possible growth model that prevails in the AP-PECVD of a-SiCN:H thin films is proposed.

Substrate-Based Noble-Metal Nanomaterials: Shape Engineering and Applications

NASA Astrophysics Data System (ADS)

Hajfathalian, Maryam

Nanostructures have potential for use in state-of-the-art applications such as sensing, imaging, therapeutics, drug delivery, and electronics. The ability to fabricate and engineer these nanoscale materials is essential for the continued development of such devices. Because the morphological features of nanomaterials play a key role in determining chemical and physical properties, there is great interest in developing and improving methods capable of controlling their size, shape, and composition. While noble nanoparticles have opened the door to promising applications in fields such as imaging, cancer targeting, photothermal treatment, drug delivery, catalysis and sensing, the synthetic processes required to form these nanoparticles on surfaces are not well-developed. Herein is a detailed account on efforts for adapting established solution-based seed-mediated synthetic protocols to structure in a substrate-based platform. These syntheses start by (i) defining heteroepitaxially oriented nanostructured seeds at site-specific locations using lithographic or directed-assembly techniques, and then (ii) transforming the seeds using either a solution or vapor phase processing route to activate kinetically- or thermodynamically-driven growth modes, to arrive at nanocrystals with complex and useful geometries. The first series of investigations highlight synthesis-routes based on heterogeneous nucleation, where templates serve as nucleation sites for metal atoms arriving in the vapor phase. In the first research direction, the vapor-phase heterogeneous nucleation of Ag on Au was carried out at high temperatures, where the Ag vapor was sourced from a sublimating foil onto adjacent Au templates. This process transformed both the composition and morphology of the initial Au Wulff-shaped nanocrystals to a homogeneous AuAg nanoprism. In the second case, the vapor-phase heterogeneous nucleation of Cu atoms on Au nanocrystal templates was investigated by placing a Cu foil next to Au templates and heating, which caused the Cu atoms from the foil to sublimate from the foil and heterogeneously nucleation on the surface of the immobilized Au seeds. This process caused the composition and morphology of the Au Wulff-shape to transform into a homogeneous AuCu nanotriangle. Lastly, we characterized the morphological features and composition, optical properties, and also the catalytic and photocatalytic performance toward hydrogenation of 4-nitrophenolate. The second series of investigations highlight synthetic routes utilizing competencies of substrate-based techniques with colloidal chemistry. We have demonstrated two substrate-based syntheses yielding bimetallic nanostructures where shape control was achieved through (i) facet-selective capping agents and (ii) additive and subtractive process. In the first case a citrate-based cubic structure has been synthesized in the presence or absence of ascorbic acid and the role of each has been considered in shape control. Reactions were carried out in which Ag+ ions were reduced onto substrate-immobilized Ag, Au, Pd, and Pt seeds. It was discovered that for syntheses lacking ascorbic acid, citrate acts as both the capping and the reducing agent, resulting in a robust nanocube growth mode; however, when ascorbic acid was included in these syntheses, then the growth mode reverted to one that advances the octahedral geometry. The conclusion of these results was that citrate, or one of its oxidation products, selectively caps (100) facets, but where this capability was compromised by ascorbic acid. In the second case, galvanic replacement reactions have been carried out on immobilized cubic and Wulff structures to create the substrate-based nanoshells and nanocages, where the prepositioned templates were chemically transformed into hollow structures. In this novel research, Wulff-shaped templates of Au, Pt, or Pd, formed through the dewetting of ultrathin films, were first transformed into core?shell structures through the reduction of Ag+ ions onto their surface and then further transformed through the galvanic replacement of Ag with Au. Detailed studies were provided highlighting discoveries related to (i) alloying, (ii) dealloying, (iii) hollowing, (iv) crystal structure and (vi) the localized surface plasmon resonance (LSPR). Overall, a series of synthetic strategies based on physical and chemical vapor deposition were devised and validated to achieve novel substrate- based nanomaterials with different shapes and compositions for a variety of applications such as sensing, plasmonics, catalysis, and photocatalysis. The novel research in this dissertation also takes advantage of competencies of substrate-based techniques with colloidal chemistry and, brings this rich and exciting chemistry and its associated functionalities to the substrate surface.

Controlling the Accumulation of Water at Oil-Solid Interfaces with Gradient Coating.

PubMed

Li, Yan; Yang, Qiaomu; Mei, Ran Andy; Cai, Meirong; Heng, Jerry Y Y; Yang, Zhongqiang

2017-07-13

In this work, we demonstrate a strategy to control the accumulation of water in the oil-solid interface using a gradient coating. Gradient chemistry on glass surface is created by vapor diffusion of organosilanes, leading to a range of contact angles from 110 to 20°. Hexadecane is placed on the gradient substrate as an oil layer, forming a "water/hexadecane/gradient solid substrate" sandwich structure. During incubation, water molecules spontaneously migrate through the micrometer-thick oil layer and result in the formation of micrometer-sized water droplets at the oil-solid interface. It turns out that water droplets at more hydrophobic regions tend to be closer to a regular spherical shape, which is attributed to their higher contact angle with the hydrophobic substrate. However, along the gradient from hydrophobic to hydrophilic, the water droplets gradually form more irregular shapes, as hydrophilic surfaces pin the edges of droplets to form a distorted morphology. It indicates that more hydrophilic surfaces containing more Si-OH groups lead to a higher electrostatic interaction with water and a higher growth rate of interfacial water droplets. This work provides further insights into the mechanism of spontaneous water accumulation at oil-solid interfaces and assists in the rational design for controlling such interfacial phenomenon.

Plasma enhanced chemical vapour deposition of silica onto Ti: Analysis of surface chemistry, morphology and functional hydroxyl groups

PubMed Central

Szili, Endre J.; Kumar, Sunil; Smart, Roger St. C.; Lowe, Rachel; Saiz, Eduardo; Voelcker, Nicolas H.

2009-01-01

Previously, we have developed and characterised a procedure for the deposition of thin silica films by a plasma enhanced chemical vapour deposition (PECVD) procedure using tetraethoxysilane (TEOS) as the main precursor. We have used the silica coatings for improving the corrosion resistance of metals and for enhancing the bioactivity of biomedical metallic implants. Recently, we have been fine-tuning the PECVD method for producing high quality and reproducible PECVD-silica (PECVD-Si) coatings on metals, primarily for biomaterial applications. In order to understand the interaction of the PECVD-Si coatings with biological species (such as proteins and cells), it is important to first analyse the properties of the silica films deposited using the optimised parameters. Therefore, this current investigation was carried out to analyse the characteristic features of PECVD-Si deposited on Ti substrates (PECVD-Si-Ti). We determined that the PECVD-Si coatings on Ti were conformal to the substrate surface, strongly adhered to the underlying substrate and were resistant to delamination. The PECVD-Si surface was composed of stoichiometric SiO2, showed a low carbon content (below 10 at.%) and was very hydrophilic (contact angle <10°). Finally, we also showed that the PECVD-Si coatings contain functional hydroxyl groups. PMID:19809536

Materials Design for Block Copolymer Lithography

NASA Astrophysics Data System (ADS)

Sweat, Daniel Patrick

Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up a wide slew of applications from directed self-assembly to biomaterial engineering.

Enzyme microheterogeneous hydration and stabilization in supercritical carbon dioxide.

PubMed

Silveira, Rodrigo L; Martínez, Julian; Skaf, Munir S; Martínez, Leandro

2012-05-17

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Fabrication of biomimetic nanomaterials and their effect on cell behavior

NASA Astrophysics Data System (ADS)

Porri, Teresa Jane

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

PubMed

Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

2016-11-01

Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical results are confirmed by comparison with experimental data on chromatographic separation of a series of linear polystyrenes. Copyright © 2016 Elsevier Inc. All rights reserved.

When lithography meets self-assembly: a review of recent advances in the directed assembly of complex metal nanostructures on planar and textured surfaces

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

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

USGS Publications Warehouse

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

1992-01-01

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

Elementary surface chemistry during CuO/Al nanolaminate-thermite synthesis: copper and oxygen deposition on aluminum (111) surfaces.

PubMed

Lanthony, Cloé; Guiltat, Mathilde; Ducéré, Jean Marie; Verdier, Agnes; Hémeryck, Anne; Djafari-Rouhani, Mehdi; Rossi, Carole; Chabal, Yves J; Estève, Alain

2014-09-10

The surface chemistry associated with the synthesis of energetic nanolaminates controls the formation of the critical interfacial layers that dominate the performances of nanothermites. For instance, the interaction of Al with CuO films or CuO with Al films needs to be understood to optimize Al/CuO nanolaminates. To that end, the chemical mechanisms occurring during early stages of molecular CuO adsorption onto crystalline Al(111) surfaces are investigated using density functional theory (DFT) calculations, leading to the systematic determination of their reaction enthalpies and associated activation energies. We show that CuO undergoes dissociative chemisorption on Al(111) surfaces, whereby the Cu and O atoms tend to separate from each other. Both Cu and O atoms form islands with different properties. Copper islanding fosters Cu insertion (via surface site exchange mechanism) into the subsurface, while oxygen islands remain stable at the surface. Above a critical local oxygen coverage, aluminum atoms are extracted from the Al surface, leading to oxygen-aluminum intermixing and the formation of aluminum oxide (γ-alumina). For Cu and O co-deposition, copper promotes oxygen-aluminum interaction by oxygen segregation and separates the resulting oxide from the Al substrate by insertion into Al and stabilization below the oxide front, preventing full mixing of Al, Cu, and O species.

Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.

PubMed

Sohail, Manzar; De Marco, Roland; Jarolímová, Zdeňka; Pawlak, Marcin; Bakker, Eric; He, Ning; Latonen, Rose-Marie; Lindfors, Tom; Bobacka, Johan

2015-09-29

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.

Computational approaches to substrate-based cell motility

DOE PAGES

Ziebert, Falko; Aranson, Igor S.

2016-07-15

Substrate-based crawling motility of eukaryotic cells is essential for many biological functions, both in developing and mature organisms. Motility dysfunctions are involved in several life-threatening pathologies such as cancer and metastasis. Motile cells are also a natural realization of active, self-propelled ‘particles’, a popular research topic in nonequilibrium physics. Finally, from the materials perspective, assemblies of motile cells and evolving tissues constitute a class of adaptive self-healing materials that respond to the topography, elasticity, and surface chemistry of the environment and react to external stimuli. Although a comprehensive understanding of substrate-based cell motility remains elusive, progress has been achieved recentlymore » in its modeling on the whole cell level. Furthermore we survey the most recent advances in computational approaches to cell movement and demonstrate how these models improve our understanding of complex self-organized systems such as living cells.« less

Multistructural biomimetic substrates for controlled cellular differentiation

NASA Astrophysics Data System (ADS)

Orza, Anamaria I.; Mihu, Carmen; Soritau, Olga; Diudea, Mircea; Florea, Adrian; Matei, Horea; Balici, Stefana; Mudalige, Thilak; Kanarpardy, Ganesh K.; Biris, Alexandru S.

2014-02-01

Multidimensional scaffolds are considered to be ideal candidates for regenerative medicine and tissue engineering based on their potential to provide an excellent microenvironment and direct the fate of the cultured cells. More recently, the use of stem cells in medicine has opened a new technological opportunity for controlled tissue formation. However, the mechanism through which the substrate directs the differentiation of stem cells is still rather unclear. Data concerning its specific surface chemistry, topology, and its signaling ability need to be further understood and analyzed. In our study, atomic force microscopy was used to study the stiffness, roughness, and topology of the collagen (Coll) and metallized collagen (MC) substrates, proposed as an excellent substrate for regenerative medicine. The importance of signaling molecules was studied by constructing a new hybrid signaling substrate that contains both collagen and laminin extracellular matrix (ECM) proteins. The cellular response—such as attachment capability, proliferation and cardiac and neuronal phenotype expression on the metallized and non-metallized hybrid substrates (collagen + laminin)—was studied using MTT viability assay and immunohistochemistry studies. Our findings indicate that such hybrid materials could play an important role in the regeneration of complex tissues.

Thin Films and Interfaces of AN Organic Semiconductor: Perylenetetracarboxylic Dianhydride

NASA Astrophysics Data System (ADS)

Hirose, Yutaka

Structural and electronic properties of thin films of an archetype organic molecular semiconductor, 3,4,9,10 -perylenetetracarboxylic dianhydride, (PTCDA) and of their interfaces are investigated. The first part of the thesis focuses on the growth of PTCDA thin films on graphite and GaAs. Molecular order in the direction parallel to the substrate is found to depend critically on the substrate surface properties, as revealed by marked differences in the crystallinity of films grown on graphite and Se-passivated GaAs surfaces (long range order), on the c(4 x 4) GaAs surface (medium range order), and on the (2 x 4)-c(2 x 8) GaAs surface (short range order). These results are discussed in terms of interface bonding between molecules and the substrate. The second part deals with the electronic and chemical structure of PTCDA thin films and the band lineup of the PTCDA/GaAs heterojunction investigated by Ultraviolet - and X-ray Photoemission Spectroscopies. A basic understanding of the valence band structure and chemical states is obtained with the help of a semi-empirical molecular orbital calculation. At the PTCDA/GaAs interface, the PTCDA highest occupied molecular orbital is found to be ~0.7 eV below the GaAs valence band maximum. This result is discussed in light of previous electrical measurements. Third, chemistry of metal deposition on PTCDA is investigated by synchrotron radiation photoemission spectroscopy. Al, Ti, In, and Sn are found to be highly reactive against PTCDA, yielding a considerable interfacial layer with a large density of states in the PTCDA gap. Ag and Au are found to be inert against PTCDA, producing abrupt interfaces. These results are found to be directly correlated with the electrical properties. Finally, chemistry of contacts formed by reversing the sequence of deposition, i.e. PTCDA on reactive metals (In, Sn, and Ti) is explored. The interfacial layers are found to be considerably smaller than for metals on PTCDA, in accordance with the reverse order of heats of adsorption of the two materials. The resulting interfaces are more abrupt presumably leading to more rectifying character of the electrical contacts.

Synergetic topography and chemistry cues guiding osteogenic differentiation in bone marrow stromal cells through ERK1/2 and p38 MAPK signaling pathway.

PubMed

Zhang, Xinran; Li, Haotian; Lin, Chucheng; Ning, Congqin; Lin, Kaili

2018-01-30

Both the topographic surface and chemical composition modification can enhance rapid osteogenic differentiation and bone formation. Till now, the synergetic effects of topography and chemistry cues guiding biological responses have been rarely reported. Herein, the ordered micro-patterned topography and classically essential trace element of strontium (Sr) ion doping were selected to imitate topography and chemistry cues, respectively. The ordered micro-patterned topography on Sr ion-doped bioceramics was successfully duplicated using the nylon sieve as the template. Biological response results revealed that the micro-patterned topography design or Sr doping could promote cell attachment, ALP activity, and osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSCs). Most importantly, the samples both with micro-patterned topography and Sr doping showed the highest promotion effects, and could synergistically activate the ERK1/2 and p38 MAPK signaling pathways. The results suggested that the grafts with both specific topography and chemistry cues have synergetic effects on osteogenic activity of BMSCs and provide an effective approach to design functional bone grafts and cell culture substrates.

Covalent Immobilization of Microtubules on Glass Surfaces for Molecular Motor Force Measurements and Other Single-Molecule Assays

PubMed Central

Nicholas, Matthew P.; Rao, Lu; Gennerich, Arne

2014-01-01

Rigid attachment of microtubules (MTs) to glass cover slip surfaces is a prerequisite for a variety of microscopy experiments in which MTs are used as substrates for MT-associated proteins, such as the molecular motors kinesin and cytoplasmic dynein. We present an MT-surface coupling protocol in which aminosilanized glass is formylated using the cross-linker glutaraldehyde, fluorescence-labeled MTs are covalently attached, and the surface is passivated with highly pure beta-casein. The technique presented here yields rigid MT immobilization while simultaneously blocking the remaining glass surface against nonspecific binding by polystyrene optical trapping microspheres. This surface chemistry is straightforward and relatively cheap and uses a minimum of specialized equipment or hazardous reagents. These methods provide a foundation for a variety of optical tweezers experiments with MT-associated molecular motors and may also be useful in other assays requiring surface-immobilized proteins. PMID:24633798

Controlled Spalling in (100)-Oriented Germanium by Electroplating

NASA Astrophysics Data System (ADS)

Crouse, Dustin Ray

This work investigates controlled spalling as a method to exfoliate thin films of various thickness from rigid, crystalline germanium (Ge) substrates and to enable substrate reuse for III-V single junction photovoltaic devices. Technological limitations impeding wide-spread adoption of flexible electronics and high-material-cost photovoltaic devices have motivated significant interest in a method to remove devices from their substrates. DC magnetron sputtering has been previously utilized to remove semiconductor devices of various thicknesses from Ge substrates, but this method is expensive and time-consuming. Controlled spalling via high-speed electrodeposition is a fast, inexpensive exfoliation method that utilizes a tensile-stressed metal layer deposited on a (100)-oriented Ge substrate and an external force to mechanically propagate a crack parallel to the surface at a desired depth in the substrate material. Suo and Hutchinson's quantitative models describe critical combinations of film thickness and strain mismatch between a film and substrate at which a stressed bilayer system spontaneously spalls; however, fine control over a wide steady-state spall depth range has been limited by the ability to experimentally tailor strain mismatch caused by residual stress within deposited stressor layers. This work investigates the effect of tuning electroplating current density and electrolyte chemistry on the residual stress in a nickel stressor film and their impact on the achievable spall depth range. Steady-state spall depth is found to increase with increasing stressor layer thickness and decrease with increasing residual stress. By tailoring residual stress through adjusting plating conditions and the electrolyte's phosphorous concentration, wide control over spall depth within Ge substrates from sub-micron to 76microm-thicknesses were achieved. To assess the viability of utilizing controlled spalling for substrate reuse, this dissertation demonstrates the first III-V solar cells (GaInAsP, Eg 1.7 eV) grown directly on a spalled-Ge substrate without any additional surface preparation. Widespread adoption of high-efficiency III-V solar cells has been limited by expensive deposition processes and high material cost of substrates. Substrate reuse offers a promising route towards enabling III-V devices to become cost-competitive for one-sun terrestrial applications. In this study, the quality of spalled Ge surfaces is characterized to assess lattice matching capability between the device layer materials and the substrate. GaAs films grown on spalled Ge substrates by hydride vapor phase epitaxy were single-crystal in nature. III-V solar cells grown on spalled and pristine Ge substrates show nearly equivalent efficiency of 8%, despite the roughness of the spalled-Ge substrate. Principles of fractography were used to deduce that surface roughness originated from non-uniform crack propagation and mixed-mode loading during the spalling process.

Titanium nitride films for micro-supercapacitors: Effect of surface chemistry and film morphology on the capacitance

NASA Astrophysics Data System (ADS)

Achour, Amine; Porto, Raul Lucio; Soussou, Mohamed-Akram; Islam, Mohammad; Boujtita, Mohammed; Aissa, Kaltouma Ait; Le Brizoual, Laurent; Djouadi, Abdou; Brousse, Thierry

2015-12-01

Electrochemical capacitors (EC) in the form of packed films can be integrated in various electronic devices as power source. A fabrication process of EC electrodes, which is compatible with micro-fabrication, should be addressed for practical applications. Here, we show that titanium nitride films with controlled porosity can be deposited on flat silicon substrates by reactive DC-sputtering for use as high performance micro-supercapacitor electrodes. A superior volumetric capacitance as high as 146.4 F cm-3, with an outstanding cycling stability over 20,000 cycles, was measured in mild neutral electrolyte of potassium sulfate. The specific capacitance of the films as well as their capacitance retentions were found to depend on thickness, porosity and surface chemistry of electrodes. The one step process used to fabricate these TiN electrodes and the wide use of this material in the field of semiconductor technology make it promising for miniaturized energy storage systems.

Interplay between discharge physics, gas phase chemistry and surface processes in hydrocarbon plasmas

NASA Astrophysics Data System (ADS)

Hassouni, Khaled

2013-09-01

In this paper we present two examples that illustrate two different contexts of the interplay between plasma-surface interaction process and discharge physics and gas phase chemistry in hydrocarbon discharges. In the first example we address the case of diamond deposition processes and illustrate how a detailed investigation of the discharge physics, collisional processes and transport phenomena in the plasma phase make possible to accurately predict the key local-parameters, i.e., species density at the growing substrate, as function of the macroscopic process parameters, thus allowing for a precise control of diamond deposition process. In the second example, we illustrate how the interaction between a rare gas pristine discharge and carbon (graphite) electrode induce a dramatic change on the discharge nature, i.e., composition, ionization kinetics, charge equilibrium, etc., through molecular growth and clustering processes, solid particle formation and dusty plasma generation. Work done in collaboration with Alix Gicquel, Francois Silva, Armelle Michau, Guillaume Lombardi, Xavier Bonnin, Xavier Duten, CNRS, Universite Paris 13.

Recent Progress in SERS Biosensing

PubMed Central

Bantz, Kyle C.; Meyer, Audrey F.; Wittenberg, Nathan J.; Im, Hyungsoon; Kurtuluş, Özge; Lee, Si Hoon; Lindquist, Nathan C.

2011-01-01

This perspective gives an overview of recent developments in surface-enhanced Raman scattering (SERS) for biosensing. We focus this review on SERS papers published in the last 10 years and to specific applications of detecting biological analytes. Both intrinsic and extrinsic SERS biosensing schemes have been employed to detect and identify small molecules, nucleic acids, lipids, peptides, and proteins, as well as for in vivo and cellular sensing. Current SERS substrate technologies along with a series of advancements in surface chemistry, sample preparation, intrinsic/extrinsic signal transduction schemes, and tip-enhanced Raman spectroscopy are discussed. The progress covered herein shows great promise for widespread adoption of SERS biosensing. PMID:21509385

Porous multi-component material for the capture and separation of species of interest

DOEpatents

Addleman, Raymond S.; Chouyyok, Wilaiwan; Li, Xiaohong S.; Cinson, Anthony D.; Gerasimenko, Aleksandr A

2016-06-21

A method and porous multi-component material for the capture, separation or chemical reaction of a species of interest is disclosed. The porous multi-component material includes a substrate and a composite thin film. The composite thin film is formed by combining a porous polymer with a nanostructured material. The nanostructured material may include a surface chemistry for the capture of chemicals or particles. The composite thin film is coupled to the support or device surface. The method and material provides a simple, fast, and chemically and physically benign way to integrate nanostructured materials into devices while preserving their chemical activity.

Fly ash-TiO2 nanocomposite material for multi-pollutants wastewater treatment.

PubMed

Visa, Maria; Andronic, Luminita; Duta, Anca

2015-03-01

This paper reports on the synthesis, characterization and adsorption properties of a novel nano-composite obtained using the hydrothermal method applied to a fly ash-TiO2 slurry and hexadecyltrimethyl-ammonium bromide, as surface controlling agent. The new adsorbent was investigated in terms of crystallinity (XRD), surface properties (AFM, SEM, and porosity and BET surface) and surface chemistry (EDX, FTIR). The nanocomposite's properties were sequentially tested in adsorption and photocatalysis processes applied to multi-pollutant synthetic wastewaters loaded with copper cations and two industrial dyes: the acid dye Bemacid Blau and the reactive dye Bemacid Rot; the nano-composite substrate allowed reaching high removal efficiencies, above 90%, both in adsorption and in photodegradation experiments, in optimised conditions. Copyright © 2014. Published by Elsevier Ltd.

NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2014-03-01

NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Processing of ammonia-containing ices by heavy ions and its relevance to outer Solar System surfaces

NASA Astrophysics Data System (ADS)

Pilling, Sergio; Seperuelo Duarte, Eduardo; da Silveira, Enio F.; Domaracka, Alicja; Balanzat, Emmanuel; Rothard, Hermann; Boduch, Philippe

Ammonia-containing ices have been detected or postulated as important components of the icy surfaces of planetary satellites (e.g. Enceladus, Miranda), in the outer Solar System objects (e.g. Charon, Quaoar) and in Oort cloud comets. We present experimental studies of the interaction of heavy, highly-charged, and energetic ions with ammonia-containing ices (pure NH3 ; NH3 :CO; NH3 :H2 O and NH3 :H2 O:CO) in an attempt to simulate the physical chemistry induced by heavy-ion cosmic rays and heavy-ion solar wind particles at outer Solar System surfaces. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared spectrometer (FTIR) at different ion fluences. The dissociation cross-section and sputtering yield of ammonia and other ice compounds have been determined. Half-life of frozen ammonia due to heavy ion bombardment at different Solar System surfaces has been estimated. Radiolysis products have been identified and their implications for the chemistry on outer Solar System surfaces are discussed.

Surface functionalized nanofibrillar cellulose (NFC) film as a platform for immunoassays and diagnostics.

PubMed

Orelma, Hannes; Filpponen, Ilari; Johansson, Leena-Sisko; Osterberg, Monika; Rojas, Orlando J; Laine, Janne

2012-12-01

We introduce a new method to modify films of nanofibrillated cellulose (NFC) to produce non-porous, water-resistant substrates for diagnostics. First, water resistant NFC films were prepared from mechanically disintegrated NFC hydrogel, and then their surfaces were carboxylated via TEMPO-mediated oxidation. Next, the topologically functionalized film was activated via EDS/NHS chemistry, and its reactivity verified with bovine serum albumin and antihuman IgG. The surface carboxylation, EDC/NHS activation and the protein attachment were confirmed using quartz crystal microbalance with dissipation, contact angle measurements, conductometric titrations, X-ray photoelectron spectroscopy and fluorescence microscopy. The surface morphology of the prepared films was investigated using confocal laser scanning microscopy and atomic force microscopy. Finally, we demonstrate that antihuman IgG can be immobilized on the activated NFC surface using commercial piezoelectric inkjet printing.

Super-SERS-active and highly effective antimicrobial Ag nanodendrites

NASA Astrophysics Data System (ADS)

Li, H. B.; Liu, P.; Liang, Y.; Xiao, J.; Yang, G. W.

2012-07-01

We have developed simple and green electrochemistry to synthesize Ag nanostructures with high purity, good crystallinity and smooth surface for applications as super-SERS (surface-enhanced Raman scattering), SERS-active substrates and with highly effective antimicrobial activities. This synthesis takes place in a clean and slow reaction environment without any chemical additives, which ensures an ultrahigh active surface of the as-synthesized Ag nanostructures owing to their purity, good crystallinity and smooth morphology. Using this method, we synthesized nearly perfect Ag nanodendrites (NDs), which exhibit super-SERS sensitivity when they are used to detect the SERS spectra of rhodamine 6G at concentrations as low as 5 × 10-16 M, and have an ultrahigh electromagnetic (EM) enhancement factor of the order of 1013, breaking through the theoretical limit of EM enhancement. Meanwhile, the as-synthesized Ag NDs possess highly effective antimicrobial activities for Escherichia coli, Candida albicans and Staphylococcus aureus, which are over 10 times that of silver nanoparticles. Additionally, the basic physics and chemistry involved in the fabrication of Ag nanostructures are pursued. These investigations show that silver nanostructures with highly active surfaces can make the most of Ag nanostructures functioning as super-SERS-active substrates and multiple antibiotics.

Corrosion Control through a Better Understanding of the Metallic Substrate/Organic Coating/Interface

DTIC Science & Technology

1989-02-06

Mdssbauer Spectroscopy to Studies of Electrodeposits and the Chemistry of Metal Surfaces," Henry Leidheiser, Jr., J. Electrochem. Soc. 135(2), 5C-11C (1988...VanderHart, D. L. J.agn. Res, 1982, 48, 35. -21- (22) Venkatachalam, C. M.; Urry, D. W. J. Magn. Res, 1980, 41, 313. (23) Deck, P. PhD Thesis , Lehigh...that can serve as nucleation sites for the formation of an aqueous phase. Reduction in the probability that nucleation sites exist at the interface

Hydrogen Abstraction from Individual Thiophenol Molecules Adsorbed on Cu(111)

NASA Astrophysics Data System (ADS)

Rao, Bommisetty; Kwon, Ki-Young; Liu, Anwei; Zhang, Jin-Tao; Bartels, Ludwig

2004-03-01

Thiol compounds on metal surfaces have been studied intensively because of their ability to form self-assembled monolayers (SAMs). However, the transition from the thiol to the surface thiolate is difficult to investigate in detail in the solution phase. Here we report on STM measurements that address the adsorption of a variety of substituted thiophenols on Cu(111) at 15K in vacuum. At this temperature, adsorption does not cause immediate scission of the S-H bond. We confirmed this by STM-based vibrational spectroscopy. Consequently, the sulfur atom of the thiol group adsorbs on-top of a substrate atom, which results in a sufficient separation of the aryl group from the substrate to allow its free rotation even at 15K. Asymmetrically substituted thiophenols result in STM images of pronounced helicity, which indicates that the molecules cannot tilt upright to exchange their adsorption side. Attachment of electrons from the tunneling current can cause hydrogen abstraction from the thiophenols, which locks them into the substrate. We investigated the dependence of the yield of the hydrogen abstraction on the thiophenol substituent identity and position. We find pronounced variations which may follow the Hammett Equation known from Standard Organic Chemistry.

Cooperative control of blood compatibility and re-endothelialization by immobilized heparin and substrate topography.

PubMed

Ding, Yonghui; Yang, Meng; Yang, Zhilu; Luo, Rifang; Lu, Xiong; Huang, Nan; Huang, Pingbo; Leng, Yang

2015-03-01

A wide variety of environmental cues provided by the extracellular matrix, including biophysical and biochemical cues, are responsible for vascular cell behavior and function. In particular, substrate topography and surface chemistry have been shown to regulate blood and vascular compatibility individually. The combined impact of chemical and topographic cues on blood and vascular compatibility, and the interplay between these two types of cues, are subjects that are currently being explored. In the present study, a facile polydopamine-mediated approach is introduced for immobilization of heparin on topographically patterned substrates, and the combined effects of these cues on blood compatibility and re-endothelialization are systematically investigated. The results show that immobilized heparin and substrate topography cooperatively modulate anti-coagulation activity, endothelial cell (EC) attachment, proliferation, focal adhesion formation and endothelial marker expression. Meanwhile, the substrate topography is the primary determinant of cell alignment and elongation, driving in vivo-like endothelial organization. Importantly, combining immobilized heparin with substrate topography empowers substantially greater competitive ability of ECs over smooth muscle cells than each cue individually. Moreover, a model is proposed to elucidate the cooperative interplay between immobilized heparin and substrate topography in regulating cell behavior. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface interaction of polyimide with oxygen ECR plasma

NASA Astrophysics Data System (ADS)

Naddaf, M.; Balasubramanian, C.; Alegaonkar, P. S.; Bhoraskar, V. N.; Mandle, A. B.; Ganeshan, V.; Bhoraskar, S. V.

2004-07-01

Polyimide (Kapton-H), was subjected to atomic oxygen from an electron cyclotron resonance plasma. An optical emission spectrometer was used to characterize the atomic oxygen produced in the reactor chamber. The energy of the ions was measured using a retarding field analyzer, placed near the substrate. The density of atomic oxygen in the plasma was estimated using a nickel catalytic probe. The surface wettability of the polyimide samples monitored by contact angle measurements showed considerable improvement when treated with plasma. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopic studies showed that the atomic oxygen in the plasma is the main specie affecting the surface chemistry and adhesion properties of polyimide. The improvement in the surface wettability is attributed to the high degree of cross-linking and large concentration of polar groups generated in the surface region of polyimide, after plasma treatment. The changes in the surface region of polyimide were observed by atomic force microscopic analysis.

Oxygen plasma treatment and deposition of CN{sub x} on a fluorinated polymer matrix composite for improved erosion resistance

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

Muratore, C.; Korenyi-Both, A.; Bultman, J. E.

2007-07-15

The use of polymer matrix composites in aerospace propulsion applications is currently limited by insufficient resistance to erosion by abrasive media. Erosion resistant coatings may provide necessary protection; however, adhesion to many high temperature polymer matrix composite (PMC) materials is poor. A low pressure oxygen plasma treatment process was developed to improve adhesion of CN{sub x} coatings to a carbon reinforced, fluorinated polymer matrix composite. Fullerene-like CN{sub x} was selected as an erosion resistant coating for its high hardness-to-elastic modulus ratio and elastic resilience which were expected to reduce erosion from media incident at different angles (normal or glancing) relativemore » to the surface. In situ x-ray photoelectron spectroscopy was used to evaluate the effect of the plasma treatment on surface chemistry, and electron microscopy was used to identify changes in the surface morphology of the PMC substrate after plasma exposure. The fluorine concentration at the surface was significantly reduced and the carbon fibers were exposed after plasma treatment. CN{sub x} coatings were then deposited on oxygen treated PMC substrates. Qualitative tests demonstrated that plasma treatment improved coating adhesion resulting in an erosion resistance improvement of a factor of 2 compared to untreated coated composite substrates. The combination of PMC pretreatment and coating with CN{sub x} reduced the erosion rate by an order of magnitude for normally incident particles.« less

Highly ordered nanowire arrays on plastic substrates for ultrasensitive flexible chemical sensors.

PubMed

McAlpine, Michael C; Ahmad, Habib; Wang, Dunwei; Heath, James R

2007-05-01

The development of a robust method for integrating high-performance semiconductors on flexible plastics could enable exciting avenues in fundamental research and novel applications. One area of vital relevance is chemical and biological sensing, which if implemented on biocompatible substrates, could yield breakthroughs in implantable or wearable monitoring systems. Semiconducting nanowires (and nanotubes) are particularly sensitive chemical sensors because of their high surface-to-volume ratios. Here, we present a scalable and parallel process for transferring hundreds of pre-aligned silicon nanowires onto plastic to yield highly ordered films for low-power sensor chips. The nanowires are excellent field-effect transistors, and, as sensors, exhibit parts-per-billion sensitivity to NO2, a hazardous pollutant. We also use SiO2 surface chemistries to construct a 'nano-electronic nose' library, which can distinguish acetone and hexane vapours via distributed responses. The excellent sensing performance coupled with bendable plastic could open up opportunities in portable, wearable or even implantable sensors.

A Generic Wet Impregnation Method for Preparing Substrate-Supported Platinum Group Metal and Alloy Nanoparticles with Controlled Particle Morphology.

PubMed

Zhang, Changlin; Oliaee, Shirin Norooz; Hwang, Sang Youp; Kong, Xiangkai; Peng, Zhenmeng

2016-01-13

Mass production of shape-controlled platinum group metal (PGM) and alloy nanoparticles is of high importance for their many fascinating properties in catalysis, electronics, and photonics. Despite of successful demonstrations at milligram scale using wet chemistry syntheses in many fundamental studies, there is still a big gap between the current methods and their real applications due to the complex synthetic procedures, scale-up difficulty, and surface contamination problem of the made particles. Here we report a generic wet impregnation method for facile, surfactant-free, and scalable preparation of nanoparticles of PGMs and their alloys on different substrate materials with controlled particle morphology and clean surface, which bridges the outstanding properties of these nanoparticles to practical important applications. The underlying particle growth and shape formation mechanisms were investigated using a combination of ex situ and in situ characterizations and were attributed to their different interactions with the applied gas molecules.

Highly ordered nanowire arrays on plastic substrates for ultrasensitive flexible chemical sensors

NASA Astrophysics Data System (ADS)

McAlpine, Michael C.; Ahmad, Habib; Wang, Dunwei; Heath, James R.

2007-05-01

The development of a robust method for integrating high-performance semiconductors on flexible plastics could enable exciting avenues in fundamental research and novel applications. One area of vital relevance is chemical and biological sensing, which if implemented on biocompatible substrates, could yield breakthroughs in implantable or wearable monitoring systems. Semiconducting nanowires (and nanotubes) are particularly sensitive chemical sensors because of their high surface-to-volume ratios. Here, we present a scalable and parallel process for transferring hundreds of pre-aligned silicon nanowires onto plastic to yield highly ordered films for low-power sensor chips. The nanowires are excellent field-effect transistors, and, as sensors, exhibit parts-per-billion sensitivity to NO2, a hazardous pollutant. We also use SiO2 surface chemistries to construct a `nano-electronic nose' library, which can distinguish acetone and hexane vapours via distributed responses. The excellent sensing performance coupled with bendable plastic could open up opportunities in portable, wearable or even implantable sensors.

Highly ordered nanowire arrays on plastic substrates for ultrasensitive flexible chemical sensors

PubMed Central

McAlpine, Michael C.; Ahmad, Habib; Wang, Dunwei; Heath, James R.

2013-01-01

The development of a robust method for integrating high-performance semiconductors on flexible plastics could enable exciting avenues in fundamental research and novel applications. One area of vital relevance is chemical and biological sensing, which if implemented on biocompatible substrates, could yield breakthroughs in implantable or wearable monitoring systems. Semiconducting nanowires (and nanotubes) are particularly sensitive chemical sensors because of their high surface-to-volume ratios. Here, we present a scalable and parallel process for transferring hundreds of pre-aligned silicon nanowires onto plastic to yield highly ordered films for low-power sensor chips. The nanowires are excellent field-effect transistors, and, as sensors, exhibit parts-per-billion sensitivity to NO2, a hazardous pollutant. We also use SiO2 surface chemistries to construct a ‘nano-electronic nose’ library, which can distinguish acetone and hexane vapours via distributed responses. The excellent sensing performance coupled with bendable plastic could open up opportunities in portable, wearable or even implantable sensors. PMID:17450146

Surface properties and electromagnetic excitation of a piezoelectric gallium phosphate biosensor.

PubMed

Vasilescu, Alina; Ballantyne, Scott M; Cheran, Larisa-Emilia; Thompson, Michael

2005-02-01

The surface properties of GaPO4 have been studied by secondary ion mass spectrometry, X-ray photoelectron spectroscopy and electromagnetic acoustic wave excitation in order to explore the potential of this relatively new piezoelectric material as a biosensor. The X-ray photoelectron spectrum of the substrate shows a Ga-rich surface (Ga:P = 1.4), while the negative secondary ion mass spectrum is similar to that of other phosphates, with PO3- and PO2- being the main fragments derived from the substrate. Surface analysis reveals that the linker protein for biotinylated moieties, neutravidin, is both readily chemisorbed to bare gallium phosphate at pH 7.5 and attached to p-hydroxy benzaldehyde-treated devices, establishing the possibility to exploit the surface chemistry of the phosphate for the fabrication of an electrode-free acoustic wave biosensor. Preliminary results regarding the detection of the adsorption of neutravidin with an electromagnetic field-excited GaPO4 device incorporated in a FIA configuration showed comparable results with those obtained with a quartz-sensor equivalent. The frequency shift for the adsorbed protein layer at the device fundamental frequency was 200 Hz and the noise was routinely around 13 Hz. The possibility to use the electrodeless acoustic GaPO4 device at higher harmonics in the liquid phase has also been confirmed.

Understanding improved osteoblast behavior on select nanoporous anodic alumina

PubMed Central

Ni, Siyu; Li, Changyan; Ni, Shirong; Chen, Ting; Webster, Thomas J

2014-01-01

The aim of this study was to prepare different sized porous anodic alumina (PAA) and examine preosteoblast (MC3T3-E1) attachment and proliferation on such nanoporous surfaces. In this study, PAA with tunable pore sizes (25 nm, 50 nm, and 75 nm) were fabricated by a two-step anodizing procedure in oxalic acid. The surface morphology and elemental composition of PAA were characterized by field emission scanning electron microscopy and X-ray photoelectron spectroscopy analysis. The nanopore arrays on all of the PAA samples were highly regular. X-ray photoelectron spectroscopy analysis suggested that the chemistry of PAA and flat aluminum surfaces were similar. However, contact angles were significantly greater on all of the PAA compared to flat aluminum substrates, which consequently altered protein adsorption profiles. The attachment and proliferation of preosteoblasts were determined for up to 7 days in culture using field emission scanning electron microscopy and a Cell Counting Kit-8. Results showed that nanoporous surfaces did not enhance initial preosteoblast attachment, whereas preosteoblast proliferation dramatically increased when the PAA pore size was either 50 nm or 75 nm compared to all other samples (P<0.05). Thus, this study showed that one can alter surface energy of aluminum by modifying surface nano-roughness alone (and not changing chemistry) through an anodization process to improve osteoblast density, and, thus, should be further studied as a bioactive interface for orthopedic applications. PMID:25045263

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Biological Behavior of Osteoblast Cell and Apatite Forming Ability of the Surface Modified Ti Alloys.

PubMed

Zhao, Jingming; Hwang, K H; Choi, W S; Shin, S J; Lee, J K

2016-02-01

Titanium as one kind of biomaterials comes in direct contact with the body, making evaluation of biocompatibility an important aspect to biomaterials development. Surface chemistry of titanium plays an important role in osseointegration. Different surface modification alters the surface chemistry and result in different biological response. In this study, three kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coating successfully formed on the Ti surfaces in simulated body fluid. Strong mixed acid increased the roughness of the metal surface, because the porous and rough surface allows better adhesion between Ca-P coatings and substrates. After modification of titanium surface by mixed acidic solution and subsequently H2O2/HCL treatment evaluation of biocompatibility was conducted from hydroxyapatite formation by biomimetic process and cell viability on modified titanium surface. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Results from this study indicated that surface treatment methods affect the surface morphology, type of TiO2 layer formed and subsequent apatite deposition and biological responses. The thermo scientific alamarblue cell viability assay reagent is used to quantitatively measure the viability of mammalian cell lines, bacteria and fungi by incorporating a rapid, sensitive and reliable fluorometric/colorimetric growth indicator, without any toxic and side effect to cell line. In addition, mixed acid treatment uses a lower temperature and shorter time period than widely used alkali treatment.

Engineered microtopographies and surface chemistries direct cell attachment and function

NASA Astrophysics Data System (ADS)

Magin, Chelsea Marie

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

Elemental and compound semiconductor surface chemistry: Intelligent interfacial design facilitated through novel functionalization and deposition strategies

NASA Astrophysics Data System (ADS)

Porter, Lon Alan, Jr.

The fundamental understanding of silicon surface chemistry is an essential tool for silicon's continued dominance of the semiconductor industry in the years to come. By tapping into the vast library of organic functionalities, the synthesis of organic monolayers may be utilized to prepare interfaces, tailored to a myriad of applications ranging from silicon VLSI device optimization and MEMS to physiological implants and chemical sensors. Efforts in our lab to form stable organic monolayers on porous silicon through direct silicon-carbon linkages have resulted in several efficient functionalization methods. In the first chapter of this thesis a comprehensive review of these methods, and many others is presented. The following chapter and the appendix serve to demonstrate both potential applications and studies aimed at developing a fundamental understanding of the chemistry behind the organic functionalization of silicon surfaces. The remainder of this thesis attempts to demonstrate new methods of metal deposition onto both elemental and compound semiconductor surfaces. Currently, there is considerable interest in producing patterned metallic structures with reduced dimensions for use in technologies such as ULSI device fabrication, MEMS, and arrayed nanosensors, without sacrificing throughput or cost effectiveness. Research in our laboratory has focused on the preparation of precious metal thin films on semiconductor substrates via electroless deposition. Continuous metallic films form spontaneously under ambient conditions, in the absence of a fluoride source or an externally applied current. In order to apply this metallization method toward the development of useful technologies, patterning utilizing photolithography, microcontact printing, and scanning probe nanolithography has been demonstrated.

Biodegradable Nanotopography Combined with Neurotrophic Signals Enhances Contact Guidance and Neuronal Differentiation of Human Neural Stem Cells.

PubMed

Yang, Kisuk; Park, Esther; Lee, Jong Seung; Kim, Il-Sun; Hong, Kwonho; Park, Kook In; Cho, Seung-Woo; Yang, Hee Seok

2015-10-01

Biophysical cues provided by nanotopographical surfaces have been used as stimuli to guide neurite extension and regulate neural stem cell (NSC) differentiation. Here, we fabricated biodegradable polymer substrates with nanoscale topography for enhancing human NSC (hNSC) differentiation and guided neurite outgrowth. The substrate was constructed from biodegradable poly(lactic-co-glycolic acid) (PLGA) using solvent-assisted capillary force lithography. We found that precoating with 3,4-dihydroxy-l-phenylalanine (DOPA) facilitated the immobilization of poly-l-lysine and fibronectin on PLGA substrates via bio-inspired catechol chemistry. The DOPA-coated nanopatterned substrates directed cellular alignment along the patterned grooves by contact guidance, leading to enhanced focal adhesion, skeletal protein reorganization, and neuronal differentiation of hNSCs as indicated by highly extended neurites from cell bodies and increased expression of neuronal markers (Tuj1 and MAP2). The addition of nerve growth factor further enhanced neuronal differentiation of hNSCs, indicating a synergistic effect of biophysical and biochemical cues on NSC differentiation. These bio-inspired PLGA nanopatterned substrates could potentially be used as implantable biomaterials for improving the efficacy of hNSCs in treating neurodegenerative diseases. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diameter and Geometry Control of Vertically Aligned SWNTs through Catalyst Manipulation

NASA Astrophysics Data System (ADS)

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

2009-03-01

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

Hierarchical roughness of sticky and non-sticky superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Raza, Muhammad; Kooij, Stefan; van Silfhout, Arend; Zandvliet, Harold; Poelsema, Bene

2011-11-01

The importance of superhydrophobic substrates (contact angle >150° with sliding angle <10°) in modern technology is undeniable. We present a simple colloidal route to manufacture superstructured arrays with single- and multi-length-scaled roughness to obtain sticky and non-sticky superhydrophobic surfaces. The largest length scale is provided by (multi-)layers of silica spheres (1 μm, 500nm and 150nm diameter). Decoration with gold nanoparticles (14nm, 26nm and 47nm) gives rise to a second length scale. To lower the surface energy, gold nanoparticles are functionalized with dodecanethiol and the silica spheres by perfluorooctyltriethoxysilane. The morphology was examined by helium ion microscopy (HIM), while wettability measurements were performed by using the sessile drop method. We conclude that wettability can be controlled by changing the surface chemistry and/or length scales of the structures. To achieve truly non-sticky superhydrophobic surfaces, hierarchical roughness plays a vital role.

Effects of coal mining, forestry, and road construction on southern Appalachian stream invertebrates and habitats.

PubMed

Gangloff, Michael M; Perkins, Michael; Blum, Peter W; Walker, Craig

2015-03-01

Coal has been extracted via surface and sub-surface mining for decades throughout the Appalachian Mountains. New interest in ridge-top mining has raised concerns about possible waterway impacts. We examined effects of forestry, mining, and road construction-based disturbance on physico-chemistry and macroinvertebrate communities in east-central Tennessee headwater streams. Although 11 of 30 sites failed Tennessee's biocriteria scoring system, invertebrate richness was moderately high and we did not find significant differences in any water chemistry or habitat parameters between sites with passing and failing scores. However, conductivity and dissolved solid concentrations appeared elevated in the majority of study streams. Principal components (PCs) analysis indicated that six PCs accounted for ~77 % of among-site habitat variability. One PC associated with dissolved oxygen and specific conductance explained the second highest proportion of among-site variability after catchment area. Specific conductance was not correlated with catchment area but was strongly correlated with mining activity. Composition and success of multivariate models using habitat PCs to predict macroinvertebrate metrics was highly variable. PC scores associated with water chemistry and substrate composition were most frequently included in significant models. These results suggest that impacts of historical and current coal mining remain a source of water quality and macroinvertebrate community impairment in this region, but effects are subtle. Our results suggest that surface mining may have chronic and system-wide effects on habitat conditions and invertebrate communities in Cumberland Plateau streams.

Proline adsorption on TiO 2(1 1 0) single crystal surface: A study by high resolution photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Fleming, G. J.; Adib, K.; Rodriguez, J. A.; Barteau, M. A.; Idriss, H.

2007-12-01

The surface chemistry and binding of DL-proline were investigated on the oxidised (stoichiometric) and reduced (sub-stoichiometric) TiO 2(1 1 0) single crystal surfaces. TiO 2 was chosen as the substrate as it best represents the surface of a biomedical implant, which bio-molecules interact with during the healing of bone/teeth fractures (molecular recognition). High resolution X-ray photoelectron spectroscopy (HR-XPS) studies of the C1s and N1s regions revealed that DL-proline is present in two forms (dissociated and zwitterionic) on the oxidised TiO 2 surface. On TiO 2(1 1 0) surfaces reduced by Ar + sputtering, a significant increase in the amount of zwitterionic proline at the surface was detected when compared with the oxidised surface. Study of the temperature effect showed that in both cases the zwitterionic structure was the less stable structure. The reason for its relative instability appears to be thermodynamic.

Sexual dimorphism in the attachment ability of the ladybird beetle Coccinella septempunctata on soft substrates

NASA Astrophysics Data System (ADS)

Heepe, Lars; Petersen, Dennis S.; Tölle, Lisa; Wolff, Jonas O.; Gorb, Stanislav N.

2017-01-01

Many insects possess adhesive foot pads, which enable reliable attachment to diverse and unpredictable substrates. The function of these adhesive organs was shown to be affected by environmental conditions such as substrate roughness, chemistry, and ambient humidity. So far, the attachment ability of insects and also that of spiders and geckos has been tested on rigid substrates only. However, the natural habitats of climbing animals may provide a variety of substrate stiffness ranging from rigid rock surfaces to soft, biofilm covered substrates. In order to test the effect of different substrate stiffness on the attachment ability of insects, we have performed friction experiments with female and male ladybird beetles Coccinella septempunctata on smooth silicone elastomer substrates of different stiffness, using a centrifugal force tester. Whereas in females, the attachment ability was not affected by the substrate stiffness within the range of tested stiffness, males showed decreasing attachment ability with decreasing substrate stiffness. This sexual dimorphism in attachment ability is explained by the presence of a specialized, discoidal seta type in males, which is not present in females. It is argued that discoidal setae, when softer if compared to the substrate, may show an advantageous peak-free interfacial stress distribution when being pulled off the substrate. For such setae being stiffer if compared the substrate, they potentially show increased edge stress concentration. In this case, lower pull-off forces are expected, in agreement with the experimentally obtained results. With the present study, we demonstrate for the first time that the substrate stiffness may have an effect on the attachment ability of climbing animals, which may also be of relevance for technical and medical applications involving adhesion to soft substrates.

Plant surface wax affects parasitoid's response to host footprints

NASA Astrophysics Data System (ADS)

Rostás, Michael; Ruf, Daniel; Zabka, Vanessa; Hildebrandt, Ulrich

2008-10-01

The plant surface is the substrate upon which herbivorous insects and natural enemies meet and thus represents the stage for interactions between the three trophic levels. Plant surfaces are covered by an epicuticular wax layer which is highly variable depending on species, cultivar or plant part. Differences in wax chemistry may modulate ecological interactions. We explored whether caterpillars of Spodoptera frugiperda, when walking over a plant surface, leave a chemical trail (kairomones) that can be detected by the parasitoid Cotesia marginiventris. Chemistry and micromorphology of cuticular waxes of two barley eceriferum wax mutants ( cer-za.126, cer-yp.949) and wild-type cv. Bonus (wt) were assessed. The plants were then used to investigate potential surface effects on the detectability of caterpillar kairomones. Here we provide evidence that C. marginiventris responds to chemical footprints of its host. Parasitoids were able to detect the kairomone on wild-type plants and on both cer mutants but the response to cer-yp.949 (reduced wax, high aldehyde fraction) was less pronounced. Experiments with caterpillar-treated wt and mutant leaves offered simultaneously, confirmed this observation: no difference in wasp response was found when wt was tested against cer-za.126 (reduced wax, wt-like chemical composition) but wt was significantly more attractive than cer-yp.949. This demonstrates for the first time that the wax layer can modulate the detectability of host kairomones.

Interactions of Deuterium Plasma with Lithiated and Boronized Surfaces in NSTX-U

NASA Astrophysics Data System (ADS)

Krstic, Predrag

2015-09-01

The main research goal of the presented research has been to understand the changes in surface composition and chemistry at the nanoscopic temporal and spatial scales for long pulse Plasma Facing Components (PFCs) and link these to the overall machine performance of the National Spherical Torus Experiment Upgrade (NSTX-U). A study is presented of the lithium surface science, with atomic spatial and temporal resolutions. The dynamic surface responds and evolves in a mixed material environments (D, Li, C, B, O, Mo, W) with impingement of plasma particles in the energy range below 100 eV. The results, obtained by quantum-classical molecular dynamics, include microstructure changes, erosion, surface chemistry, deuterium implantation and permeation. Main objectives of the research are i) a comparison of Li and B deposition on carbon, ii) the role of oxygen and other impurities e.g. boron, carbon in the lithium performance, and iii) how this performance will change when lithium is applied to a high-Z refractory metal substrate (Mo, W). In addition to predicting and understanding the phenomenology of the processes, we will show plasma induced erosion of PFCs, including chemical and physical sputtering yields at various temperatures (300-700 K) as well as deuterium uptake/recycling. This work is supported by the U.S. Department of Energy Office of Science, Office of Fusion Energy Science, Award Number DE-SC0013752.

Bioinspired, roughness-induced, water and oil super-philic and super-phobic coatings prepared by adaptable layer-by-layer technique

PubMed Central

Brown, Philip S.; Bhushan, Bharat

2015-01-01

Coatings with specific surface wetting properties are of interest for anti-fouling, anti-fogging, anti-icing, self-cleaning, anti-smudge, and oil-water separation applications. Many previous bioinspired surfaces are of limited use due to a lack of mechanical durability. Here, a layer-by-layer technique is utilized to create coatings with four combinations of water and oil repellency and affinity. An adapted layer-by-layer approach is tailored to yield specific surface properties, resulting in a durable, functional coating. This technique provides necessary flexibility to improve substrate adhesion combined with desirable surface chemistry. Polyelectrolyte binder, SiO2 nanoparticles, and silane or fluorosurfactant layers are deposited, combining surface roughness and necessary chemistry to result in four different coatings: superhydrophilic/superoleophilic, superhydrophobic/superoleophilic, superhydrophobic/superoleophobic, and superhydrophilic/superoleophobic. The superoleophobic coatings display hexadecane contact angles >150° with tilt angles <5°, whilst the superhydrophobic coatings display water contact angles >160° with tilt angles <2°. One coating combines both oleophobic and hydrophobic properties, whilst others mix and match oil and water repellency and affinity. Coating durability was examined through the use of micro/macrowear experiments. These coatings display transparency acceptable for some applications. Fabrication via this novel combination of techniques results in durable, functional coatings displaying improved performance compared to existing work where either durability or functionality is compromised. PMID:26353971

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals

NASA Astrophysics Data System (ADS)

Carey, Benjamin J.; Ou, Jian Zhen; Clark, Rhiannon M.; Berean, Kyle J.; Zavabeti, Ali; Chesman, Anthony S. R.; Russo, Salvy P.; Lau, Desmond W. M.; Xu, Zai-Quan; Bao, Qiaoliang; Kevehei, Omid; Gibson, Brant C.; Dickey, Michael D.; Kaner, Richard B.; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-02-01

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (~1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals.

PubMed

Carey, Benjamin J; Ou, Jian Zhen; Clark, Rhiannon M; Berean, Kyle J; Zavabeti, Ali; Chesman, Anthony S R; Russo, Salvy P; Lau, Desmond W M; Xu, Zai-Quan; Bao, Qiaoliang; Kevehei, Omid; Gibson, Brant C; Dickey, Michael D; Kaner, Richard B; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-02-17

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

Atomic layer deposition of magnesium fluoride via bis(ethylcyclopentadienyl)magnesium and anhydrous hydrogen fluoride

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

Hennessy, John, E-mail: hennessy@caltech.edu; Jewell, April D.; Greer, Frank

2015-01-15

A new process has been developed to deposit magnesium fluoride (MgF{sub 2}) thin films via atomic layer deposition (ALD) for use as optical coatings in the ultraviolet. MgF{sub 2} was deposited in a showerhead style ALD reactor using bis(ethylcyclopentadienyl)magnesium and anhydrous hydrogen fluoride (HF) as precursors at substrate temperatures from 100 to 250 °C. The use of HF was observed to result in improved morphology and reduced impurity content compared to other reported MgF{sub 2} ALD approaches that use metal fluoride precursors as the fluorine-containing chemistry. Characterization of these films has been performed using spectroscopic ellipsometry, atomic force microscopy, and x-raymore » photoelectron spectroscopy for material deposited on silicon substrates. Films at all substrate temperatures were transparent at wavelengths down to 190 nm and the low deposition temperature combined with low surface roughness makes these coatings good candidates for a variety of optical applications in the far ultraviolet.« less

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals

PubMed Central

Carey, Benjamin J.; Ou, Jian Zhen; Clark, Rhiannon M.; Berean, Kyle J.; Zavabeti, Ali; Chesman, Anthony S. R.; Russo, Salvy P.; Lau, Desmond W. M.; Xu, Zai-Quan; Bao, Qiaoliang; Kavehei, Omid; Gibson, Brant C.; Dickey, Michael D.; Kaner, Richard B.; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-01-01

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes. PMID:28211538

High process yield rates of thermoplastic nanofluidic devices using a hybrid thermal assembly technique.

PubMed

Uba, Franklin I; Hu, Bo; Weerakoon-Ratnayake, Kumuditha; Oliver-Calixte, Nyote; Soper, Steven A

2015-02-21

Over the past decade, thermoplastics have been used as alternative substrates to glass and Si for microfluidic devices because of the diverse and robust fabrication protocols available for thermoplastics that can generate high production rates of the desired structures at low cost and with high replication fidelity, the extensive array of physiochemical properties they possess, and the simple surface activation strategies that can be employed to tune their surface chemistry appropriate for the intended application. While the advantages of polymer microfluidics are currently being realized, the evolution of thermoplastic-based nanofluidic devices is fraught with challenges. One challenge is assembly of the device, which consists of sealing a cover plate to the patterned fluidic substrate. Typically, channel collapse or substrate dissolution occurs during assembly making the device inoperable resulting in low process yield rates. In this work, we report a low temperature hybrid assembly approach for the generation of functional thermoplastic nanofluidic devices with high process yield rates (>90%) and with a short total assembly time (16 min). The approach involves thermally sealing a high T(g) (glass transition temperature) substrate containing the nanofluidic structures to a cover plate possessing a lower T(g). Nanofluidic devices with critical feature sizes ranging between 25-250 nm were fabricated in a thermoplastic substrate (T(g) = 104 °C) and sealed with a cover plate (T(g) = 75 °C) at a temperature significantly below the T(g) of the substrate. Results obtained from sealing tests revealed that the integrity of the nanochannels remained intact after assembly and devices were useful for fluorescence imaging at high signal-to-noise ratios. The functionality of the assembled devices was demonstrated by studying the stretching and translocation dynamics of dsDNA in the enclosed thermoplastic nanofluidic channels.

Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation.

PubMed

Payne, Karl Ap; Quezada, Carolina P; Fisher, Karl; Dunstan, Mark S; Collins, Fraser A; Sjuts, Hanno; Levy, Colin; Hay, Sam; Rigby, Stephen Ej; Leys, David

2015-01-22

Organohalide chemistry underpins many industrial and agricultural processes, and a large proportion of environmental pollutants are organohalides. Nevertheless, organohalide chemistry is not exclusively of anthropogenic origin, with natural abiotic and biological processes contributing to the global halide cycle. Reductive dehalogenases are responsible for biological dehalogenation in organohalide respiring bacteria, with substrates including polychlorinated biphenyls or dioxins. Reductive dehalogenases form a distinct subfamily of cobalamin (B12)-dependent enzymes that are usually membrane associated and oxygen sensitive, hindering detailed studies. Here we report the characterization of a soluble, oxygen-tolerant reductive dehalogenase and, by combining structure determination with EPR (electron paramagnetic resonance) spectroscopy and simulation, show that a direct interaction between the cobalamin cobalt and the substrate halogen underpins catalysis. In contrast to the carbon-cobalt bond chemistry catalysed by the other cobalamin-dependent subfamilies, we propose that reductive dehalogenases achieve reduction of the organohalide substrate via halogen-cobalt bond formation. This presents a new model in both organohalide and cobalamin (bio)chemistry that will guide future exploitation of these enzymes in bioremediation or biocatalysis.

Surface immobilized azomethine for multiple component exchange.

PubMed

Lerond, Michael; Bélanger, Daniel; Skene, W G

2017-09-27

Diazonium chemistry concomitant with in situ electrochemical reduction was used to graft an aryl aldehyde to indium-tin oxide (ITO) coated glass substrates. This served as an anchor for preparing electroactive azomethines that were covalently bonded to the transparent electrode. The immobilized azomethines could undergo multiple step-wise component exchanges with different arylamines. The write-erase-write sequences were electrochemically confirmed. The azomethines could also be reversibly hydrolyzed. This was exploited for multiple azomethine-hydrolysis cycles resulting in discrete electroactive immobilized azomethines. The erase-rewrite sequences were also electrochemically confirmed.

Polyurethane acrylates as effective substrates for sustained in vitro culture of human myotubes.

PubMed

Andriani, Yosephine; Chua, Jason Min-Wen; Chua, Benjamin Yan-Jiang; Phang, In Yee; Shyh-Chang, Ng; Tan, Wui Siew

2017-07-15

Muscular disease has debilitating effects with severe damage leading to death. Our knowledge of muscle biology, disease and treatment is largely derived from non-human cell models, even though non-human cells are known to differ from human cells in their biochemical responses. Attempts to develop highly sought after in vitro human cell models have been plagued by early cell delamination and difficulties in achieving human myotube culture in vitro. In this work, we developed polyurethane acrylate (PUA) materials to support long-term in vitro culture of human skeletal muscle tissue. Using a constant base with modulated crosslink density we were able to vary the material modulus while keeping surface chemistry and roughness constant. While previous studies have focused on materials that mimic soft muscle tissue with stiffness ca. 12kPa, we investigated materials with tendon-like surface moduli in the higher 150MPa to 2.4GPa range, which has remained unexplored. We found that PUA of an optimal modulus within this range can support human myoblast proliferation, terminal differentiation and sustenance beyond 35days, without use of any extracellular protein coating. Results show that PUA materials can serve as effective substrates for successful development of human skeletal muscle cell models and are suitable for long-term in vitro studies. We developed polyurethane acrylates (PUA) to modulate the human skeletal muscle cell growth and maturation in vitro by controlling surface chemistry, morphology and tuning material's stiffness. PUA was able to maintain muscle cell viability for over a month without any detectable signs of material degradation. The best performing PUA prevented premature cell detachment from the substrate which often hampered long-term muscle cell studies. It also supported muscle cell maturation up to the late stages of differentiation. The significance of these findings lies in the possibility to advance studies on muscle cell biology, disease and therapy by using human muscle cells instead of relying on the widely used animal-based in vitro models. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Functionalization of Titanium with Chitosan via Silanation: Evaluation of Biological and Mechanical Performances

PubMed Central

Renoud, Pauline; Toury, Bérangère; Benayoun, Stéphane; Attik, Ghania; Grosgogeat, Brigitte

2012-01-01

Complications in dentistry and orthopaedic surgery are mainly induced by peri-implant bacterial infections and current implant devices do not prevent such infections. The coating of antibacterial molecules such as chitosan on its surface would give the implant bioactive properties. The major challenge of this type of coating is the attachment of chitosan to a metal substrate. In this study, we propose to investigate the functionalization of titanium with chitosan via a silanation. Firstly, the surface chemistry and mechanical properties of such coating were evaluated. We also verified if the coated chitosan retained its biocompatibility with the peri-implant cells, as well as its antibacterial properties. FTIR and Tof-SIMS analyses confirmed the presence of chitosan on the titanium surface. This coating showed great scratch resistance and was strongly adhesive to the substrate. These mechanical properties were consistent with an implantology application. The Chitosan-coated surfaces showed strong inhibition of Actinomyces naeslundii growth; they nonetheless showed a non significant inhibition against Porphyromonas gingivalis after 32 hours in liquid media. The chitosan-coating also demonstrated good biocompatibility to NIH3T3 fibroblasts. Thus this method of covalent coating provides a biocompatible material with improved bioactive properties. These results proved that covalent coating of chitosan has significant potential in biomedical device implantation. PMID:22859940

Chemistry of Sulfur-Contaminated Soil Substrate from a Former Frasch Extraction Method Sulfur Mine Leachate with Various Forms of Litter in a Controlled Experiment.

PubMed

Likus-Cieślik, Justyna; Pietrzykowski, Marcin; Chodak, Marcin

2018-01-01

The impact of tree litter on soil chemistry leachate and sulfurous substrates of mine soils from former Jeziórko sulfur mine was investigated. Composites were used: soil substrate (less contaminated at mean 5090 mg kg -1  S or high contaminated at 42,500 mg kg -1  S) + birch or pine litter and control substrate (no litter). The composites were rinsed with distilled water over 12 weeks. In the obtained leachate, pH, EC, dissolved organic carbon, N, Ca, Mg, Al, and S were determined. Physicochemical parameters of the substrates and their basal respiration rate were determined. Rinsing and litter application lowered sulfur concentration in high contamination substrates. Pine litter application decreased EC and increased pH of the low-contaminated substrate. The substrate pH remained at low phytotoxic level (i.e., below 3.0), resulting in the low biological activity of the composites. Birch litter application increased leaching of N and Mg, indicating the possibility of an intensification of soil-forming processes in contaminated sites.

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.

PEG-coated gold nanorod monoclonal antibody conjugates in preclinical research with optoacoustic tomography, photothermal therapy, and sensing

NASA Astrophysics Data System (ADS)

Liopo, Anton V.; Conjusteau, André; Oraevsky, Alexander A.

2012-02-01

Gold nanorods (GNR) with a peak absorption wavelength of 760 nm were prepared using a seed-mediated method. A novel protocol has been developed to replace hexadecyltrimethylammonium bromide (CTAB) on the surface of GNR with 16-mercaptohexadecanoic acid (MHDA) and metoxy-poly(ethylene glycol)-thiol (PEG), and the monoclonal antibodies: HER2 or CD33. The physical chemistry property of the conjugates was monitored through optical and zetapotential measurements to confirm surface chemistry. The plasmon resonance is kept in the near infrared area, and changes from strong positive charge for GNR-CTAB to slightly negative for GNR-PEG-mAb conjugates are observed. The conjugates were investigated for different cells lines: breast cancer cells and human leukemia lines in vivo applications. These results demonstrate successful tumor accumulation of our modified PEG-MHDA conjugates of GNR for HER2/neu in both overexpressed breast tumors in nude mice, and for thermolysis of human leukemia cells in vitro. The conjugates are non-toxic and can be used in pre-clinical applications, as well as molecular and optoacoustic imaging, and quantitative sensing of biological substrates.

Surface trimming of silicon photonics devices using controlled reactive ion etching chemistry

NASA Astrophysics Data System (ADS)

Chandran, S.; Das, B. K.

2015-06-01

Surface trimming of rib waveguides fabricated in 5-μm SOI substrate has been carried out successfully without any significant increase of propagation losses. A reactive ion etching chemistry has been optimized for trimming and an empirical model has been developed to obtain the resulting waveguide geometries. This technique has been used to demonstrate smaller footprint devices like multimode interference based power splitters and ring resonators after defining them photolithographically with relatively large cross-section rib waveguides. We have been also successful to fabricate 2D tapered spot-size converter useful for monolithic integration of waveguides with varying heights and widths. The taper length is again precisely controlled by photolithographic definition. Minimum insertion loss of such a spot-size converter integrated between waveguides with 3-μm height difference has been recorded to be ∼2 dB. It has been also shown that the overall fiber-to-chip coupling loss can be reduced by >3 dB by using such spot-size converters at the input/output side of the waveguides.

Chemical Interaction-Guided, Metal-Free Growth of Large-Area Hexagonal Boron Nitride on Silicon-Based Substrates.

PubMed

Behura, Sanjay; Nguyen, Phong; Debbarma, Rousan; Che, Songwei; Seacrist, Michael R; Berry, Vikas

2017-05-23

Hexagonal boron nitride (h-BN) is an ideal platform for interfacing with two-dimensional (2D) nanomaterials to reduce carrier scattering for high-quality 2D electronics. However, scalable, transfer-free growth of hexagonal boron nitride (h-BN) remains a challenge. Currently, h-BN-based 2D heterostructures require exfoliation or chemical transfer of h-BN grown on metals resulting in small areas or significant interfacial impurities. Here, we demonstrate a surface-chemistry-influenced transfer-free growth of large-area, uniform, and smooth h-BN directly on silicon (Si)-based substrates, including Si, silicon nitride (Si 3 N 4 ), and silicon dioxide (SiO 2 ), via low-pressure chemical vapor deposition. The growth rates increase with substrate electronegativity, Si < Si 3 N 4 < SiO 2 , consistent with the adsorption rates calculated for the precursor molecules via atomistic molecular dynamics simulations. Under graphene with high grain density, this h-BN film acts as a polymer-free, planar-dielectric interface increasing carrier mobility by 3.5-fold attributed to reduced surface roughness and charged impurities. This single-step, chemical interaction guided, metal-free growth mechanism of h-BN for graphene heterostructures establishes a potential pathway for the design of complex and integrated 2D-heterostructured circuitry.

Bioorthogonal chemistry: strategies and recent development

PubMed Central

Ramil, Carlo P.; Lin, Qing

2013-01-01

The use of covalent chemistry to track biomolecules in their native environment—a focus of bioorthogonal chemistry—has received considerable interests recently among chemical biologists and organic chemists alike. To facilitate wider adoption of bioorthogonal chemistry in biomedical research, a central effort in the last few years has been focused on the optimization of a few known bioorthogonal reactions, particularly with respective to reaction kinetics improvement, novel genetic encoding systems, and fluorogenic reactions for bioimaging. During these optimizations, three strategies have emerged, including the use of ring strain for substrate activation in the cycloaddition reactions, the discovery of new ligands and privileged substrates for accelerated metal-catalysed reactions, and the design of substrates with pre-fluorophore structures for rapid “turn-on” fluorescence after selective bioorthogonal reactions. In addition, new bioorthogonal reactions based on either modified or completely unprecedented reactant pairs have been reported. Finally, increasing attention has been directed toward the development of mutually exclusive bioorthogonal reactions and their applications in multiple labeling of a biomolecule in cell culture. In this feature article, we wish to present the recent progress in bioorthogonal reactions through the selected examples that highlight the above-mentioned strategies. Considering increasing sophistication in bioorthogonal chemistry development, we strive to project several exciting opportunities where bioorthogonal chemistry can make a unique contribution to biology in near future. PMID:24145483

Waterless TiO{sub 2} atomic layer deposition using titanium tetrachloride and titanium tetraisopropoxide

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

Anderson, Virginia R.; Cavanagh, Andrew S.; Abdulagatov, Aziz I.

2014-01-15

The surface chemistry for TiO{sub 2} atomic layer deposition (ALD) typically utilizes water or other oxidants that can oxidize underlying substrates such as magnetic disks or semiconductors. To avoid this oxidation, waterless or oxidant-free surface chemistry can be used that involves titanium halides and titanium alkoxides. In this study, waterless TiO{sub 2} ALD was accomplished using titanium tetrachloride (TiCl{sub 4}) and titanium tetraisopropoxide (TTIP). In situ transmission Fourier transform infrared (FTIR) studies were employed to study the surface species and the reactions during waterless TiO{sub 2} ALD. At low temperatures between 125 and 225  °C, the FTIR absorbance spectra revealed thatmore » the isopropoxide species remained on the surface after TTIP exposures. The TiCl{sub 4} exposures then removed the isopropoxide species and deposited additional titanium species. At high temperatures between 250 and 300  °C, the isopropoxide species were converted to hydroxyl species by β-hydride elimination. The observation of propene gaseous reaction product by quadrupole mass spectrometry (QMS) confirmed the β-hydride elimination reaction pathway. The TiCl{sub 4} exposures then easily reacted with the hydroxyl species. QMS studies also observed the 2-chloropropane and HCl gaseous reaction products and monitored the self-limiting nature of the TTIP reaction. Additional studies examined the waterless TiO{sub 2} ALD growth at low and high temperature. Quartz crystal microbalance measurements observed growth rates of ∼3 ng/cm{sup 2} at a low temperature of 150  °C. Much higher growth rates of ∼15 ng/cm{sup 2} were measured at a higher temperature of 250  °C under similar reaction conditions. X-ray reflectivity analysis measured a growth rate of 0.55 ± 0.05 Å/cycle at 250  °C. X-ray photoelectron depth-profile studies showed that the TiO{sub 2} films contained low Cl concentrations <1 at. %. This waterless TiO{sub 2} ALD process using TiCl{sub 4} and TTIP should be valuable to prevent substrate oxidation during TiO{sub 2} ALD on oxygen-sensitive substrates.« less

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.

Infrared spectroscopy and surface chemistry of beta-Ga(2)O(3) nanoribbons.

PubMed

Bermudez, V M; Prokes, S M

2007-12-04

The structure and surface chemistry of crystalline beta-Ga2O3 nanoribbons (NRs), deposited in a thin layer on various metallic and dielectric substrates (mainly on Au), have been characterized using vibrational spectroscopy. The results have been analyzed with the aid of a previous ab initio theoretical model for the beta-Ga2O3 surface structure. Raman spectra and normal-incidence infrared (IR) transmission data show little if any difference from corresponding results for bulk single crystals. For a layer formed on a metallic substrate, IR reflection-absorption spectroscopy (IRRAS) shows longitudinal-optic (LO) modes that are red-shifted by approximately 37 cm-1 relative to those of a bulk crystal. Evidence is also seen for a bonding interaction at the Ga2O3/Au interface following heating in room air. Polarization-modulated IRRAS has been used to study the adsorption of pyridine under steady-state conditions in ambient pressures as high as approximately 5 Torr. The characteristic nu19b and nu8a modes of adsorbed pyridine exhibit little or no shift from the corresponding gas-phase values. This indicates that the surface is only weakly acidic, consistent with the theoretical prediction that singly unsaturated octahedral Ga sites are the only reactive cation sites on the NR surface. However, evidence for adsorption at defect sites is seen in the form of more strongly shifted modes that saturate in intensity at low pyridine coverage. The effect of H atoms, formed by thermal cracking of H2, has also been studied. No Ga-H or O-H bonds are observed on the pristine NR surface. This suggests that the previously reported presence of such species on Ga2O3 powders heated in H2 is a result of a partial reduction of the oxide surface. The heat of adsorption of atomic H on the pristine beta-Ga2O3(100) surface at 0 K is computed to be -1.79 eV per H at saturation (average of Ga-H and O-H sites), whereas a value of +0.45 eV per H is found for the dissociative adsorption of H2. This suggests that rapid recombinative desorption of H2 may limit the coverage of chemisorbed H on this surface.

Desert Research and Technology Studies Exposure of Lotus Coated Electrodynamic Shield Samples. Part 2

NASA Technical Reports Server (NTRS)

Margiotta, Danielle V.; McKittrick, Kristin R.; Straka, Sharon A.; Jones, Craig B.

2012-01-01

The passive Lotus dust mitigation coating currently being developed at NASA's Goddard Space Flight Center (GSFC), was selected by the Habitation Demonstration Unit Deep Space Habitat (HDU-DSH) for participation in the 2011 Desert Research and Technology Studies (D-RaTS). Based on the unique surface architecture of the Lotus leaf, the nano-engineered Lotus coating seeks to replicate these structures on space flight and habitation surfaces. By decreasing both the surface energy and area for particle attachment, the Lotus coating greatly diminishes dust accumulation on surfaces. This is a problem that can be encountered on lunar, Martian, and asteroid missions. Two different application methods of this coating were tested in summer 2011 at the D-RaTS site: the wet chemistry applied version and combustion chemical vapor deposition (CCVD) applied version. These Lotus coatings, along with two common thermal control coatings, were combined with the active dust mitigation electrodynamic shield (EDS) technology developed at Kennedy Space Center (KSC). The EDS technology uses an electrified grid to remove dust particles from the surface of a Kapton (Trademark) substrate. The Lotus coating and thermal control coatings were applied to these Kapton (Trademark) substrates for testing. The combination of these two innovations was theorized to be an applicable countermeasure for addressing dust accumulation during long-duration human space exploration. This theory was tested and characterized prior to, during, and after D-RaTS exposure.

A chemical stability study of trimethylsilane plasma nanocoatings for coronary stents.

PubMed

Jones, John Eric; Yu, Qingsong; Chen, Meng

2017-01-01

Trimethylsilane (TMS) plasma nanocoatings were deposited onto stainless steel coupons in direct current (DC) and radio frequency (RF) glow discharges and additional NH 3 /O 2 plasma treatment to tailor the coating surface properties. The chemical stability of the nanocoatings were evaluated after 12 week storage under dry condition (25 °C) and immersion in simulated body fluid (SBF) at 37 °C. It was found that nanocoatings did not impact surface roughness of underlying stainless steel substrates. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were used to characterize surface chemistry and compositions. Both DC and RF nanocoatings had Si- and C-rich composition; and the O- and N-contents on the surfaces were substantially increased after NH 3 /O 2 plasma treatment. Contact angle measurements showed that DC-TMS nanocoating with NH 3 /O 2 treatment generated very hydrophilic surfaces. DC-TMS nanocoatings with NH 3 /O 2 treatment showed minimal surface chemistry change after 12 week immersion in SBF. However, nitrogen functionalities on RF-TMS coating with NH 3 /O 2 post treatment were not as stable as in DC case. Cell culture studies revealed that the surfaces with DC coating and NH 3 /O 2 post treatment demonstrated substantially improved proliferation of endothelial cells over the 12 week storage period at both dry and wet conditions, as compared to other coated surfaces. Therefore, DC nanocoatings with NH 3 /O 2 post treatment may be chemically stable for long-term properties, including shelf-life storage and exposure to the bloodstream for coronary stent applications.

Substrate-Directed Catalytic Selective Chemical Reactions.

PubMed

Sawano, Takahiro; Yamamoto, Hisashi

2018-05-04

The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

On the relationships between Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

DOE PAGES

Tang, J. Y.

2015-09-03

The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state formore » the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ] T of v with respect the total enzyme concentration [ E ] T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ] T of v with respect to the total substrate concentration [ S ] T. Meanwhile, the reverse Michaelis–Menten kinetics persistently under-predicts ∂ ln v / ∂ ln k 2 + and ∂ ln v / ∂ ln [ E ] T, and persistently over-predicts ∂ ln v / ∂ ln k 1 + and ∂ ln v / ∂ ln [ S ] T. In contrast, the Equilibrium Chemistry Approximation kinetics always gives consistent predictions of ∂ ln v / ∂ ln k 2 +, ∂ ln v / ∂ ln k 1 +, ∂ ln v / ∂ ln [ E ] T and ∂ ln v / ∂ ln [ S ] T. Since the Equilibrium Chemistry Approximation kinetics includes the advantages from both the Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics and it is applicable for almost the whole range of substrate and enzyme abundances, soil biogeochemical modelers therefore no longer need to choose when to use the Michaelis–Menten kinetics or the reverse Michaelis–Menten kinetics. I expect removing this choice ambiguity will make it easier to formulate more robust and consistent land biogeochemical models.« less

Mass Spectrometry to Identify New Biomarkers of Nerve Agent Exposure

DTIC Science & Technology

2008-04-01

of its structural chemistry using p-nitrophenyl esters as substrates. Pharm Res 21:285-292. Salvi A, Carrupt PA, Mayer JM and Testa B (1997) Esterase...Otagiri, M. (2004) Esterase-like activity of serum albumin: characterization of its structural chemistry using p-nitrophenyl esters as substrates. Pharm...The diethylphosphate group was found on Tyr 411 and Tyr 138. Annual report Oksana Lockridge W81XWH-07-2-0034 13 RESULTS The structures of the

Producing desired ice faces

PubMed Central

Shultz, Mary Jane; Brumberg, Alexandra; Bisson, Patrick J.; Shultz, Ryan

2015-01-01

The ability to prepare single-crystal faces has become central to developing and testing models for chemistry at interfaces, spectacularly demonstrated by heterogeneous catalysis and nanoscience. This ability has been hampered for hexagonal ice, Ih––a fundamental hydrogen-bonded surface––due to two characteristics of ice: ice does not readily cleave along a crystal lattice plane and properties of ice grown on a substrate can differ significantly from those of neat ice. This work describes laboratory-based methods both to determine the Ih crystal lattice orientation relative to a surface and to use that orientation to prepare any desired face. The work builds on previous results attaining nearly 100% yield of high-quality, single-crystal boules. With these methods, researchers can prepare authentic, single-crystal ice surfaces for numerous studies including uptake measurements, surface reactivity, and catalytic activity of this ubiquitous, fundamental solid. PMID:26512102

Membrane on a Chip: A Functional Tethered Lipid Bilayer Membrane on Silicon Oxide Surfaces

PubMed Central

Atanasov, Vladimir; Knorr, Nikolaus; Duran, Randolph S.; Ingebrandt, Sven; Offenhäusser, Andreas; Knoll, Wolfgang; Köper, Ingo

2005-01-01

Tethered membranes have been proven during recent years to be a powerful and flexible biomimetic platform. We reported in a previous article on the design of a new architecture based on the self-assembly of a thiolipid on ultrasmooth gold substrates, which shows extremely good electrical sealing properties as well as functionality of a bilayer membrane. Here, we describe the synthesis of lipids for a more modular design and the adaptation of the linker part to silane chemistry. We were able to form a functional tethered bilayer lipid membrane with good electrical sealing properties covering a silicon oxide surface. We demonstrate the functional incorporation of the ion carrier valinomycin and of the ion channel gramicidin. PMID:16127170

Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit

PubMed Central

2011-01-01

Self-assembled monolayer (SAM) with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry. PMID:21812994

Antibody immobilization on to polystyrene substrate--on-chip immunoassay for horse IgG based on fluorescence.

PubMed

Darain, Farzana; Gan, Kai Ling; Tjin, Swee Chuan

2009-06-01

A simple microfluidic immunoassay card was developed based on polystyrene (PS) substrate for the detection of horse IgG, an inexpensive model analyte using fluorescence microscope. The primary antibody was captured onto the PS based on covalent bonding via a self-assembled monolayer (SAM) of thiol to pattern the surface chemistry on a gold-coated PS. The immunosensor chip layers were fabricated from sheets by CO(2) laser ablation. The functionalized PS surfaces after each step were characterized by contact angle measurement, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). After the antibody-antigen interaction as a sandwich immunoassay with a fluorescein isothiocyanate (FITC)-conjugated secondary antibody, the intensity of fluorescence was measured on-chip to determine the concentration of the target analyte. The present immunosensor chip showed a linear response range for horse IgG between 1 microg/ml and 80 microg/ml (r = 0.971, n = 3). The detection limit was found to be 0.71 microg/ml. The developed microfluidic system can be extended for various applications including medical diagnostics, microarray detection and observing protein-protein interactions.

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

PubMed Central

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

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.

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].

The challenges of sequencing by synthesis.

PubMed

Fuller, Carl W; Middendorf, Lyle R; Benner, Steven A; Church, George M; Harris, Timothy; Huang, Xiaohua; Jovanovich, Stevan B; Nelson, John R; Schloss, Jeffery A; Schwartz, David C; Vezenov, Dmitri V

2009-11-01

DNA sequencing-by-synthesis (SBS) technology, using a polymerase or ligase enzyme as its core biochemistry, has already been incorporated in several second-generation DNA sequencing systems with significant performance. Notwithstanding the substantial success of these SBS platforms, challenges continue to limit the ability to reduce the cost of sequencing a human genome to $100,000 or less. Achieving dramatically reduced cost with enhanced throughput and quality will require the seamless integration of scientific and technological effort across disciplines within biochemistry, chemistry, physics and engineering. The challenges include sample preparation, surface chemistry, fluorescent labels, optimizing the enzyme-substrate system, optics, instrumentation, understanding tradeoffs of throughput versus accuracy, and read-length/phasing limitations. By framing these challenges in a manner accessible to a broad community of scientists and engineers, we hope to solicit input from the broader research community on means of accelerating the advancement of genome sequencing technology.

Peptide–Nanowire Hybrid Materials for Selective Sensing of Small Molecules

PubMed Central

McAlpine, Michael C.; Agnew, Heather D.; Rohde, Rosemary D.; Blanco, Mario; Ahmad, Habib; Stuparu, Andreea D.; Goddard, William A.

2013-01-01

The development of a miniaturized sensing platform for the selective detection of chemical odorants could stimulate exciting scientific and technological opportunities. Oligopeptides are robust substrates for the selective recognition of a variety of chemical and biological species. Likewise, semiconducting nanowires are extremely sensitive gas sensors. Here we explore the possibilities and chemistries of linking peptides to silicon nanowire sensors for the selective detection of small molecules. The silica surface of the nanowires is passivated with peptides using amide coupling chemistry. The peptide/nanowire sensors can be designed, through the peptide sequence, to exhibit orthogonal responses to acetic acid and ammonia vapors, and can detect traces of these gases from “chemically camouflaged” mixtures. Through both theory and experiment, we find that this sensing selectivity arises from both acid/base reactivity and from molecular structure. These results provide a model platform for what can be achieved in terms of selective and sensitive “electronic noses.” PMID:18576642

ZnO synthesis by high vacuum plasma-assisted chemical vapor deposition using dimethylzinc and atomic oxygen

NASA Astrophysics Data System (ADS)

Barnes, Teresa M.; Hand, Steve; Leaf, Jackie; Wolden, Colin A.

2004-09-01

Zinc oxide thin films were produced by high vacuum plasma-assisted chemical vapor deposition (HVP-CVD) from dimethylzinc (DMZn) and atomic oxygen. HVP-CVD is differentiated from conventional remote plasma-enhanced CVD in that the operating pressures of the inductively coupled plasma (ICP) source and the deposition chamber are decoupled. Both DMZn and atomic oxygen effuse into the deposition chamber under near collisionless conditions. The deposition rate was measured as a function of DMZn and atomic oxygen flux on glass and silicon substrates. Optical emission spectroscopy and quadrupole mass spectrometry (QMS) were used to provide real time analysis of the ICP source and the deposition chamber. The deposition rate was found to be first order in DMZn pressure and zero order in atomic oxygen density. All films demonstrated excellent transparency and were preferentially orientated along the c-axis. The deposition chemistry occurs exclusively through surface-mediated reactions, since the collisionless transport environment eliminates gas-phase chemistry. QMS analysis revealed that DMZn was almost completely consumed, and desorption of unreacted methyl radicals was greatly accelerated in the presence of atomic oxygen. Negligible zinc was detected in the gas phase, suggesting that Zn was efficiently consumed on the substrate and walls of the reactor.

A novel route to prepare a multilayer system via the combination of interface-mediated catalytic chain transfer polymerization and thiol-ene click chemistry.

PubMed

Zengin, Adem; Caykara, Tuncer

2017-05-01

Herein, we have designed a novel multilayer system composed of poly(methyl methacrylate) [poly(MMA)] brush, biotin, streptavidin and protein-A on a silicon substrate to attach onanti-immunoglobulin G (anti-IgG). poly(MMA) brush with vinyl end-group was first synthesized by the interface-mediated catalytic chain transfer polymerization. The brush was then modified with cysteamine molecules to generate the polymer chains with amine end-group via a thiol-ene click chemistry. The amine end-groups of poly(MMA) chains were also modified with biotin units to ensure selective connection points for streptavidin molecules. Finally, a multilayer system on the silicon substrate was formed by using streptavidin and protein-A molecules, respectively. This multilayer system was employed to attach anti-IgG molecules in a highly oriented manner and provide anti-IgG molecular functional configuration on the multilayer. High reproducibility of the amount of anti-IgG adsorption and homogeneous anti-IgG adsorption layer on the silicon surface could be provided by this multilayer system. The multilayer system with protein A may be opened the door for designing an efficient immunoassay protein chip. Copyright © 2017. Published by Elsevier B.V.

Conformal Robotic Stereolithography

PubMed Central

Stevens, Adam G.; Oliver, C. Ryan; Kirchmeyer, Matthieu; Wu, Jieyuan; Chin, Lillian; Polsen, Erik S.; Archer, Chad; Boyle, Casey; Garber, Jenna

2016-01-01

Abstract Additive manufacturing by layerwise photopolymerization, commonly called stereolithography (SLA), is attractive due to its high resolution and diversity of materials chemistry. However, traditional SLA methods are restricted to planar substrates and planar layers that are perpendicular to a single-axis build direction. Here, we present a robotic system that is capable of maskless layerwise photopolymerization on curved surfaces, enabling production of large-area conformal patterns and the construction of conformal freeform objects. The system comprises an industrial six-axis robot and a custom-built maskless projector end effector. Use of the system involves creating a mesh representation of the freeform substrate, generation of a triangulated toolpath with curved layers that represents the target object to be printed, precision mounting of the substrate in the robot workspace, and robotic photopatterning of the target object by coordinated motion of the robot and substrate. We demonstrate printing of conformal photopatterns on spheres of various sizes, and construction of miniature three-dimensional objects on spheres without requiring support features. Improvement of the motion accuracy and development of freeform toolpaths would enable construction of polymer objects that surpass the size and support structure constraints imparted by traditional SLA systems. PMID:29577062

Insights into the mechanism and catalysis of oxime coupling chemistry at physiological pH.

PubMed

Wang, Shujiang; Gurav, Deepanjali; Oommen, Oommen P; Varghese, Oommen P

2015-04-07

The dynamic covalent-coupling reaction involving α-effect nucleophiles has revolutionized bioconjugation approaches, due to its ease and high efficiency. Key to its success is the discovery of aniline as a nucleophilic catalyst, which made this reaction feasible under physiological conditions. Aniline however, is not so effective for keto substrates. Here, we investigate the mechanism of aniline activation in the oxime reaction with aldehyde and keto substrates. We also present carboxylates as activating agents that can promote the oxime reaction with both aldehyde and keto substrates at physiological pH. This rate enhancement circumvents the influence of α-effect by forming H-bonds with the rate-limiting intermediate, which drives the reaction to completion. The combination of aniline and carboxylates had a synergistic effect, resulting in a ∼14-31-fold increase in reaction rate at pD 7.4 with keto substrates. The biocompatibility and efficiency of carboxylate as an activating agent is demonstrated by performing cell-surface oxime labeling at physiological pH using acetate, which showed promising results that were comparable with aniline. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Automated scanning probe lithography with n-alkanethiol self assembled monolayers on Au(111): Application for teaching undergraduate laboratories

PubMed Central

Brown, Treva T.; LeJeune, Zorabel M.; Liu, Kai; Hardin, Sean; Li, Jie-Ren; Rupnik, Kresimir; Garno, Jayne C.

2010-01-01

Controllers for scanning probe instruments can be programmed for automated lithography to generate desired surface arrangements of nanopatterns of organic thin films, such as n-alkanethiol self-assembled monolayers (SAMs). In this report, atomic force microscopy (AFM) methods of lithography known as nanoshaving and nanografting are used to write nanopatterns within organic thin films. Commercial instruments provide software to control the length, direction, speed, and applied force of the scanning motion of the tip. For nanoshaving, higher forces are applied to an AFM tip to selectively remove regions of the matrix monolayer, exposing bare areas of the gold substrate. Nanografting is accomplished by force-induced displacement of molecules of a matrix SAM, followed immediately by the surface self-assembly of n-alkanethiol molecules from solution. Advancements in AFM automation enable rapid protocols for nanolithography, which can be accomplished within the tight time restraints of undergraduate laboratories. Example experiments with scanning probe lithography (SPL) will be described in this report that were accomplished by undergraduate students during laboratory course activities and research internships in the chemistry department of Louisiana State University. Students were introduced to principles of surface analysis and gained “hands-on” experience with nanoscale chemistry. PMID:21483651

Modeling of the oxygen reduction reaction for dense LSM thin films

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

Yang, Tao; Liu, Jian; Yu, Yang

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE PAGES

Yang, Tao; Liu, Jian; Yu, Yang; ...

2017-10-17

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Simple realization of efficient barrier performance of a single layer silicon nitride film via plasma chemistry.

PubMed

Lee, Jun Suk; Sahu, Bibhuti Bhusan; Han, Jeon Geon

2016-11-30

Due to the problem of degradation by moisture or oxygen, there is growing interest in efficient gas diffusion barriers for organic optoelectronic devices. Additionally, for the continuous and long-term operation of a device, dedicated flexible thin film encapsulation is required, which is the foremost challenge. Many efforts are being undertaken in the plasma assisted deposition process control for the optimization of film properties. Control of the plasma density along with the energy of the principal plasma species is critical to inducing alteration of the plasma reactivity, chemistry, and film properties. Here, we have used the radio frequency (RF) plasma enhanced chemical vapor deposition (PECVD) technique to deposit amorphous silicon nitride (SiN x ) barrier films onto a plastic substrate at different pressures. A large part of our efforts is devoted to a detailed study of the process parameters controlling the plasma treatment. Numerous plasma diagnostic techniques combined with various characterization tools are purposefully used to characterize and investigate the plasma environment and the associated film properties. This contribution also reports a study of the correlations between the plasma chemistry and the chemical, mechanical, barrier, and optical properties of the deposited films. The data reveal that the film possesses a very low stress for the condition where the net energy imparted on the substrate is at a minimum. Simultaneously, a relatively high ion flux and high energy of the ions impinging on the film growth surfaces are crucial for controlling the film stress and the resulting barrier properties.

Investigating the interplay between substrate stiffness and ligand chemistry in directing mesenchymal stem cell differentiation within 3D macro-porous substrates.

PubMed

Haugh, Matthew G; Vaughan, Ted J; Madl, Christopher M; Raftery, Rosanne M; McNamara, Laoise M; O'Brien, Fergal J; Heilshorn, Sarah C

2018-07-01

Dimensionality can have a profound impact on stiffness-mediated differentiation of mesenchymal stem cells (MSCs). However, while we have begun to understand cellular response when encapsulated within 3D substrates, the behavior of cells within macro-porous substrates is relatively underexplored. The goal of this study was to determine the influence of macro-porous topographies on stiffness-mediated differentiation of MSCs. We developed macro-porous recombinant elastin-like protein (ELP) substrates that allow independent control of mechanical properties and ligand chemistry. We then used computational modeling to probe the impact of pore topography on the mechanical stimulus that cells are exposed to within these substrates, and finally we investigated stiffness induced biases towards adipogenic and osteogenic differentiation of MSCs within macro-porous substrates. Computational modeling revealed that there is significant heterogeneity in the mechanical stimuli that cells are exposed to within porous substrates and that this heterogeneity is predominantly due to the wide range of possible cellular orientations within the pores. Surprisingly, MSCs grown within 3D porous substrates respond to increasing substrate stiffness by up-regulating both osteogenesis and adipogenesis. These results demonstrate that within porous substrates the behavior of MSCs diverges from previously observed responses to substrate stiffness, emphasizing the importance of topography as a determinant of cellular behavior. Copyright © 2018 Elsevier Ltd. All rights reserved.

Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation

PubMed Central

Fisher, Karl; Dunstan, Mark S; Collins, Fraser A; Sjuts, Hanno; Levy, Colin; Hay, Sam; Rigby, Stephen EJ; Leys, David

2015-01-01

Organohalide chemistry underpins many industrial and agricultural processes, and a large proportion of environmental pollutants are organohalides1. Nevertheless, organohalide chemistry is not exclusively of anthropogenic origin, with natural abiotic and biological processes contributing to the global halide cycle2–3. Reductive dehalogenases are responsible for biological dehalogenation in organohalide respiring bacteria4–5, with substrates including the notorious polychlorinated biphenyls (PCBs) or dioxins6–7. These proteins form a distinct subfamily of cobalamin (B12) dependent enzymes that are usually membrane-associated and oxygen-sensitive, hindering detailed studies8–12. We report the characterisation of a soluble, oxygen-tolerant reductive dehalogenase and, by combining structure determination with EPR spectroscopy and simulation, show that a direct interaction between the cobalamin cobalt and the substrate halogen underpins catalysis. In contrast to the carbon-Co bond chemistry catalyzed by the other cobalamin-dependent subfamilies13 we propose that reductive dehalogenases achieve reduction of the organohalide substrate via halogen-Co bond formation. This presents a new paradigm in both organohalide and cobalamin (bio)chemistry that will guide future exploitation of these enzymes in bioremediation or biocatalysis. PMID:25327251

Surface engineering approaches to micropattern surfaces for cell-based assays.

PubMed

Falconnet, Didier; Csucs, Gabor; Grandin, H Michelle; Textor, Marcus

2006-06-01

The ability to produce patterns of single or multiple cells through precise surface engineering of cell culture substrates has promoted the development of cellular bioassays that provide entirely new insights into the factors that control cell adhesion to material surfaces, cell proliferation, differentiation and molecular signaling pathways. The ability to control shape and spreading of attached cells and cell-cell contacts through the form and dimension of the cell-adhesive patches with high precision is important. Commitment of stem cells to different specific lineages depends strongly on cell shape, implying that controlled microenvironments through engineered surfaces may not only be a valuable approach towards fundamental cell-biological studies, but also of great importance for the design of cell culture substrates for tissue engineering. Furthermore, cell patterning is an important tool for organizing cells on transducers for cell-based sensing and cell-based drug discovery concepts. From a material engineering standpoint, patterning approaches have greatly profited by combining microfabrication technologies, such as photolithography, with biochemical functionalization to present to the cells biological cues in spatially controlled regions where the background is rendered non-adhesive ("non-fouling") by suitable chemical modification. The focus of this review is on the surface engineering aspects of biologically motivated micropatterning of two-dimensional (flat) surfaces with the aim to provide an introductory overview and critical assessment of the many techniques described in the literature. In particular, the importance of non-fouling surface chemistries, the combination of hard and soft lithography with molecular assembly techniques as well as a number of less well known, but useful patterning approaches, including direct cell writing, are discussed.

Pollenkitt wetting mechanism enables species-specific tunable pollen adhesion.

PubMed

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

2013-03-05

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

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

Managing oils pumplessly on open surfaces

NASA Astrophysics Data System (ADS)

Ghosh, Aritra; Morrissette, Jared; Mates, Joseph; Megaridis, Constantine

2017-11-01

Passive management of low-surface-tension liquids (e.g. oils) can be achieved by tuning curvature of liquid volumes (Laplace pressure) on juxtaposed oleophobic/oleophilic domains. Recent advancements in material chemistry in repelling low-surface-tension liquids has enabled researchers to fabricate surfaces and transport oils without the aid of gravity or using a pump. Liquid transport on such surfaces harnesses the force arising from the spatial contrast of surface energy on the substrate, providing rapid fluid actuation. In this work, we demonstrate and study the liquid transport dynamics (velocity, acceleration) in open air for several oils of interest (Jet A, hexadecane, mineral oil) with varying surface tension and viscosity. High-speed image analysis of the motion of the bulk liquid is performed using a droplet-shape tracking algorithm; dominant forces are identified and model predictions are compared with experimental data. Experimental and analytical tools offer new insight on a problem that is relevant to open-surface passive oil transport devices like propellant management devices, oil tankers and many more. Office of Naval Research, Air Force Research Laboratory.

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

PubMed

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

2014-02-01

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

On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

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

Tang, J. Y.

The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate concentration [ S] T. Meanwhile, the reverse Michaelis–Menten kinetics persistently underpredicts ∂ ln v / ∂ ln k 2 + and ∂ ln v / ∂ ln [ E] T, and persistently overpredicts ∂ ln v / ∂ ln k 1 + and ∂ ln v / ∂ ln [ S] T. In contrast, the equilibrium chemistry approximation kinetics always gives consistent predictions of ∂ ln v / ∂ ln k 2 +, ∂ ln v / ∂ ln k 1 +, ∂ ln v / ∂ ln [ E] T, and ∂ ln v / ∂ ln [ S] T, indicating that ECA-based models will be more calibratable if the modeled processes do obey the law of mass action. Since the equilibrium chemistry approximation kinetics includes advantages from both the Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics and it is applicable for almost the whole range of substrate and enzyme abundances, land biogeochemical modelers therefore no longer need to choose when to use the Michaelis–Menten kinetics or the reverse Michaelis–Menten kinetics. I expect that removing this choice ambiguity will make it easier to formulate more robust and consistent land biogeochemical models.« less

On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

DOE PAGES

Tang, J. Y.

2015-12-01

The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate concentration [ S] T. Meanwhile, the reverse Michaelis–Menten kinetics persistently underpredicts ∂ ln v / ∂ ln k 2 + and ∂ ln v / ∂ ln [ E] T, and persistently overpredicts ∂ ln v / ∂ ln k 1 + and ∂ ln v / ∂ ln [ S] T. In contrast, the equilibrium chemistry approximation kinetics always gives consistent predictions of ∂ ln v / ∂ ln k 2 +, ∂ ln v / ∂ ln k 1 +, ∂ ln v / ∂ ln [ E] T, and ∂ ln v / ∂ ln [ S] T, indicating that ECA-based models will be more calibratable if the modeled processes do obey the law of mass action. Since the equilibrium chemistry approximation kinetics includes advantages from both the Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics and it is applicable for almost the whole range of substrate and enzyme abundances, land biogeochemical modelers therefore no longer need to choose when to use the Michaelis–Menten kinetics or the reverse Michaelis–Menten kinetics. I expect that removing this choice ambiguity will make it easier to formulate more robust and consistent land biogeochemical models.« less

The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings

PubMed Central

Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

2017-01-01

Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders’ concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings. PMID:28243071

The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings.

PubMed

Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

2017-01-01

Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders' concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings.

Improving bioactivity of inert bioceramics by a novel Mg-incorporated solution treatment

NASA Astrophysics Data System (ADS)

Dehestani, Mahdi; Zemlyanov, Dmitry; Adolfsson, Erik; Stanciu, Lia A.

2017-12-01

Zirconia/alumina ceramics possess outstanding mechanical properties for dental and orthopedic applications, but due to their poor surface bioactivities they exhibit a weak bone-bonding ability. This work proposes an effective 30-min solution treatment which could successfully induce formation of bone-like apatite on the surface of 3Y-TZP and a ternary composite composed of yttria-stabilized zirconia, ceria-stabilized zirconia, and alumina (35 vol% 3Y-TZP + 35 vol% 12Ce-TZP + 30 vol% Al2O3) after 3 weeks immersion in simulated body fluid (SBF). XRD was used for phase identification in the ceramic materials. The influence of solution treatment on the surface chemistry and its role on apatite formation were investigated via SEM, EDS and XPS. In vitro apatite-forming ability for the solution-treated and untreated samples of the composite and individual substrates of 3Y-TZP, 12Ce-TZP, and Al2O3 was evaluated by immersion in SBF. Apatite crystals were formed only on 3Y-TZP and composite substrates, implying that it is mainly the 3Y-TZP constituent that contributes to the bioactivity of the composite. Further, it was found from the XPS analysis that the zirconia material with higher phase stability (12Ce-TZP) produced less Zrsbnd OH functional groups on its surface after solution treatment which accounts for its weaker bioactivity compared to 3Y-TZP.

Zirconium-based conversion film formation on zinc, aluminium and magnesium oxides and their interactions with functionalized molecules

NASA Astrophysics Data System (ADS)

Fockaert, L. I.; Taheri, P.; Abrahami, S. T.; Boelen, B.; Terryn, H.; Mol, J. M. C.

2017-11-01

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.

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.).

Suspension chemistry and electrophoretic deposition of zirconia electrolyte on conducting and non-conducting substrates

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

Das, Debasish; Basu, Rajendra N., E-mail: rnbasu@cgcri.res.in

2013-09-01

Graphical abstract: - Highlights: • Stable suspension of yttria stabilized zirconia (YSZ) obtained in isopropanol medium. • Suspension chemistry and process parameters for electrophoretic deposition optimized. • Deposited film quality changed with iodine and water (dispersants) concentration. • Dense YSZ film (∼5 μm) fabricated onto non-conducting porous NiO-YSZ anode substrate. - Abstract: Suspensions of 8 mol% yttria stabilized zirconia (YSZ) particulates in isopropanol medium are prepared using acetylacetone, iodine and water as dispersants. The effect of dispersants concentration on suspension stability, particle size distribution, electrical conductivity and pH of the suspensions are studied in detail to optimize the suspension chemistry.more » Electrophoretic deposition (EPD) has been conducted to produce thin and dense YSZ electrolyte films. Deposition kinetics have been studied in depth and good quality films on conducting substrate are obtained at an applied voltage of 15 V for 3 min. YSZ films are also fabricated on non-conducting NiO-YSZ anode substrate using a steel plate on the reverse side of the substrate. Upon co-firing at 1400 °C for 6 h a dense YSZ film of thickness ∼5 μm is obtained. Such a half cell (anode + electrolyte) can be used to fabricate a solid oxide fuel cell on applying a suitable cathode layer.« less

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Click chemistry modification of natural keratin fibers for sustained shrink-resist performance.

PubMed

Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

2015-01-01

This paper introduces a novel chemical treatment for achieving sustained shrink-resist performance on natural keratin fibers. The new treatment involves the controlled reduction of keratin in the cuticle region of the fiber, and the application of a water soluble diacrylate, namely glycerol 1,3-diglycerolate diacrylate (GDA), on the reduced keratin substrate. The acrylate groups of the GDA react with cysteine residues in the reduced keratin through thiol-ene click reactions at room temperature, leading to GDA grafting and the formation of GDA crosslinks in the keratin structure. The modified substrates were characterized by infrared spectroscopy and scanning electron microscopy, and assessed for its shrink-resistance and wet burst strength. This chemical modification has shown to alter the fiber surface morphology and hydrophilicity, resulting in substantially improved shrink-resistance with good fiber strength retention. Possible shrink-resistance mechanisms were also discussed. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Modification of Semiconductor Surfaces through Si-N Linkages by Wet-Chemistry Approaches and Modular Functionalization of Zinc Oxide Surfaces for Chemical Protection of Material Morphology

NASA Astrophysics Data System (ADS)

Gao, Fei

Semiconductor substrates are widely used in many applications. Multiple practical uses involving these materials require the ability to tune their physical and chemical properties to adjust those to a specific application. In recent years, surface and interface reactions have affected dramatically device fabrication and material design. Novel surface functionalization techniques with diverse chemical approaches make the desired physical, thermal, electrical, and mechanical properties attainable. Meanwhile, the modified surface can serve as one of the most important key steps for further assembly process in order to make novel devices and materials. In the following chapters, novel chemical approaches to the functionalization of silicon and zinc oxide substrates will be reviewed and discussed. The specific functionalities including amines, azides, and alkynes on surfaces of different materials will be applied to address subsequent attachment of large molecules and assembly processes. This research is aimed to develop new strategies for manipulating the surface properties of semiconductor materials in a controlled way. The findings of these investigations will be relevant for future applications in molecular and nanoelectronics, sensing, and solar energy conversion. The ultimate goals of the projects are: 1) Preparation of an oxygen-and carbon-free silicon surface based exclusively on Si-N linkages for further modification protocols.. This project involves designing the surface reaction of hydrazine on chlorine-terminated silicon surface, introduction of additional functional group through dehydrohalogenation condensation reaction and direct covalent attachment of C60. 2) Demonstrating alternative method to anchor carbon nanotubes to solid substrates directly through the carbon cage.. This project targets surface modification of silicon and gold substrates with amine-terminated organic monolayers and the covalent attachment of nonfunctionalized and carboxylic acid-functionalized carbon nanotubes. 3) Designing a universal method for the modular functionalization of zinc oxide surface for the chemical protection of material morphology.. This project involves surface modification of zinc oxide nanopowder under vacuum condition with propiolic acid, followed by "click" reaction. A combination of spectroscopy and microscopy techniques was utilized to study the surface functionalization and assembly processes. Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and time of fight secondary ion mass spectroscopy (ToF-SIMS) were employed to elucidate the chemical structure of the modified surface. Atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were combined to obtain the surface morphological information. Density functional theory (DFT) calculations were applied to confirm the experimental results and to suggest plausible reaction mechanisms. Other complementary techniques for these projects also include nuclear magnetic resonance (NMR) spectroscopy to identify the chemical species on the surface and charge-carrier lifetime measurements to evaluate the electronic property of C60-modified silicon surface.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Oxidation and reduction under cover: Chemistry at the confined space between ultra-thin nanoporous silicates and Ru(0001)

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

J. Anibal Boscoboinik; Zhong, Jian -Qiang; Kestell, John

2016-03-23

The oxidation and reduction of Ru(0001) surfaces at the confined space between two-dimensional nanoporous silica frameworks and Ru(0001) have been investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). The porous nature of the frameworks and the weak interaction between the silica and the ruthenium substrate allow oxygen and hydrogen molecules to go through the nanopores and react with the metal at the interface between the silica framework and the metal surface. In this work, three types of two-dimensional silica frameworks have been used to study their influence in the oxidation and reduction of the ruthenium surface at elevated pressuresmore » and temperatures. These frameworks are bilayer silica (0.5 nm thick), bilayer aluminosilicate (0.5 nm thick), and zeolite MFI nanosheets (3 nm thick). It is found that the silica frameworks stay essentially intact under these conditions, but they strongly affect the oxidation of ruthenium, with the 0.5 nm thick aluminosilicate bilayer completely inhibiting the oxidation. Furthermore, the latter is believed to be related to the lower chemisorbed oxygen content arising from electrostatic interactions between the negatively charged aluminosilicate framework and the Ru(0001) substrate.« less

A Molecular Smart Surface for Spatio-Temporal Studies of Cell Mobility

PubMed Central

Lee, Eun-ju; Luo, Wei; Chan, Eugene W. L.; Yousaf, Muhammad N.

2015-01-01

Active migration in both healthy and malignant cells requires the integration of information derived from soluble signaling molecules with positional information gained from interactions with the extracellular matrix and with other cells. How a cell responds and moves involves complex signaling cascades that guide the directional functions of the cytoskeleton as well as the synthesis and release of proteases that facilitate movement through tissues. The biochemical events of the signaling cascades occur in a spatially and temporally coordinated manner then dynamically shape the cytoskeleton in specific subcellular regions. Therefore, cell migration and invasion involve a precise but constantly changing subcellular nano-architecture. A multidisciplinary effort that combines new surface chemistry and cell biological tools is required to understand the reorganization of cytoskeleton triggered by complex signaling during migration. Here we generate a class of model substrates that modulate the dynamic environment for a variety of cell adhesion and migration experiments. In particular, we use these dynamic substrates to probe in real-time how the interplay between the population of cells, the initial pattern geometry, ligand density, ligand affinity and integrin composition affects cell migration and growth. Whole genome microarray analysis indicates that several classes of genes ranging from signal transduction to cytoskeletal reorganization are differentially regulated depending on the nature of the surface conditions. PMID:26030281

40 CFR 230.11 - Factual determinations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... the physical, chemical, and biological components of the aquatic environment in light of subparts C... including downstream flows, and normal water fluctuation. Consideration shall be given to water chemistry... characteristics and elevation, water or substrate chemistry, nutrients, currents, circulation, fluctuation, and...

40 CFR 230.11 - Factual determinations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... the physical, chemical, and biological components of the aquatic environment in light of subparts C... including downstream flows, and normal water fluctuation. Consideration shall be given to water chemistry... characteristics and elevation, water or substrate chemistry, nutrients, currents, circulation, fluctuation, and...

40 CFR 230.11 - Factual determinations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... the physical, chemical, and biological components of the aquatic environment in light of subparts C... including downstream flows, and normal water fluctuation. Consideration shall be given to water chemistry... characteristics and elevation, water or substrate chemistry, nutrients, currents, circulation, fluctuation, and...

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

PubMed

Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

2015-10-20

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

Hollow Nanospheres Array Fabrication via Nano-Conglutination Technology.

PubMed

Zhang, Man; Deng, Qiling; Xia, Liangping; Shi, Lifang; Cao, Axiu; Pang, Hui; Hu, Song

2015-09-01

Hollow nanospheres array is a special nanostructure with great applications in photonics, electronics and biochemistry. The nanofabrication technique with high resolution is crucial to nanosciences and nano-technology. This paper presents a novel nonconventional nano-conglutination technology combining polystyrenes spheres (PSs) self-assembly, conglutination and a lift-off process to fabricate the hollow nanospheres array with nanoholes. A self-assembly monolayer of PSs was stuck off from the quartz wafer by the thiol-ene adhesive material, and then the PSs was removed via a lift-off process and the hollow nanospheres embedded into the thiol-ene substrate was obtained. Thiolene polymer is a UV-curable material via "click chemistry" reaction at ambient conditions without the oxygen inhibition, which has excellent chemical and physical properties to be attractive as the adhesive material in nano-conglutination technology. Using the technique, a hollow nanospheres array with the nanoholes at the diameter of 200 nm embedded into the rigid thiol-ene substrate was fabricated, which has great potential to serve as a reaction container, catalyst and surface enhanced Raman scattering substrate.

Structural and elastoplastic properties of β -Ga2O3 films grown on hybrid SiC/Si substrates

NASA Astrophysics Data System (ADS)

Osipov, A. V.; Grashchenko, A. S.; Kukushkin, S. A.; Nikolaev, V. I.; Osipova, E. V.; Pechnikov, A. I.; Soshnikov, I. P.

2018-04-01

Structural and mechanical properties of gallium oxide films grown on (001), (011) and (111) silicon substrates with a buffer layer of silicon carbide are studied. The buffer layer was fabricated by the atom substitution method, i.e., one silicon atom per unit cell in the substrate was substituted by a carbon atom by chemical reaction with carbon monoxide. The surface and bulk structure properties of gallium oxide films have been studied by atomic-force microscopy and scanning electron microscopy. The nanoindentation method was used to investigate the elastoplastic characteristics of gallium oxide, and also to determine the elastic recovery parameter of the films under study. The ultimate tensile strength, hardness, elastic stiffness constants, elastic compliance constants, Young's modulus, linear compressibility, shear modulus, Poisson's ratio and other characteristics of gallium oxide have been calculated by quantum chemistry methods based on the PBESOL functional. It is shown that all these properties of gallium oxide are essentially anisotropic. The calculated values are compared with experimental data. We conclude that a change in the silicon orientation leads to a significant reorientation of gallium oxide.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Synthesis and processing of ELISA polymer substitute: The influence of surface chemistry and morphology on detection sensitivity

NASA Astrophysics Data System (ADS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Rothan, Hussin A.; Yusof, Rohana; van der Marel, Cees; Koole, Leo H.

2014-10-01

Despite the known drawbacks of enzyme-linked immunosorbent assay (ELISA), one of the deficiencies that have relatively been ignored is the performance of ELISA substrate itself. Polystyrene (PS), as the cost effective material of choice for mass production of ELISA well-plates, has shown obvious lacks of suitable physical and chemical properties for protein attachment. The general concept of this work was to develop a potential substrate that can be suggested as a material of choice for production of a new generation of ELISA analytical kits. Spin-coated thin films of polymethyl methacrylate-co-methacrylic acid (PMMA-co-MAA) on silicon surfaces were designed and processed for detection of dengue virus. Coated surfaces of different molar ratios have been investigated as carboxyl-functionalized layers for obtaining platform for biomolecule immobilization with high level of protein activity. To improve the sensitivity of detection, we have used amine functional "spacers", hexamethylenediamine (HMDA) and polyethyleneimine (PEI), which were covalently bonded to the surfaces of PMMA-co-MAA coatings. Results demonstrate that the variation of surface concentration of carboxyl groups of PMMA-co-MAA can be used to control the amine surface concentration after carbodiimide coupling with HMDA and PEI spacers. The presence of amine spacers increases hydrophilicity of the coatings and significantly impacts the polymer surface morphology. In particular, protein immobilization via amine-bearing spacers has been achieved in two effective steps: (1) carbodiimide bonding between amine spacer molecules and PMMA-co-MAA polymer coatings; and (2) covalent immobilization of antibody via glutaraldehyde reaction with amine groups from amine-treated surfaces. The application of PEI spacer in comparison to HMDA has shown much higher intensity of detection signal in ELISA experiment, indicating better immobilization efficiency and preservation of antibody activity upon attachment to the polymer surface.

Nanoscale definition of substrate materials to direct human adult stem cells towards tissue specific populations.

PubMed

Curran, Judith M; Chen, Rui; Stokes, Robert; Irvine, Eleanor; Graham, Duncan; Gubbins, Earl; Delaney, Deany; Amro, Nabil; Sanedrin, Raymond; Jamil, Haris; Hunt, John A

2010-03-01

The development of homogenously nano-patterned chemically modified surfaces that can be used to initiate a cellular response, particularly stem cell differentiation, in a highly controlled manner without the need for exogenous biological factors has never been reported, due to that fact that precisely defined and reproducible systems have not been available that can be used to study cell/material interactions and unlock the potential of a material driven cell response. Until now material driven stem cell (furthermore any cell) responses have been variable due to the limitations in definition and reproducibility of the underlying substrate and the lack of true homogeneity of modifications that can dictate a cellular response at a sub-micron level that can effectively control initial cell interactions of all cells that contact the surface. Here we report the successful design and use of homogenously molecularly nanopatterned surfaces to control initial stem cell adhesion and hence function. The highly specified nano-patterned arrays were compared directly to silane modified bulk coated substrates that have previously been proven to initiate mesenchymal stem cell (MSC) differentiation in a heterogenous manner, the aim of this study was to prove the efficiency of these previously observed cell responses could be enhanced by the incorporation of nano-patterns. Nano-patterned surfaces were prepared by Dip Pen Nanolithography (DPN) to produce arrays of 70 nm sized dots separated by defined spacings of 140, 280 and 1000 nm with terminal functionalities of carboxyl, amino, methyl and hydroxyl and used to control cell growth. These nanopatterned surfaces exhibited unprecedented control of initial cell interactions and will change the capabilities for stem cell definition in vitro and then cell based medical therapies. In addition to highlighting the ability of the materials to control stem cell functionality on an unprecedented scale this research also introduces the successful scale-up of DPN and the novel chemistries and systems to facilitate the production of homogeneously patterned substrates (5 mm2) that are applicable for use in in vitro cell conditions over prolonged periods for complete control of material driven cell responses.

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level.

PubMed

Park, Joon B; Graciani, Jesus; Evans, Jaime; Stacchiola, Dario; Ma, Shuguo; Liu, Ping; Nambu, Akira; Sanz, Javier Fernández; Hrbek, Jan; Rodriguez, José A

2009-03-31

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO(2)(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeO(x)/TiO(2)(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce(3+) oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO(2)(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H(2)O + CO --> H(2) + CO(2)) or for the oxidation of carbon monoxide (2CO + O(2) --> 2CO(2)). The enhanced stability of the Ce(3+) state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

Plateau-Rayleigh Crystal Growth of Nanowire Heterostructures: Strain-Modified Surface Chemistry and Morphological Control in One, Two, and Three Dimensions.

PubMed

Day, Robert W; Mankin, Max N; Lieber, Charles M

2016-04-13

One-dimensional (1D) structures offer unique opportunities for materials synthesis since crystal phases and morphologies that are difficult or impossible to achieve in macroscopic crystals can be synthesized as 1D nanowires (NWs). Recently, we demonstrated one such phenomenon unique to growth on a 1D substrate, termed Plateau-Rayleigh (P-R) crystal growth, where periodic shells develop along a NW core to form diameter-modulated NW homostructures with tunable morphologies. Here we report a novel extension of the P-R crystal growth concept with the synthesis of heterostructures in which Ge (Si) is deposited on Si (Ge) 1D cores to generate complex NW morphologies in 1, 2, or 3D. Depositing Ge on 50 nm Si cores with a constant GeH4 pressure yields a single set of periodic shells, while sequential variation of GeH4 pressure can yield multimodulated 1D NWs with two distinct sets of shell periodicities. P-R crystal growth on 30 nm cores also produces 2D loop structures, where Ge (Si) shells lie primarily on the outside (inside) of a highly curved Si (Ge) core. Systematic investigation of shell morphology as a function of growth time indicates that Ge shells grow in length along positive curvature Si cores faster than along straight Si cores by an order of magnitude. Short Ge deposition times reveal that shells develop on opposite sides of 50 and 100 nm Si cores to form straight 1D morphologies but that shells develop on the same side of 20 nm cores to produce 2D loop and 3D spring structures. These results suggest that strain mediates the formation of 2 and 3D morphologies by altering the NW's surface chemistry and that surface diffusion of heteroatoms on flexible freestanding 1D substrates can facilitate this strain-mediated mechanism.

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1972

1972-01-01

Short articles on the kinetics of the hydrogen peroxide-iodide ion reaction, simulation of fluidization catalysis, the use of Newman projection diagrams to represent steric relationships in organic chemistry, the use of synthetic substrates for proteolytic enzyme reactions, and two simple clock reactions"--hydrolysis of halogenoalkanes and…

Alkylamine capped metal nanoparticle "inks" for printable SERS substrates, electronics and broadband photodetectors.

PubMed

Polavarapu, Lakshminarayana; Manga, Kiran Kumar; Yu, Kuai; Ang, Priscilla Kailian; Cao, Hanh Duyen; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua

2011-05-01

We report a facile and general method for the preparation of alkylamine capped metal (Au and Ag) nanoparticle "ink" with high solubility. Using these metal nanoparticle "inks", we have demonstrated their applications for large scale fabrication of highly efficient surface enhanced Raman scattering (SERS) substrates by a facile solution processing method. These SERS substrates can detect analytes down to a few nM. The flexible plastic SERS substrates have also been demonstrated. The annealing temperature dependent conductivity of the nanoparticle films indicated a transition temperature above which high conductivity was achieved. The transition temperature could be tailored to the plastic compatible temperatures by using proper alkylamine as the capping agent. The ultrafast electron relaxation studies of the nanoparticle films demonstrated that faster electron relaxation was observed at higher annealing temperatures due to stronger electronic coupling between the nanoparticles. The applications of these highly concentrated alkylamine capped metal nanoparticle inks for the printable electronics were demonstrated by printing the oleylamine capped gold nanoparticles ink as source and drain for the graphene field effect transistor. Furthermore, the broadband photoresponse properties of the Au and Ag nanoparticle films have been demonstrated by using visible and near-infrared lasers. These investigations demonstrate that these nanoparticle "inks" are promising for applications in printable SERS substrates, electronics, and broadband photoresponse devices. © The Royal Society of Chemistry 2011

Biofilm attachment reduction on bioinspired, dynamic, micro-wrinkling surfaces

NASA Astrophysics Data System (ADS)

Epstein, Alexander K.; Hong, Donggyoon; Kim, Philseok; Aizenberg, Joanna

2013-09-01

Most bacteria live in multicellular communities known as biofilms that are adherent to surfaces in our environment, from sea beds to plumbing systems. Biofilms are often associated with clinical infections, nosocomial deaths and industrial damage such as bio-corrosion and clogging of pipes. As mature biofilms are extremely challenging to eradicate once formed, prevention is advantageous over treatment. However, conventional surface chemistry strategies are either generally transient, due to chemical masking, or toxic, as in the case of leaching marine antifouling paints. Inspired by the nonfouling skins of echinoderms and other marine organisms, which possess highly dynamic surface structures that mechanically frustrate bio-attachment, we have developed and tested a synthetic platform based on both uniaxial mechanical strain and buckling-induced elastomer microtopography. Bacterial biofilm attachment to the dynamic substrates was studied under an array of parameters, including strain amplitude and timescale (1-100 mm s-1), surface wrinkle length scale, bacterial species and cell geometry, and growth time. The optimal conditions for achieving up to ˜ 80% Pseudomonas aeruginosa biofilm reduction after 24 h growth and ˜ 60% reduction after 48 h were combinatorially elucidated to occur at 20% strain amplitude, a timescale of less than ˜ 5 min between strain cycles and a topography length scale corresponding to the cell dimension of ˜ 1 μm. Divergent effects on the attachment of P. aeruginosa, Staphylococcus aureus and Escherichia coli biofilms showed that the dynamic substrate also provides a new means of species-specific biofilm inhibition, or inversely, selection for a desired type of bacteria, without reliance on any toxic or transient surface chemical treatments.

Characterization of Carboxylic Acid Reductases as Enzymes in the Toolbox for Synthetic Chemistry.

PubMed

Finnigan, William; Thomas, Adam; Cromar, Holly; Gough, Ben; Snajdrova, Radka; Adams, Joseph P; Littlechild, Jennifer A; Harmer, Nicholas J

2017-03-20

Carboxylic acid reductase enzymes (CARs) meet the demand in synthetic chemistry for a green and regiospecific route to aldehydes from their respective carboxylic acids. However, relatively few of these enzymes have been characterized. A sequence alignment with members of the ANL (Acyl-CoA synthetase/ NRPS adenylation domain/Luciferase) superfamily of enzymes shed light on CAR functional dynamics. Four unstudied enzymes were selected by using a phylogenetic analysis of known and hypothetical CARs, and for the first time, a thorough biochemical characterization was performed. Kinetic analysis of these enzymes with various substrates shows that they have a broad but similar substrate specificity. Electron-rich acids are favored, which suggests that the first step in the proposed reaction mechanism, attack by the carboxylate on the α-phosphate of adenosine triphosphate (ATP), is the step that determines the substrate specificity and reaction kinetics. The effects of pH and temperature provide a clear operational window for the use of these CARs, whereas an investigation of product inhibition by NADP + , adenosine monophosphate, and pyrophosphate indicates that the binding of substrates at the adenylation domain is ordered with ATP binding first. This study consolidates CARs as important and exciting enzymes in the toolbox for sustainable chemistry and provides specifications for their use as a biocatalyst.

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces

NASA Technical Reports Server (NTRS)

Cross, Jon B.

1990-01-01

Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

UV activation of polymeric high aspect ratio microstructures: ramifications in antibody surface loading for circulating tumor cell selection.

PubMed

Jackson, Joshua M; Witek, Małgorzata A; Hupert, Mateusz L; Brady, Charles; Pullagurla, Swathi; Kamande, Joyce; Aufforth, Rachel D; Tignanelli, Christopher J; Torphy, Robert J; Yeh, Jen Jen; Soper, Steven A

2014-01-07

The need to activate thermoplastic surfaces using robust and efficient methods has been driven by the fact that replication techniques can be used to produce microfluidic devices in a high production mode and at low cost, making polymer microfluidics invaluable for in vitro diagnostics, such as circulating tumor cell (CTC) analysis, where device disposability is critical to mitigate artifacts associated with sample carryover. Modifying the surface chemistry of thermoplastic devices through activation techniques can be used to increase the wettability of the surface or to produce functional scaffolds to allow for the covalent attachment of biologics, such as antibodies for CTC recognition. Extensive surface characterization tools were used to investigate UV activation of various surfaces to produce uniform and high surface coverage of functional groups, such as carboxylic acids in microchannels of different aspect ratios. We found that the efficiency of the UV activation process is highly dependent on the microchannel aspect ratio and the identity of the thermoplastic substrate. Colorimetric assays and fluorescence imaging of UV-activated microchannels following EDC/NHS coupling of Cy3-labeled oligonucleotides indicated that UV-activation of a PMMA microchannel with an aspect ratio of ~3 was significantly less efficient toward the bottom of the channel compared to the upper sections. This effect was a consequence of the bulk polymer's damping of the modifying UV radiation due to absorption artifacts. In contrast, this effect was less pronounced for COC. Moreover, we observed that after thermal fusion bonding of the device's cover plate to the substrate, many of the generated functional groups buried into the bulk rendering them inaccessible. The propensity of this surface reorganization was found to be higher for PMMA compared to COC. As an example of the effects of material and microchannel aspect ratios on device functionality, thermoplastic devices for the selection of CTCs from whole blood were evaluated, which required the immobilization of monoclonal antibodies to channel walls. From our results, we concluded the CTC yield and purity of isolated CTCs were dependent on the substrate material with COC producing the highest clinical yields for CTCs as well as better purities compared to PMMA.

Hydroxylation of organic polymer surface: method and application.

PubMed

Yang, Peng; Yang, Wantai

2014-03-26

It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.

Microbial trace fossils in Antarctica and the search for evidence of early life on Mars

NASA Technical Reports Server (NTRS)

Friedmann, E. Imre; Friedmann, Roseli O.

1989-01-01

It is possible to hypothesize that, if microbial life evolved on early Mars, fossil remnants of these organisms may be preserved on the surface. However, the cooling and drying of Mars probably resembled a cold desert and such an environment is not suitable for the process of fossilization. The frigid Ross Desert of Antarctica is probably the closest terrestrial analog to conditions that may have prevailed on the surface of the cooling and drying Mars. In this desert, cryptoendolithic microbial communities live in the airspaces of porous rocks, the last habitable niche in a hostile outside environment. The organisms produce characteristic chemical and physical changes in the rock substrate. Environmental changes (deterioration of conditions) may result in the death of the community. Although no cellular structures are fossilized, the conspicuous changes in the rock substrate are preserved as trace fossils. Likewise, microbial trace fossils (without cellular structures) may also be preserved on Mars: Discontinuities in structure or chemistry of the rock that are independent of physical or chemical gradients may be of biological origin. Ross Desert trace fossils can be used as a model for planning search strategies and for instrument design to find evidence of past Martian life.

Electrochemical study on the corrosion resistance of plasma nanocoated 316L stainless steel in albumin- and lysozyme-containing electrolytes

PubMed Central

Jones, John Eric; Chen, Meng; Chou, Ju; Yu, Qingsong

2017-01-01

The physiological corrosion resistance of plasma nanocoated 316L stainless steel was studied in protein-containing electrolytes using electrochemical methods. Plasma nanocoatings with thicknesses of 20–30 nm were deposited onto 316L stainless steel coupons in a glow discharge of trimethylsilane (TMS) or its mixture with oxygen gas under various gas ratios. The surface chemistries of the plasma nanocoatings were characterized using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Corrosion properties of the plasma nanocoated 316L stainless steel coupons were assessed using potentiodynamic polarization, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) in phosphate-buffered saline (PBS) electrolytes that contain bovine serum albumin (BSA) or lysozyme. It was found that BSA adsorption on the plasma nanocoated 316L coupons was heavily favored. BSA adsorption on the plasma nanocoating surfaces could block charge-transfer reactions between the electrolyte and 316L substrate, and thus stabilize the 316L substrates from further corrosion. In contrast, lysozyme adsorption on the plasma nanocoated specimens was not as pronounced and mildly influenced the corrosion properties of the plasma nanocoated 316L stainless steel. PMID:29422723

Controlling the Morphology of Side Chain Liquid Crystalline Block Copolymer Thin Films through Variations in Liquid Crystalline Content

PubMed Central

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T.

2009-01-01

In this paper we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the inter-material dividing surface (IMDS). By manipulating the strength of these interactions the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nano-patterning applications without manipulation of the surface chemistry or the application of external fields. PMID:18763835

Protein-releasing conductive anodized alumina membranes for nerve-interface materials.

PubMed

Altuntas, Sevde; Buyukserin, Fatih; Haider, Ali; Altinok, Buket; Biyikli, Necmi; Aslim, Belma

2016-10-01

Nanoporous anodized alumina membranes (AAMs) have numerous biomedical applications spanning from biosensors to controlled drug delivery and implant coatings. Although the use of AAM as an alternative bone implant surface has been successful, its potential as a neural implant coating remains unclear. Here, we introduce conductive and nerve growth factor-releasing AAM substrates that not only provide the native nanoporous morphology for cell adhesion, but also induce neural differentiation. We recently reported the fabrication of such conductive membranes by coating AAMs with a thin C layer. In this study, we investigated the influence of electrical stimulus, surface topography, and chemistry on cell adhesion, neurite extension, and density by using PC 12 pheochromocytoma cells in a custom-made glass microwell setup. The conductive AAMs showed enhanced neurite extension and generation with the electrical stimulus, but cell adhesion on these substrates was poorer compared to the naked AAMs. The latter nanoporous material presents chemical and topographical features for superior neuronal cell adhesion, but, more importantly, when loaded with nerve growth factor, it can provide neurite extension similar to an electrically stimulated CAAM counterpart. Copyright © 2016 Elsevier B.V. All rights reserved.

Microplasma generator and methods therefor

DOEpatents

Hopwood, Jeffrey A

2015-04-14

A low-temperature, atmospheric-pressure microplasma generator comprises at least one strip of metal on a dielectric substrate. A first end of the strip is connected to a ground plane and the second end of the strip is adjacent to a grounded electrode, with a gap being defined between the second end of the strip and the grounded electrode. High frequency power is supplied to the strip. The frequency is selected so that the length of the strip is an odd integer multiple of 1/4 of the wavelength traveling on the strip. A microplasma forms in the gap between the second end of the strip and the grounded electrode due to electric fields in that region. A microplasma generator array comprises a plurality of strongly-coupled resonant strips in close proximity to one another. At least one of the strips has an input for high-frequency electrical power. The remaining strips resonate due to coupling from the at least one powered strip. The array can provide a continuous line or ring of plasma. The microplasma generator can be used to alter the surface of a substrate, such as by adding material (deposition), removal of material (etching), or modifying surface chemistry.

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content.

PubMed

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T

2008-10-01

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface. By manipulating the strength of these interactions, the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nanopatterning applications without manipulation of the surface chemistry or the application of external fields.

Deposition and disinfection of Escherichia coli O157:H7 on naturally occurring photoactive materials in a parallel plate chamber†

PubMed Central

Taylor, Alicia A.; Chowdhury, Indranil; Gong, Amy S.; Cwiertny, David M.; Walker, Sharon L.

2014-01-01

Dissolved organic matter in combination with iron oxides has been shown to facilitate photochemical disinfection through the production of reactive oxygen species (ROS) under UV and visible light. However, due to the extremely short lifetime of these radicals, the disinfection effciency is limited by the successful transport of ROS to bacterial surfaces. This study was designed to quantitatively investigate three collector surfaces with various potentials to produce ROS [bare quartz, hematite (α-Fe2O3) coated quartz, and Suwannee River humic acid (SRHA)] and the effects of extracellular polymeric substance (EPS) (full or partial coating) and solution chemistry (ionic strength, IS) on the interactions between bacteria and the ROS-producing substrates. With few exceptions, bacterial deposition studies in a parallel plate (PP) flow chamber have revealed increasing cell adhesion with IS. Furthermore, interactions between collector surfaces and cells can be explained by electrostatic forces, with negatively charged SRHA reducing and positively charged α-Fe2O3 enhancing bacterial deposition significantly. Increased deposition was also observed with full EPS content, indicating the ability of EPS to facilitate interaction between cells and surfaces in the aquatic environment. In complementary disinfection studies conducted with simulated light, viability loss was observed for cells fully coated with EPS when attached to α-Fe2O3 under all IS conditions. Based upon our prior study in which EPS was found to not inhibit hydroxyl radical activity toward bacteria, we proposed that EPS might therefore promote disinfection by facilitating cell attachment to ROS-producing surfaces where higher concentrations of ROS are expected at closer proximities to reactive substrates (e.g., SRHA and α-Fe2O3). Our findings on the mechanism and controlling factors of cell interactions with photoactive substrates provide insight as to the role of ionic strength in photochemical disinfection processes. PMID:24362649

Nanoscale Compositional Relations in Lunar Rock Patina: Deciphering Sources for Patina Components on an Apollo 17 Station 6 Boulder

NASA Technical Reports Server (NTRS)

Christoffersen, R.; Noble, S. K.; Keller, L. P.

2014-01-01

Space weathering on the Moon and other airless bodies modifies the surfaces of regolith grains as well as the space-exposed surfaces of larger rocks and boulders. As space weathering witness plates, rocks and boulders are distinguished from regolith grains based on their ability to persist as physically intact substrates over longer time scales before being disaggregated by impact processes. Because lunar surfaces, including exposed rocks, quickly develop an optically thick layer of patina, it is important to understand the compositional relationship between patinas and their underlying rock substrates, particularly to support remote-sensing of rocky lunar terrains. Based on analytical TEM techniques, supported by focused ion beam (FIB) cross-sectioning, we have begun to systematize the multi-layer microstructural complexity of patinas on rock samples with a range of space exposure histories. Our on-going work has particularly focused on lunar rock 76015, both because it has a long (approx. 22 my) exposure history, and because its surface was exposed to patina development approximately 1 m off the regolith surface on a boulder in the Apollo 17 Station 6 boulder field. Potential sources for the 76015 patina therefore include impact-melted and vaporized material derived from the local rock substrate, as well as from the mix of large boulders and regolith in the Station 6 area. While similar, there are differences in the mineralogy and chemistry of the rocks and regolith at Station 6. We were interested to see if these, or other sources, could be distinguished in the average composition, as well as the compositional nanostratigraphy of the 76015 patina. To date we have acquired a total of 9 TEM FIB cross-sections from the 76015 patina, giving us reasonable confidence of being able to arrive at an integrated average for the patina major element composition based on analytical TEM methods.

Ion implantation modified stainless steel as a substrate for hydroxyapatite deposition. Part I. Surface modification and characterization.

PubMed

Pramatarova, L; Pecheva, E; Krastev, V; Riesz, F

2007-03-01

Material surfaces play critical role in biology and medicine since most biological reactions occur on surfaces and interfaces. There are many examples showing that the surface properties of the materials control and are directly involved in biological reactions and processes in-vitro like blood compatibility, protein absorption, cell development, etc. The rules that govern the diversity of biological surface phenomenon are fundamental physical laws. Stainless steel doped with Cr, Ni and Mo is widely used material in medicine and dentistry due to its excellent corrosion resistance and mechanical properties. The interest in this material has stimulated extensive studies on improving its bone-bonding properties. This paper describes the surface modification of Cr-Ni stainless steel (AISI 316) by a whole surface sequential implantation of Ca and P ions (the basic ions of hydroxyapatite). Three groups of stainless steel samples are prepared: (i) ion-implanted, (ii) ion-implanted and thermally treated at 600( composite function)C in air for 1 h and (iii) initials. The surface chemistry and topography before and after the surface modification are characterized by X-ray photoelectron spectroscopy, Auger electron spectroscopy, magic mirror method, atomic force microscopy and contact angle measurements.

Substrate quality alters the microbial mineralization of added substrate and soil organic carbon

NASA Astrophysics Data System (ADS)

Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Schaeffer, S. M.

2014-09-01

The rate and extent of decomposition of soil organic carbon (SOC) is dependent, among other factors, on substrate chemistry and microbial dynamics. Our objectives were to understand the influence of substrate chemistry on microbial decomposition of carbon (C), and to use model fitting to quantify differences in pool sizes and mineralization rates. We conducted an incubation experiment for 270 days using four uniformly labeled 14C substrates (glucose, starch, cinnamic acid and stearic acid) on four different soils (a temperate Mollisol, a tropical Ultisol, a sub-arctic Andisol, and an arctic Gelisol). The 14C labeling enabled us to separate CO2 respired from added substrates and from native SOC. Microbial gene copy numbers were quantified at days 4, 30 and 270 using quantitative polymerase chain reaction (qPCR). Substrate C respiration was always higher for glucose than other substrates. Soils with cinnamic and stearic acid lost more native SOC than glucose- and starch-amended soils. Cinnamic and stearic acid amendments also exhibited higher fungal gene copy numbers at the end of incubation compared to unamended soils. We found that 270 days were sufficient to model the decomposition of simple substrates (glucose and starch) with three pools, but were insufficient for more complex substrates (cinnamic and stearic acid) and native SOC. This study reveals that substrate quality exerts considerable control on the microbial decomposition of newly added and native SOC, and demonstrates the need for multi-year incubation experiments to constrain decomposition parameters for the most recalcitrant fractions of SOC and complex substrates.

Substrate quality alters microbial mineralization of added substrate and soil organic carbon

NASA Astrophysics Data System (ADS)

Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Schaeffer, S. M.

2014-03-01

The rate and extent of decomposition of soil organic carbon (SOC) is dependent on substrate chemistry and microbial dynamics. Our objectives were to understand the influence of substrate chemistry on microbial processing of carbon (C), and to use model fitting to quantify differences in pool sizes and mineralization rates. We conducted an incubation experiment for 270 days using four uniformly-labeled 14C substrates (glucose, starch, cinnamic acid and stearic acid) on four different soils (a temperate Mollisol, a tropical Ultisol, a sub-arctic Andisol, and an arctic Gelisol). The 14C labeling enabled us to separate CO2 respired from added substrates and from native SOC. Microbial gene copy numbers were quantified at days 4, 30 and 270 using quantitative polymerase chain reaction (qPCR). Substrate C respiration was always higher for glucose than other substrates. Soils with cinnamic and stearic acid lost more native SOC than glucose- and starch-amended soils, despite an initial delay in respiration. Cinnamic and stearic acid amendments also exhibited higher fungal gene copy numbers at the end of incubation compared to unamended soils. We found that 270 days was sufficient to model decomposition of simple substrates (glucose and starch) with three pools, but was insufficient for more complex substrates (cinnamic and stearic acid) and native SOC. This study reveals that substrate quality imparts considerable control on microbial decomposition of newly added and native SOC, and demonstrates the need for multi-year incubation experiments to constrain decomposition parameters for the most recalcitrant fractions of SOC and added substrates.

Microbial Populations of Stony Meteorites: Substrate Controls on First Colonizers.

PubMed

Tait, Alastair W; Gagen, Emma J; Wilson, Siobhan A; Tomkins, Andrew G; Southam, Gordon

2017-01-01

Finding fresh, sterilized rocks provides ecologists with a clean slate to test ideas about first colonization and the evolution of soils de novo. Lava has been used previously in first colonizer studies due to the sterilizing heat required for its formation. However, fresh lava typically falls upon older volcanic successions of similar chemistry and modal mineral abundance. Given enough time, this results in the development of similar microbial communities in the newly erupted lava due to a lack of contrast between the new and old substrates. Meteorites, which are sterile when they fall to Earth, provide such contrast because their reduced and mafic chemistry commonly differs to the surfaces on which they land; thus allowing investigation of how community membership and structure respond to this new substrate over time. We conducted 16S rRNA gene analysis on meteorites and soil from the Nullarbor Plain, Australia. We found that the meteorites have low species richness and evenness compared to soil sampled from directly beneath each meteorite. Despite the meteorites being found kilometers apart, the community structure of each meteorite bore more similarity to those of other meteorites (of similar composition) than to the community structure of the soil on which it resided. Meteorites were dominated by sequences that affiliated with the Actinobacteria with the major Operational Taxonomic Unit (OTU) classified as Rubrobacter radiotolerans. Proteobacteria and Bacteroidetes were the next most abundant phyla. The soils were also dominated by Actinobacteria but to a lesser extent than the meteorites. We also found OTUs affiliated with iron/sulfur cycling organisms Geobacter spp. and Desulfovibrio spp. This is an important finding as meteorites contain abundant metal and sulfur for use as energy sources. These ecological findings demonstrate that the structure of the microbial community in these meteorites is controlled by the substrate, and will not reach homeostasis with the Nullarbor community, even after ca. 35,000 years. Our findings show that meteorites provide a unique, sterile substrate with which to test ideas relating to first-colonizers. Although meteorites are colonized by microorganisms, the microbial population is unlikely to match the community of the surrounding soil on which they fall.

Microbial Populations of Stony Meteorites: Substrate Controls on First Colonizers

PubMed Central

Tait, Alastair W.; Gagen, Emma J.; Wilson, Siobhan A.; Tomkins, Andrew G.; Southam, Gordon

2017-01-01

Finding fresh, sterilized rocks provides ecologists with a clean slate to test ideas about first colonization and the evolution of soils de novo. Lava has been used previously in first colonizer studies due to the sterilizing heat required for its formation. However, fresh lava typically falls upon older volcanic successions of similar chemistry and modal mineral abundance. Given enough time, this results in the development of similar microbial communities in the newly erupted lava due to a lack of contrast between the new and old substrates. Meteorites, which are sterile when they fall to Earth, provide such contrast because their reduced and mafic chemistry commonly differs to the surfaces on which they land; thus allowing investigation of how community membership and structure respond to this new substrate over time. We conducted 16S rRNA gene analysis on meteorites and soil from the Nullarbor Plain, Australia. We found that the meteorites have low species richness and evenness compared to soil sampled from directly beneath each meteorite. Despite the meteorites being found kilometers apart, the community structure of each meteorite bore more similarity to those of other meteorites (of similar composition) than to the community structure of the soil on which it resided. Meteorites were dominated by sequences that affiliated with the Actinobacteria with the major Operational Taxonomic Unit (OTU) classified as Rubrobacter radiotolerans. Proteobacteria and Bacteroidetes were the next most abundant phyla. The soils were also dominated by Actinobacteria but to a lesser extent than the meteorites. We also found OTUs affiliated with iron/sulfur cycling organisms Geobacter spp. and Desulfovibrio spp. This is an important finding as meteorites contain abundant metal and sulfur for use as energy sources. These ecological findings demonstrate that the structure of the microbial community in these meteorites is controlled by the substrate, and will not reach homeostasis with the Nullarbor community, even after ca. 35,000 years. Our findings show that meteorites provide a unique, sterile substrate with which to test ideas relating to first-colonizers. Although meteorites are colonized by microorganisms, the microbial population is unlikely to match the community of the surrounding soil on which they fall. PMID:28713354

On the influence of substrate morphology and surface area on phytofauna

USGS Publications Warehouse

Becerra-Munoz, S.; Schramm, H.L.

2007-01-01

The independent effects and interactions between substrate morphology and substrate surface area on invertebrate density or biomass colonizing artificial plant beds were assessed in a clear-water and a turbid playa lake in Castro County, Texas, USA. Total invertebrate density and biomass were consistently greater on filiform substrates than on laminar substrates with equivalent substrate surface areas. The relationship among treatments (substrates with different morphologies and surface areas) and response (invertebrate density or biomass) was assessed with equally spaced surface areas. Few statistically significant interactions between substrate morphology and surface area were detected, indicating that these factors were mostly independent from each other in their effect on colonizing invertebrates. Although infrequently, when substrate morphology and surface area were not independent, the effects of equally spaced changes in substrate surface area on the rate of change of phytofauna density or biomass per unit of substrate surface area were dependent upon substrate morphology. The absence of three-way interactions indicated that effects of substrate morphology and substrate area on phytofauna density or biomass were independent of environmental conditions outside and inside exclosures. ?? 2006 Springer Science+Business Media B.V.

Electrowetting for Digital Microfluidics

NASA Astrophysics Data System (ADS)

Hunt, Tom; Adamson, Kristi; Issadore, David; Westervelt, Robert

2006-03-01

Droplet based chemistry promises to greatly impact biomedical research, providing new avenues for high throughput, low volume assays such as drug screening. Electrowetting on Dielectric (EWOD) is an excellent technique for manipulating microscopic drops of liquid. EWOD uses buried electrodes to locally change the surface energy between a droplet and a substrate. We present microfabricated devices for moving droplets with EWOD. One example of such a device consists of a series of 16 interdigitated electrodes, decreasing in size from 1mm to 20 microns. Each electrode is addressable by an independent, computer controlled, high voltage supply. This work made possible by a gift from Phillip Morris and the NSEC NSF grant PHY-0117795.

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

NASA Technical Reports Server (NTRS)

Kress, M. E.; Tielens, A. G. G. M.; Roberge, W. G.

1998-01-01

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Engineering Extreme Hydrophobic and Super Slippery Water Shedding Surfaces

NASA Astrophysics Data System (ADS)

McHale, Glen

2017-04-01

The intrinsic water repellency of a material is fundamentally determined by its surface chemistry, but alone this does not determine the ability of a surface to shed water. Physical factors such as the surface texture/topography, rigidity/flexibility, granularity/porosity combined with the intrinsic wetting properties of the liquid with the surface and whether it is infused by a lubricating liquid are equally important. In this talk I will outline fundamental, but simple, ideas on the topographic enhancement of surface chemistry to create superhydrophobicity, the adhesion of particles to liquid-air interfaces to create liquid marbles, elastocapillarity to create droplet wrapping, and lubricant impregnated surfaces to create completely mobile droplets [1-3]. I will discuss how these ideas have their origins in natural systems and surfaces, such as Lotus leaves, galling aphids and the Nepenthes pitcher plant. I will show how we have applied these concepts to study the wetting of granular systems, such as sand, to understand extreme soil water repellency. I will argue that relaxing the assumption that a solid substrate is fixed in shape and arrangement, can lead to the formation of liquid marbles, whereby a droplet self-coats in a hydrophobic powder/grains. I will show that the concepts of wetting and porosity blur as liquids penetrate into a porous or granular substrate. I will also discuss how lubricant impregnated super slippery surfaces can be used to study a pure constant contact angle mode of droplet evaporation [4]. Finally, I will show dewetting of a surface is not simply a video reversal of wetting [5], and I will give an example of the use of perfect hydrophobicity using the Leidenfrost effect to create a new type of low friction mechanical and hear engine [6]. References: [1] Shirtcliffe, N. J., et al., An introduction to superhydrophobicity. Advances in Colloid and Interface Science, vol. 161, pp.124-138 (2010). [2] McHale, G. & Newton, M. I. Liquid marbles: topical context within soft matter and recent progress. Soft Matter, vol. 11, pp. 2530-2546 (2015). [3] Geraldi, N. R., et al., Capillary origami and superhydrophobic membrane surfaces. Applied Physics Letters, vol. 102, art. 214104 (2013). [4] Guan, J. H. et al., Evaporation of sessile droplets on Slippery Liquid-Infused Porous Surfaces (SLIPS). Langmuir, vol. 31, pp. 11781-11789 (2015). [5] Edwards, A. M. J., et al., Not spreading in reverse: The dewetting of a liquid film into a single drop. Science Advances, vol. 2, art. e1600183-e1600183 (2016). [6] Wells, G. G., et al., A sublimation heat engine. Nature Communications, vol. 6, art. 6390 (2015). Acknowledgement: This work has been financially supported by the UK EPSRC and Reece Innovation Ltd, and developed in collaboration with co-workers at Northumbria, Nottingham Trent, Edinburgh, Swansea and Durham Universities.

SUPECA kinetics for scaling redox reactions in networks of mixed substrates and consumers and an example application to aerobic soil respiration

NASA Astrophysics Data System (ADS)

Tang, Jin-Yun; Riley, William J.

2017-09-01

Several land biogeochemical models used for studying carbon-climate feedbacks have begun explicitly representing microbial dynamics. However, to our knowledge, there has been no theoretical work on how to achieve a consistent scaling of the complex biogeochemical reactions from microbial individuals to populations, communities, and interactions with plants and mineral soils. We focus here on developing a mathematical formulation of the substrate-consumer relationships for consumer-mediated redox reactions of the form A + BE→ products, where products could be, e.g., microbial biomass or bioproducts. Under the quasi-steady-state approximation, these substrate-consumer relationships can be formulated as the computationally difficult full equilibrium chemistry problem or approximated analytically with the dual Monod (DM) or synthesizing unit (SU) kinetics. We find that DM kinetics is scaling inconsistently for reaction networks because (1) substrate limitations are not considered, (2) contradictory assumptions are made regarding the substrate processing rate when transitioning from single- to multi-substrate redox reactions, and (3) the product generation rate cannot be scaled from one to multiple substrates. In contrast, SU kinetics consistently scales the product generation rate from one to multiple substrates but predicts unrealistic results as consumer abundances reach large values with respect to their substrates. We attribute this deficit to SU's failure to incorporate substrate limitation in its derivation. To address these issues, we propose SUPECA (SU plus the equilibrium chemistry approximation - ECA) kinetics, which consistently imposes substrate and consumer mass balance constraints. We show that SUPECA kinetics satisfies the partition principle, i.e., scaling invariance across a network of an arbitrary number of reactions (e.g., as in Newton's law of motion and Dalton's law of partial pressures). We tested SUPECA kinetics with the equilibrium chemistry solution for some simple problems and found SUPECA outperformed SU kinetics. As an example application, we show that a steady-state SUPECA-based approach predicted an aerobic soil respiration moisture response function that agreed well with laboratory observations. We conclude that, as an extension to SU and ECA kinetics, SUPECA provides a robust mathematical representation of complex soil substrate-consumer interactions and can be applied to improve Earth system model (ESM) land models.