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.

Impact of surface chemistry

PubMed Central

Somorjai, Gabor A.; Li, Yimin

2011-01-01

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

Size- and orientation-selective si nanowire growth: thermokinetic effects of nanoscale plasma chemistry.

PubMed

Mehdipour, Hamid; Ostrikov, Kostya Ken

2013-02-06

A multiscale, multiphase thermokinetic model is used to show the effective control of the growth orientation of thin Si NWs for nanoelectronic devices enabled by nanoscale plasma chemistry. It is shown that very thin Si NWs with [110] growth direction can nucleate at much lower process temperatures and pressures compared to thermal chemical vapor deposition where [111]-directed Si NWs are predominantly grown. These findings explain a host of experimental results and offer the possibility of energy- and matter-efficient, size- and orientation-controlled growth of [110] Si NWs for next-generation nanodevices.

Inflammatory cytokine response to titanium chemical composition and nanoscale calcium phosphate surface modification.

PubMed

Hamlet, Stephen; Ivanovski, Saso

2011-05-01

Nanoscale surface modification of titanium dental implants with calcium phosphate (CaP) has been shown to achieve superior bone wound healing and osseointegration compared with smooth or microrough titanium surfaces alone. As bone healing has been shown to be influenced by the action of cytokines, this study examined whether changes in cytokine gene expression from RAW 264.7 cells cultured on commercially pure and titanium alloy (Ti-6Al-4V) microrough or nanoscale crystalline CaP-modified surfaces, may influence downstream events in bone wound healing and osseointegration. Whilst no significant difference in the attachment or proliferation of RAW 264.7 cells was observed, the nanoscale CaP-modified surface elicited a gene expression profile with marked down-regulation of a number of pro-inflammatory cytokines and chemokines. Inflammatory cytokine gene expression was further influenced by chemical composition, with lower levels of pro-inflammatory markers noted following exposure of the macrophage-like cells to titanium alloy (Ti-6Al-4V) compared with the commercially pure titanium surface. Down-regulation of pro-inflammatory cytokine gene expression (confirmed at the protein level for TNFα and CCL5), may thus facilitate the enhanced bone wound healing and osseointegration observed clinically with nanoscale calcium phosphate-modified implant surfaces. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

Organic chemistry on solid surfaces

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zaera, Francisco

2006-07-01

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

Evaporation of nanoscale water on a uniformly complete wetting surface at different temperatures.

PubMed

Guo, Yuwei; Wan, Rongzheng

2018-05-03

The evaporation of nanoscale water films on surfaces affects many processes in nature and industry. Using molecular dynamics (MD) simulations, we show the evaporation of a nanoscale water film on a uniformly complete wetting surface at different temperatures. With the increase in temperature, the growth of the water evaporation rate becomes slow. Analyses show that the hydrogen bond (H-bond) lifetimes and orientational autocorrelation times of the outermost water film decrease slowly with the increase in temperature. Compared to a thicker water film, the H-bond lifetimes and orientational autocorrelation times of a monolayer water film are much slower. This suggests that the lower evaporation rate of the monolayer water film on a uniformly complete wetting surface may be caused by the constriction of the water rotation due to the substrate. This finding may be helpful for controlling nanoscale water evaporation within a certain range of temperatures.

Interlocked by nanoscale sculpturing: pure aluminum copper contacts (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gerngross-Baytekin, Melike; Gerngross, Mark Daniel; Carstensen, Jürgen; Adelung, Rainer

2017-06-01

Connecting metals reliable with different corrosion potential is a well-known challenge. An extreme example are copper aluminum contacts. Galvanic corrosion occurs if the two different metals are in contact with each other and an electrolyte, the aluminum becomes susceptible to corrosion under current flow. Usually, antioxidant pastes containing metals are employed but create difficulties e.g. for fatigue resistant power electronic connections. The recently described process of nanoscale sculpturing [1] offers an alternative. Usually, if the surface of metals like aluminium are prepared they are just arbitrary cuts through the bulk. There is no optimization of the surface grain structure towards stability at all. Neither the crystalline facets in the grains are in their most stable orientation nor is the protective oxide shell the most stable one. The nanoscale sculpturing approach is carving out the most stable grains and planes by chemical or electrochemical treatment. The decisive trick is that the chemistry is targeting towards the instable oxide and not the metal. Aluminium sample surfaces including alloys like AA575 exhibit afterwards single crystalline surface facets covered with nanoscale stable oxide films. Galvanically deposited copper forms extremely reliable interlocked connections on top, even allowing for soldering on top of their surface.

Early osteoblast responses to orthopedic implants: Synergy of surface roughness and chemistry of bioactive ceramic coating.

PubMed

Aniket; Reid, Robert; Hall, Benika; Marriott, Ian; El-Ghannam, Ahmed

2015-06-01

Pro-osteogenic stimulation of bone cells by bioactive ceramic-coated orthopedic implants is influenced by both surface roughness and material chemistry; however, their concomitant impact on osteoblast behavior is not well understood. The aim of this study is to investigate the effects of nano-scale roughness and chemistry of bioactive silica-calcium phosphate nanocomposite (SCPC50) coated Ti-6Al-4V on modulating early bone cell responses. Cell attachment was higher on SCPC50-coated substrates compared to the uncoated controls; however, cells on the uncoated substrate exhibited greater spreading and superior quality of F-actin filaments than cells on the SCPC50-coated substrates. The poor F-actin filament organization on SCPC50-coated substrates is thought to be due to the enhanced calcium uptake by the ceramic surface. Dissolution analyses showed that an increase in surface roughness was accompanied by increased calcium uptake, and increased phosphorous and silicon release, all of which appear to interfere with F-actin assembly and osteoblast morphology. Moreover, cell attachment onto the SCPC50-coated substrates correlated with the known adsorption of fibronectin, and was independent of surface roughness. High-throughput genome sequencing showed enhanced expression of extracellular matrix and cell differentiation related genes. These results demonstrate a synergistic relationship between bioactive ceramic coating roughness and material chemistry resulting in a phenotype that leads to early osteoblast differentiation. © 2014 Wiley Periodicals, Inc.

Coalescence-induced jumping of nanoscale droplets on super-hydrophobic surfaces

NASA Astrophysics Data System (ADS)

Liang, Zhi; Keblinski, Pawel; Nanoscale Science; Engineering Center Team

The coalescence-induced jumping of tens of microns size droplets on super-hydrophobic surfaces has been observed in both experiments and simulations. However, whether the coalescence-induced jumping would occur for smaller, particularly nanoscale droplets, is an open question. Using molecular dynamics simulations, we demonstrate that in spite of the large internal viscous dissipation, coalescence of two nanoscale droplets on a super-hydrophobic surface can result in a jumping of the coalesced droplet from the surface with a speed of a few m/s. Similar to the coalescence-induced jumping of microscale droplets, we observe that the bridge between the coalescing nano-droplets expands and impacts the solid surface, which leads to an acceleration of the coalesced droplet by the pressure force from the solid surface. We observe that the jumping velocity decreases with the droplet size and its ratio to the inertial-capillary velocity is a constant of about 0.126, which is close to the minimum value of 0.111 predicted by continuum-level modeling of Enright et al. [R. Enright, N. Miljkovic, J. Sprittles, K. Nolan, R. Mitchell, and E. N. Wang, ACS Nano 8, 10352 (2014)].

Fabrication of a highly oriented line structure on an aluminum surface and the nanoscale patterning on the nanoscale structure using highly functional molecules

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

Watanabe, Y.; Kato, H.; Takemura, S.

2009-07-15

The surface of an Al plate was treated with a combination of chemical and electrochemical processes for fabrication of surface nanoscale structures on Al plates. Chemical treatments by using acetone and pure water under supersonic waves were conducted on an Al surface. Additional electrochemical process in H{sub 2}SO{sub 4} solution created a finer and oriented nanoscale structure on the Al surface. Dynamic force microscopy (DFM) measurement clarified that the nanoscale highly oriented line structure was successfully created on the Al surface. The line distance was estimated approximately 30-40 nm. At the next stage, molecular patterning on the highly oriented linemore » structure by functional molecules such as copper phthalocyanine (CuPc) and fullerene C{sub 60} was also conducted. CuPc or C{sub 60} molecules were deposited on the highly oriented line structure on Al. A toluene droplet containing CuPc molecules was cast on the nanostructured Al plate and was extended on the surface. CuPc or C{sub 60} deposition on the nanostructured Al surface proceeded by evaporation of toluene. DFM and x-ray photoemission spectroscopy measurements demonstrated that a unique molecular pattern was fabricated so that the highly oriented groove channels were filled with the functional molecules.« less

Boiling and quenching heat transfer advancement by nanoscale surface modification.

PubMed

Hu, Hong; Xu, Cheng; Zhao, Yang; Ziegler, Kirk J; Chung, J N

2017-07-21

All power production, refrigeration, and advanced electronic systems depend on efficient heat transfer mechanisms for achieving high power density and best system efficiency. Breakthrough advancement in boiling and quenching phase-change heat transfer processes by nanoscale surface texturing can lead to higher energy transfer efficiencies, substantial energy savings, and global reduction in greenhouse gas emissions. This paper reports breakthrough advancements on both fronts of boiling and quenching. The critical heat flux (CHF) in boiling and the Leidenfrost point temperature (LPT) in quenching are the bottlenecks to the heat transfer advancements. As compared to a conventional aluminum surface, the current research reports a substantial enhancement of the CHF by 112% and an increase of the LPT by 40 K using an aluminum surface with anodized aluminum oxide (AAO) nanoporous texture finish. These heat transfer enhancements imply that the power density would increase by more than 100% and the quenching efficiency would be raised by 33%. A theory that links the nucleation potential of the surface to heat transfer rates has been developed and it successfully explains the current finding by revealing that the heat transfer modification and enhancement are mainly attributed to the superhydrophilic surface property and excessive nanoscale nucleation sites created by the nanoporous surface.

Nanoscale patterning of Si surface using SPM scratching

NASA Astrophysics Data System (ADS)

Ogino, T.; Nishimura, S.; Shirakashi, J.

2008-03-01

Nanolithography of Si surface using scanning probe microscopy (SPM) scratching with a diamond-coated tip was systematically investigated at a low force regime below 9 μN. The groove patterns with controlled width and depth could be achieved by adjusting the applied force, scan direction and the number of scan cycles. There was no effect of scan speed on the groove size. The minimum groove width of 10 nm was obtained on Si surfaces. Furthermore, more complex nanostructures such as line and space patterns of 30 nm pith and dot arrays of 2.6×1010 cm-2 density were realized. SPM scratching with a diamond-coated tip allows nanoscale patterning of Si surfaces to be performed simply.

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

PubMed

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

2009-05-01

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

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

PubMed

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

2018-04-18

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

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

PubMed

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

2018-03-26

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

Nano-scale surface morphology, wettability and osteoblast adhesion on nitrogen plasma-implanted NiTi shape memory alloy.

PubMed

Liu, X M; Wu, S L; Chu, Paul K; Chung, C Y; Chu, C L; Chan, Y L; Lam, K O; Yeung, K W K; Lu, W W; Cheung, K M C; Luk, K D K

2009-06-01

Plasma immersion ion implantation (PIII) is an effective method to increase the corrosion resistance and inhibit nickel release from orthopedic NiTi shape memory alloy. Nitrogen was plasma-implanted into NiTi using different pulsing frequencies to investigate the effects on the nano-scale surface morphology, structure, wettability, as well as biocompatibility. X-ray photoelectron spectroscopy (XPS) results show that the implantation depth of nitrogen increases with higher pulsing frequencies. Atomic force microscopy (AFM) discloses that the nano-scale surface roughness increases and surface features are changed from islands to spiky cones with higher pulsing frequencies. This variation in the nano surface structures leads to different surface free energy (SFE) monitored by contact angle measurements. The adhesion, spreading, and proliferation of osteoblasts on the implanted NiTi surface are assessed by cell culture tests. Our results indicate that the nano-scale surface morphology that is altered by the implantation frequencies impacts the surface free energy and wettability of the NiTi surfaces, and in turn affects the osteoblast adhesion behavior.

Nanoscale Roughness and Morphology Affect the IsoElectric Point of Titania Surfaces

PubMed Central

Borghi, Francesca; Vyas, Varun; Podestà, Alessandro; Milani, Paolo

2013-01-01

We report on the systematic investigation of the role of surface nanoscale roughness and morphology on the charging behaviour of nanostructured titania (TiO2) surfaces in aqueous solutions. IsoElectric Points (IEPs) of surfaces have been characterized by direct measurement of the electrostatic double layer interactions between titania surfaces and the micrometer-sized spherical silica probe of an atomic force microscope in NaCl aqueous electrolyte. The use of a colloidal probe provides well-defined interaction geometry and allows effectively probing the overall effect of nanoscale morphology. By using supersonic cluster beam deposition to fabricate nanostructured titania films, we achieved a quantitative control over the surface morphological parameters. We performed a systematical exploration of the electrical double layer properties in different interaction regimes characterized by different ratios of characteristic nanometric lengths of the system: the surface rms roughness Rq, the correlation length ξ and the Debye length λD. We observed a remarkable reduction by several pH units of IEP on rough nanostructured surfaces, with respect to flat crystalline rutile TiO2. In order to explain the observed behavior of IEP, we consider the roughness-induced self-overlap of the electrical double layers as a potential source of deviation from the trend expected for flat surfaces. PMID:23874708

Investigating Nanoscale Electrochemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

PubMed

Zaleski, Stephanie; Wilson, Andrew J; Mattei, Michael; Chen, Xu; Goubert, Guillaume; Cardinal, M Fernanda; Willets, Katherine A; Van Duyne, Richard P

2016-09-20

The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation of heterogeneous chemical reactions with high sensitivity. Specifically, SERS methodologies are well-suited to study electron transfer (ET) reactions, which lie at the heart of numerous fundamental processes: electrocatalysis, solar energy conversion, energy storage in batteries, and biological events such as photosynthesis. Heterogeneous ET reactions are commonly monitored by electrochemical methods such as cyclic voltammetry, observing billions of electrochemical events per second. Since the first proof of detecting single molecules by redox cycling, there has been growing interest in examining electrochemistry at the nanoscale and single-molecule levels. Doing so unravels details that would otherwise be obscured by an ensemble experiment. The use of optical spectroscopies, such as SERS, to elucidate nanoscale electrochemical behavior is an attractive alternative to traditional approaches such as scanning electrochemical microscopy (SECM). While techniques such as single-molecule fluorescence or electrogenerated chemiluminescence have been used to optically monitor electrochemical events, SERS methodologies, in particular, have shown great promise for exploring electrochemistry at the nanoscale. SERS is ideally suited to study nanoscale electrochemistry because the Raman-enhancing metallic, nanoscale substrate duly serves as the working electrode material. Moreover, SERS has the ability to directly probe single molecules without redox cycling and can achieve nanoscale spatial resolution in combination with super-resolution or scanning probe microscopies. This Account summarizes the latest progress from the Van Duyne and Willets groups toward understanding nanoelectrochemistry using Raman spectroscopic methodologies. The first half of this Account highlights three techniques that have been recently used to probe few- or single-molecule electrochemical

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

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

2017-05-02

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

Detection and Identification: Instrumentation and Calibration for Air/Liquid/Surface-borne Nanoscale Particles

NASA Astrophysics Data System (ADS)

Ling, Tsz Yan; Zuo, Zhili; Pui, David Y. H.

2013-04-01

Nanoscale particles can be found in the air-borne, liquid-borne and surface-borne dispersed phases. Measurement techniques for nanoscale particles in all three dispersed phases are needed for the environmental, health and safety studies of nanomaterials. We present our studies on connecting the nanoparticle measurements in different phases to enhance the characterization capability. Microscopy analysis for particle morphology can be performed by depositing air-borne or liquid-borne nanoparticles on surfaces. Detection limit and measurement resolution of the liquid-borne nanoparticles can be enhanced by aerosolizing them and taking advantage of the well-developed air-borne particle analyzers. Sampling electrically classified air-borne virus particles with a gelatin filter provides higher collection efficiency than a liquid impinger.

Nanoscale Surface Modification of Polycrystalline Tin Sulphide Films during Plasma Treatment

NASA Astrophysics Data System (ADS)

Zimin, S. P.; Gorlachev, E. S.; Dubov, G. A.; Amirov, I. I.; Naumov, V. V.; Gremenok, V. F.; Ivanov, V. A.; Seidi, H. G.

2013-05-01

In this paper, we present a comparative research of the nanoscale modification of the surface morphology of polycrystalline SnS films on glass substrates with two different preferred growth orientations processed in inductively coupled argon plasma. We report a new effect of polycrystalline SnS film surface smoothing during plasma treatment, which can be advantageous for the fabrication of multilayer solar cell devices with SnS absorption layers.

Numerical analysis of micro-/nanoscale gas-film lubrication of sliding surface with complicated structure

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

Kawagoe, Yoshiaki; Isono, Susumu; Takeno, Takanori

2014-12-09

It has been reported that the friction between a partially polished diamond-coated surface and a metal surface was drastically reduced to zero when they are slid at a few m/s. Since the sliding was noiseless, it seems that the diamond-coated surface was levitated over the counter surface and the sliding mechanism was the gas film lubrication. Recently, the mechanism of levitation of a slider with a micro/nanoscale surface structure on a rotating disk was theoretically clarified [S. Yonemura et al., Tribol. Lett., (2014), doi:10.1007/s11249-014-0368-2]. Probably, the partially polished diamond-coated surface may be levitated by high gas pressure generated by themore » micro/nanoscale surface structure on it. In this study, in order to verify our deduction, we performed numerical simulations of sliding of partially polished diamond-coated surface by reproducing its complicated surface structure using the data measured by an atomic force microscope (AFM). As a result, we obtained the lift force which is large enough to levitate the slider used in the experiment.« less

Low temperature surface chemistry and nanostructures

NASA Astrophysics Data System (ADS)

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

2002-03-01

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

Nanoscale NMR spectroscopy and imaging of multiple nuclear species.

PubMed

DeVience, Stephen J; Pham, Linh M; Lovchinsky, Igor; Sushkov, Alexander O; Bar-Gill, Nir; Belthangady, Chinmay; Casola, Francesco; Corbett, Madeleine; Zhang, Huiliang; Lukin, Mikhail; Park, Hongkun; Yacoby, Amir; Walsworth, Ronald L

2015-02-01

Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) provide non-invasive information about multiple nuclear species in bulk matter, with wide-ranging applications from basic physics and chemistry to biomedical imaging. However, the spatial resolution of conventional NMR and MRI is limited to several micrometres even at large magnetic fields (>1 T), which is inadequate for many frontier scientific applications such as single-molecule NMR spectroscopy and in vivo MRI of individual biological cells. A promising approach for nanoscale NMR and MRI exploits optical measurements of nitrogen-vacancy (NV) colour centres in diamond, which provide a combination of magnetic field sensitivity and nanoscale spatial resolution unmatched by any existing technology, while operating under ambient conditions in a robust, solid-state system. Recently, single, shallow NV centres were used to demonstrate NMR of nanoscale ensembles of proton spins, consisting of a statistical polarization equivalent to ∼100-1,000 spins in uniform samples covering the surface of a bulk diamond chip. Here, we realize nanoscale NMR spectroscopy and MRI of multiple nuclear species ((1)H, (19)F, (31)P) in non-uniform (spatially structured) samples under ambient conditions and at moderate magnetic fields (∼20 mT) using two complementary sensor modalities.

Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

Nanoscale surface characterization using laser interference microscopy

NASA Astrophysics Data System (ADS)

Ignatyev, Pavel S.; Skrynnik, Andrey A.; Melnik, Yury A.

2018-03-01

Nanoscale surface characterization is one of the most significant parts of modern materials development and application. The modern microscopes are expensive and complicated tools, and its use for industrial tasks is limited due to laborious sample preparation, measurement procedures, and low operation speed. The laser modulation interference microscopy method (MIM) for real-time quantitative and qualitative analysis of glass, metals, ceramics, and various coatings has a spatial resolution of 0.1 nm for vertical and up to 100 nm for lateral. It is proposed as an alternative to traditional scanning electron microscopy (SEM) and atomic force microscopy (AFM) methods. It is demonstrated that in the cases of roughness metrology for super smooth (Ra >1 nm) surfaces the application of a laser interference microscopy techniques is more optimal than conventional SEM and AFM. The comparison of semiconductor test structure for lateral dimensions measurements obtained with SEM and AFM and white light interferometer also demonstrates the advantages of MIM technique.

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.

Plasmonic hot electron transport drives nano-localized chemistry

PubMed Central

Cortés, Emiliano; Xie, Wei; Cambiasso, Javier; Jermyn, Adam S.; Sundararaman, Ravishankar; Narang, Prineha; Schlücker, Sebastian; Maier, Stefan A.

2017-01-01

Nanoscale localization of electromagnetic fields near metallic nanostructures underpins the fundamentals and applications of plasmonics. The unavoidable energy loss from plasmon decay, initially seen as a detriment, has now expanded the scope of plasmonic applications to exploit the generated hot carriers. However, quantitative understanding of the spatial localization of these hot carriers, akin to electromagnetic near-field maps, has been elusive. Here we spatially map hot-electron-driven reduction chemistry with 15 nm resolution as a function of time and electromagnetic field polarization for different plasmonic nanostructures. We combine experiments employing a six-electron photo-recycling process that modify the terminal group of a self-assembled monolayer on plasmonic silver nanoantennas, with theoretical predictions from first-principles calculations of non-equilibrium hot-carrier transport in these systems. The resulting localization of reactive regions, determined by hot-carrier transport from high-field regions, paves the way for improving efficiency in hot-carrier extraction science and nanoscale regio-selective surface chemistry. PMID:28348402

Nanoscale characterization of 1D Sn-3.5Ag nanosolders and their application into nanowelding at the nanoscale

NASA Astrophysics Data System (ADS)

Zhang, Hong; Zhang, Junwei; Lan, Qianqian; Ma, Hongbin; Qu, Ke; Inkson, Beverley J.; Mellors, Nigel J.; Xue, Desheng; Peng, Yong

2014-10-01

One-dimensional Sn-3.5Ag alloy nanosolders have been successfully fabricated by a dc electrodeposition technique into nanoporous templates, and their soldering quality has been demonstrated in nanoscale electrical welding for the first time, which indicates that they can easily form remarkably reliable conductive joints. The electrical measurement shows that individual 1D Sn-3.5Ag nanosolders have a resistivity of 28.9 μΩ·cm. The morphology, crystal structure and chemistry of these nanosolders have been characterized at the nanoscale. It is found that individual 1D Sn-3.5Ag alloy nanosolders have a continuous morphology and smooth surface. XPS confirms the presence of tin and silver with a mass ratio of 96.54:3.46, and EDX elemental mappings clearly reveal that the Sn and Ag elements have a uniform distribution. Coveragent beam electron diffractions verify that the crystal phases of individual 1D Sn-3.5Ag alloy nanosolders consist of matrix β-Sn and the intermetallic compound Ag3Sn. The reflow experiments reveal that the eutectic composition of the 1D Sn-Ag alloy nanowire is shifted to the Sn rich corner. This work may contribute one of the most important tin-based alloy nanosolders for future nanoscale welding techniques, which are believed to have broad applications in nanotechnology and the future nano-industry.

Nanoscale Etching and Indentation of Silicon(001) Surface with Carbon Nanotube Tips

NASA Technical Reports Server (NTRS)

Dzegilenko, Fendor N.; Srivastava, Deepak; Saini, Subhash

1998-01-01

The possibility of nanoscale etching and indentation of Si(001)(2x1) surface by (8,0) and (10,10) carbon nanotube tips is demonstrated, for the first time, by classical molecular dynamics simulations employing Tersoff's many-body potential for a mixed C/Si/Ge system. In the nanotube tip barely touching the surface scenario atomistic etching is observed, where as in the nanoindentation scenario nanotube tip penetrates the surface without much hindrance. The results are explained in terms of the relative strength of C-C, C-Si, and Si-Si bonds.

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

NASA Technical Reports Server (NTRS)

Hoenk, Michael

2011-01-01

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

Micro to Nanoscale Engineering of Surface Precipitates Using Reconfigurable Contact Lines.

PubMed

Kabi, Prasenjit; Chaudhuri, Swetaprovo; Basu, Saptarshi

2018-02-06

Nanoscale engineering has traditionally adopted the chemical route of synthesis or optochemical techniques such as lithography requiring large process times, expensive equipment, and an inert environment. Directed self-assembly using evaporation of nanocolloidal droplet can be a potential low-cost alternative across various industries ranging from semiconductors to biomedical systems. It is relatively simple to scale and reorient the evaporation-driven internal flow field in an evaporating droplet which can direct dispersed matter into functional agglomerates. The resulting functional precipitates not only exhibit macroscopically discernible changes but also nanoscopic variations in the particulate assembly. Thus, the evaporating droplet forms an autonomous system for nanoscale engineering without the need for external resources. In this article, an indigenous technique of interfacial re-engineering, which is both simple and inexpensive to implement, is developed. Such re-engineering widens the horizon for surface patterning previously limited by the fixed nature of the droplet interface. It involves handprinting hydrophobic lines on a hydrophilic substrate to form a confinement of any selected geometry using a simple document stamp. Droplets cast into such confinements get modulated into a variety of shapes. The droplet shapes control the contact line behavior, evaporation dynamics, and complex internal flow pattern. By exploiting the dynamic interplay among these variables, we could control the deposit's macro- as well as nanoscale assembly not possible with simple circular droplets. We provide a detailed mechanism of the coupling at various length scales enabling a predictive capability in custom engineering, particularly useful in nanoscale applications such as photonic crystals.

On the Use of Analogy to Connect Core Physical and Chemical Concepts to Those at the Nanoscale

ERIC Educational Resources Information Center

Muniz, Marc N.; Oliver-Hoyo, Maria T.

2014-01-01

Nanoscale science remains at the forefront of modern scientific endeavors. As such, students in chemistry need to be prepared to navigate the physical and chemical concepts that describe the unique phenomena observed at this scale. Current approaches to integrating nanoscale topics into undergraduate chemistry curricula range from the design of…

Surface Functionalization of Exosomes Using Click Chemistry

PubMed Central

2015-01-01

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

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.

Chemical Characterization of Tribological and Biomaterial Surfaces With Nanoscale Spatial Resolution

DTIC Science & Technology

2011-02-28

interpretation of meaningful results. It was known that the presence of third bodies or transfer layers is an influential component in determining...203 (2008) 750-755. 9. Scharf T.W. Singer I.L. Role of third bodies in friction behavior of diamond-like nanocomposite coatings studied by in situ...1    AFOSR Final Performance Report Project Title: Chemical characterization of tribological and biomaterial surfaces with nanoscale spatial

Benchtop Nanoscale Patterning Using Soft Lithography

ERIC Educational Resources Information Center

Meenakshi, Viswanathan; Babayan, Yelizaveta; Odom, Teri W.

2007-01-01

This paper outlines several benchtop nanoscale patterning experiments that can be incorporated into undergraduate laboratories or advanced high school chemistry curricula. The experiments, supplemented by an online video lab manual, are based on soft lithographic techniques such as replica molding, micro-molding in capillaries, and micro-contact…

Controlled confinement of DNA at the nanoscale: nanofabrication and surface bio-functionalization

PubMed Central

Palma, Matteo; Abramson, Justin; Gorodetsky, Alon; Nuckolls, Colin; Sheetz, Michael P.; Wind, Shalom J.; Hone, James

2012-01-01

Nanopatterned arrays of biomolecules are a powerful tool to address fundamental issues in many areas of biology. DNA nanoarrays, in particular, are of interest in the study of both DNA-protein interactions as well as for biodiagnostic investigations. In this context, achieving a highly specific nanoscale assembly of oligonulceotides at surfaces is critical. In this chapter we describe a method to control the immobilization of DNA on nanopatterned surfaces: the nanofabrication and the bio-functionalization involved in the process will be discussed. PMID:21674372

Surface chemistry driven actuation in nanoporous gold

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

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

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

Surface chemistry of carbon dioxide revisited

NASA Astrophysics Data System (ADS)

Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas

2016-12-01

This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas-solid interface analysis, the present work goes further by describing surface-CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

Directed transport by surface chemical potential gradients for enhancing analyte collection in nanoscale sensors.

PubMed

Sitt, Amit; Hess, Henry

2015-05-13

Nanoscale detectors hold great promise for single molecule detection and the analysis of small volumes of dilute samples. However, the probability of an analyte reaching the nanosensor in a dilute solution is extremely low due to the sensor's small size. Here, we examine the use of a chemical potential gradient along a surface to accelerate analyte capture by nanoscale sensors. Utilizing a simple model for transport induced by surface binding energy gradients, we study the effect of the gradient on the efficiency of collecting nanoparticles and single and double stranded DNA. The results indicate that chemical potential gradients along a surface can lead to an acceleration of analyte capture by several orders of magnitude compared to direct collection from the solution. The improvement in collection is limited to a relatively narrow window of gradient slopes, and its extent strongly depends on the size of the gradient patch. Our model allows the optimization of gradient layouts and sheds light on the fundamental characteristics of chemical potential gradient induced transport.

Nanoscale Surface Characterization of Aqueous Copper Corrosion: Effects of Immersion Interval and Orthophosphate Concentration

EPA Science Inventory

Morphology changes for copper surfaces exposed to different water parameters were investigated at the nanoscale with atomic force microscopy (AFM), as influenced by changes in pH and the levels of orthophosphate ions. Synthetic water samples were designed to mimic physiological c...

Biological Response of Human Bone Marrow-Derived Mesenchymal Stem Cells to Commercial Tantalum Coatings with Microscale and Nanoscale Surface Topographies

NASA Astrophysics Data System (ADS)

Skoog, Shelby A.; Kumar, Girish; Goering, Peter L.; Williams, Brian; Stiglich, Jack; Narayan, Roger J.

2016-06-01

Tantalum is a promising orthopaedic implant coating material due to its robust mechanical properties, corrosion resistance, and excellent biocompatibility. Previous studies have demonstrated improved biocompatibility and tissue integration of surface-treated tantalum coatings compared to untreated tantalum. Surface modification of tantalum coatings with biologically inspired microscale and nanoscale features may be used to evoke optimal tissue responses. The goal of this study was to evaluate commercial tantalum coatings with nanoscale, sub-microscale, and microscale surface topographies for orthopaedic and dental applications using human bone marrow-derived mesenchymal stem cells (hBMSCs). Tantalum coatings with different microscale and nanoscale surface topographies were fabricated using a diffusion process or chemical vapor deposition. Biological evaluation of the tantalum coatings using hBMSCs showed that tantalum coatings promote cellular adhesion and growth. Furthermore, hBMSC adhesion to the tantalum coatings was dependent on surface feature characteristics, with enhanced cell adhesion on sub-micrometer- and micrometer-sized surface topographies compared to hybrid nano-/microstructures. Nanostructured and microstructured tantalum coatings should be further evaluated to optimize the surface coating features to promote osteogenesis and enhance osseointegration of tantalum-based orthopaedic implants.

Surface chemistry: Key to control and advance myriad technologies

PubMed Central

Yates, John T.; Campbell, Charles T.

2011-01-01

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

Simulations of surface stress effects in nanoscale single crystals

NASA Astrophysics Data System (ADS)

Zadin, V.; Veske, M.; Vigonski, S.; Jansson, V.; Muszinsky, J.; Parviainen, S.; Aabloo, A.; Djurabekova, F.

2018-04-01

Onset of vacuum arcing near a metal surface is often associated with nanoscale asperities, which may dynamically appear due to different processes ongoing in the surface and subsurface layers in the presence of high electric fields. Thermally activated processes, as well as plastic deformation caused by tensile stress due to an applied electric field, are usually not accessible by atomistic simulations because of the long time needed for these processes to occur. On the other hand, finite element methods, able to describe the process of plastic deformations in materials at realistic stresses, do not include surface properties. The latter are particularly important for the problems where the surface plays crucial role in the studied process, as for instance, in the case of plastic deformations at a nanovoid. In the current study by means of molecular dynamics (MD) and finite element simulations we analyse the stress distribution in single crystal copper containing a nanovoid buried deep under the surface. We have developed a methodology to incorporate the surface effects into the solid mechanics framework by utilizing elastic properties of crystals, pre-calculated using MD simulations. The method leads to computationally efficient stress calculations and can be easily implemented in commercially available finite element software, making it an attractive analysis tool.

Simple Methods for Production of Nanoscale Metal Oxide Films from Household Sources

ERIC Educational Resources Information Center

Campbell, Dean J.; Baliss, Michelle S.; Hinman, Jordan J.; Ziegenhorn, John W.; Andrews, Mark J.; Stevenson, Keith J.

2013-01-01

Production of thin metal oxide films was recently explored as part of an outreach program with a goal of producing nanoscale structures with household items. Household items coated with various metals or titanium compounds can be heated to produce colorful films with nanoscale thicknesses. As part of a materials chemistry laboratory experiment…

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.

Quantification of air plasma chemistry for surface disinfection

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Fabricating Ohmic contact on Nb-doped SrTiO{sub 3} surface in nanoscale

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

Wang, Yuhang; National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Chinese Academy of Engineering Physics, Mianyang, Sichuan 621999; Shi, Xiaolan

2016-05-09

Fabricating reliable nano-Ohmic contact on wide gap semiconductors is an important yet difficult step in oxide nanoelectronics. We fabricated Ohmic contact on the n-type wide gap oxide Nb-doped SrTiO{sub 3} in nanoscale by mechanically scratching the surface using an atomic force microscopy tip. Although contacted to high work function metal, the scratched area exhibits nearly linear IV behavior with low contact resistance, which maintains for hours in vacuum. In contrast, the unscratched area shows Fowler–Nordheim tunneling dominated Schottky rectifying behavior with high contact resistance. It was found that the Ohmic conductivity in the scratched area was drastically suppressed by oxygenmore » gas indicating the oxygen vacancy origin of the Ohmic behavior. The surface oxygen vacancy induced barrier width reduction was proposed to explain the phenomena. The nanoscale approach is also applicable to macroscopic devices and has potential application in all-oxide devices.« less

Enhancement of Water Evaporation on Solid Surfaces with Nanoscale Hydrophobic-Hydrophilic Patterns.

PubMed

Wan, Rongzheng; Wang, Chunlei; Lei, Xiaoling; Zhou, Guoquan; Fang, Haiping

2015-11-06

Using molecular dynamics simulations, we show that the evaporation of nanoscale water on hydrophobic-hydrophilic patterned surfaces is unexpectedly faster than that on any surfaces with uniform wettability. The key to this phenomenon is that, on the patterned surface, the evaporation rate from the hydrophilic region only slightly decreases due to the correspondingly increased water thickness; meanwhile, a considerable number of water molecules evaporate from the hydrophobic region despite the lack of water film. Most of the evaporated water from the hydrophobic region originates from the hydrophilic region by diffusing across the contact lines. Further analysis shows that the evaporation rate from the hydrophobic region is approximately proportional to the total length of the contact lines.

Nanoscale Reactions In Opto-magneto-electric Systems

NASA Astrophysics Data System (ADS)

Zeng, Zheng

My research is interdisciplinary in the areas of chemistry, physics and biology for better understanding of synergies between nanomaterials and opto-magneto-electric systems aimed at the practical applications in biosensor, energy (energy storage and electrocatalysis), and biomimetics, in particular, the associated electron transfer, light-matter interactions in nanoscale, such as surface plasmon resonance (SPR) (nanoplasmonics), and magnetic field effect on these phenomena with targeted nanomaterials. Specific research thrusts include: (1) investigation of surface plasmon generation from a novel nanoledge structure on thin metal film. The results are used for the nanostructure optimization for a nanofluidic-nanoplasmonic platform that may function as a multiplexed biosensor for protein biomarker detection; (2) examination of magnetic field effect on uniformly deposited metal oxide on electrospun carbon nanofiber (ECNF) scaffold for efficient energy storage (supercapacitor) and electrocatalytic energy conversion (oxygen reduction reduction). (3) magnetic response of cryptochrome 1 (CRY1) in photoinduced heterogeneous electron transfer (PHET).

Facile Fabrication of Binary Nanoscale Interface for No-Loss Microdroplet Transportation.

PubMed

Liang, Weitao; Zhu, Liqun; Li, Weiping; Xu, Chang; Liu, Huicong

2016-06-07

Binary nanoscale interfacial materials are fundamental issues in many applications for smart surfaces. A binary nanoscale interface with binary surface morphology and binary wetting behaviors has been prepared by a facile wet-chemical method. The prepared surface presents superhydrophobicity and high adhesion with the droplet at the same time. The composition, surface morphology, and wetting behaviors of the prepared surface have been systematic studied. The special wetting behaviors can be contributed to the binary nanoscale effect. The stability of the prepared surface was also investigated. As a primary application, a facile device based on the prepared binary nanoscale interface with superhydrophobicity and high adhesion was constructed for microdroplet transportation.

Modulating macrophage polarization with divalent cations in nanostructured titanium implant surfaces

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Capillary-induced crack healing between surfaces of nanoscale roughness.

PubMed

Soylemez, Emrecan; de Boer, Maarten P

2014-10-07

Capillary forces are important in nature (granular materials, insect locomotion) and in technology (disk drives, adhesion). Although well studied in equilibrium state, the dynamics of capillary formation merit further investigation. Here, we show that microcantilever crack healing experiments are a viable experimental technique for investigating the influence of capillary nucleation on crack healing between rough surfaces. The average crack healing velocity, v̅, between clean hydrophilic polycrystalline silicon surfaces of nanoscale roughness is measured. A plot of v̅ versus energy release rate, G, reveals log-linear behavior, while the slope |d[log(v̅)]/dG| decreases with increasing relative humidity. A simplified interface model that accounts for the nucleation time of water bridges by an activated process is developed to gain insight into the crack healing trends. This methodology enables us to gain insight into capillary bridge dynamics, with a goal of attaining a predictive capability for this important microelectromechanical systems (MEMS) reliability failure mechanism.

Multiresolution molecular mechanics: Surface effects in nanoscale materials

NASA Astrophysics Data System (ADS)

Yang, Qingcheng; To, Albert C.

2017-05-01

Surface effects have been observed to contribute significantly to the mechanical response of nanoscale structures. The newly proposed energy-based coarse-grained atomistic method Multiresolution Molecular Mechanics (MMM) (Yang, To (2015), [57]) is applied to capture surface effect for nanosized structures by designing a surface summation rule SRS within the framework of MMM. Combined with previously proposed bulk summation rule SRB, the MMM summation rule SRMMM is completed. SRS and SRB are consistently formed within SRMMM for general finite element shape functions. Analogous to quadrature rules in finite element method (FEM), the key idea to the good performance of SRMMM lies in that the order or distribution of energy for coarse-grained atomistic model is mathematically derived such that the number, position and weight of quadrature-type (sampling) atoms can be determined. Mathematically, the derived energy distribution of surface area is different from that of bulk region. Physically, the difference is due to the fact that surface atoms lack neighboring bonding. As such, SRS and SRB are employed for surface and bulk domains, respectively. Two- and three-dimensional numerical examples using the respective 4-node bilinear quadrilateral, 8-node quadratic quadrilateral and 8-node hexahedral meshes are employed to verify and validate the proposed approach. It is shown that MMM with SRMMM accurately captures corner, edge and surface effects with less 0.3% degrees of freedom of the original atomistic system, compared against full atomistic simulation. The effectiveness of SRMMM with respect to high order element is also demonstrated by employing the 8-node quadratic quadrilateral to solve a beam bending problem considering surface effect. In addition, the introduced sampling error with SRMMM that is analogous to numerical integration error with quadrature rule in FEM is very small.

Biomimetic patterned surfaces for controllable friction in micro- and nanoscale devices

NASA Astrophysics Data System (ADS)

Singh, Arvind; Suh, Kahp-Yang

2013-12-01

Biomimetics is the study and simulation of biological systems for desired functional properties. It involves the transformation of underlying principles discovered in nature into man-made technologies. In this context, natural surfaces have significantly inspired and motivated new solutions for micro- and nano-scale devices (e.g., Micro/Nano-Electro-Mechanical Systems, MEMS/NEMS) towards controllable friction, during their operation. As a generic solution to reduce friction at small scale, various thin films/coatings have been employed in the last few decades. In recent years, inspiration from `Lotus Effect' has initiated a new research direction for controllable friction with biomimetic patterned surfaces. By exploiting the intrinsic hydrophobicity and ability to reduce contact area, such micro- or nano-patterned surfaces have demonstrated great strength and potential for applications in MEMS/NEMS devices. This review highlights recent advancements on the design, development and performance of these biomimetic patterned surfaces. Also, we present some hybrid approaches to tackle current challenges in biomimetic tribological applications for MEMS/NEMS devices.

Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

ERIC Educational Resources Information Center

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

1980-01-01

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

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

PubMed

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

2015-09-01

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

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

PubMed

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

2018-03-07

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

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Superhydrophobic, Biomimetic Surfaces with High and Low Adhesion, Optical Transmittance, and Nanoscale Mechanical Wear Resistance

NASA Astrophysics Data System (ADS)

Ebert, Daniel R.

Superhydrophobic surfaces (defined as surfaces having water contact angle greater than 150°) show great promise for use in a rapidly growing number of engineering applications, ranging from biomedical devices to fluid drag reduction in pipelines. In nature, the surfaces of many organisms, such as certain plant leaves, are known to exhibit superhydrophobicity. In some cases, droplet adhesion is very low (droplet rolls away easily), while in other cases adhesion is high (droplet remains adhered when surface is inverted). The recent advent and development of microscopes with resolution down to a few nanometers (such as atomic force microscopes and scanning electron microscopes) has allowed for in-depth understanding of the micro- and nanoscale mechanisms employed by these plant leaves and other natural surfaces to achieve their particular wetting properties. Biomimetics (or "mimicking nature") is therefore a very promising approach for the development of engineering surfaces with desired wetting characteristics. However, research in creating biomimetic surfaces is still in its early stages, and many of the surfaces created thus far are not mechanically robust, which is required for many potential real-world applications. In addition, for applications such as self-cleaning windows and solar panels, optical transparency is required. In this thesis, a set of original studies are presented in which superhydrophobic surfaces were designed based on biomimetics and fabricated using a wide of variety of techniques. The surfaces were characterized with regard to wetting characteristics such as water contact angle and contact angle hysteresis, micro- and nanoscale mechanical durability, and in some cases optical transmittance. Theoretical wetting models served as guides both in the design and in the understanding of experimental results, especially in regard to different wetting regime and regime transition. This work provides important conclusions and valuable insight for

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.

Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template.

PubMed

Aizawa, Masato; Buriak, Jillian M

2006-05-03

Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

Nanoscale control of energy and matter in plasma-surface interactions: towards energy-efficient nanotech

NASA Astrophysics Data System (ADS)

Ostrikov, Kostya

2010-11-01

This presentation focuses on the plasma issues related to the solution of the grand challenge of directing energy and matter at nanoscales. This ability is critical for the renewable energy and energy-efficient technologies for sustainable future development. It will be discussed how to use environmentally and human health benign non-equilibrium plasma-solid systems and control the elementary processes of plasma-surface interactions to direct the fluxes of energy and matter at multiple temporal and spatial scales. In turn, this makes it possible to achieve the deterministic synthesis of self- organised arrays of metastable nanostructures in the size range beyond the reach of the present-day nanofabrication. Such structures have tantalising prospects to enhance performance of nanomaterials in virtually any area of human activity yet remain almost inaccessible because the Nature's energy minimisation rules allow only a small number of stable equilibrium states. By using precisely controlled and kinetically fast nanoscale transfer of energy and matter under non-equilibrium conditions and harnessing numerous plasma- specific controls of species creation, delivery to the surface, nucleation and large-scale self-organisation of nuclei and nanostructures, the arrays of metastable nanostructures can be created, arranged, stabilised, and further processed to meet the specific requirements of the envisaged applications. These approaches will eventually lead to faster, unprecedentedly- clean, human-health-friendly, and energy-efficient nanoscale synthesis and processing technologies for the next-generation renewable energy and light sources, biomedical devices, information and communication systems, as well as advanced functional materials for applications ranging from basic food, water, health and clean environment needs to national security and space missions.

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

PubMed

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

2012-07-01

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

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

PubMed

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

2012-03-01

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

Magmatic and fragmentation controls on volcanic ash surface chemistry

NASA Astrophysics Data System (ADS)

Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

2016-04-01

The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that

Atomistic Design and Simulations of Nanoscale Machines and Assembly

NASA Technical Reports Server (NTRS)

Goddard, William A., III; Cagin, Tahir; Walch, Stephen P.

2000-01-01

Over the three years of this project, we made significant progress on critical theoretical and computational issues in nanoscale science and technology, particularly in:(1) Fullerenes and nanotubes, (2) Characterization of surfaces of diamond and silicon for NEMS applications, (3) Nanoscale machine and assemblies, (4) Organic nanostructures and dendrimers, (5) Nanoscale confinement and nanotribology, (6) Dynamic response of nanoscale structures nanowires (metals, tubes, fullerenes), (7) Thermal transport in nanostructures.

Nanoscale functionalization and characterization of surfaces with hydrogel patterns and biomolecules

NASA Astrophysics Data System (ADS)

Dinakar, Hariharasudhan Chirra

The advent of numerous tools, ease of techniques, and concepts related to nanotechnology, in combination with functionalization via simple chemistry has made gold important for various biomedical applications. In this dissertation, the development and characterization of planar gold surfaces with responsive hydrogel patterns for rapid point of care sensing and the functionalization of gold nanoparticles for drug delivery are highlighted. Biomedical micro- and nanoscale devices that are spatially functionalized with intelligent hydrogels are typically fabricated using conventional UV-lithography. Herein, precise 3-D hydrogel patterns made up of temperature responsive crosslinked poly(N-isopropylacrylamide) over gold were synthesized. The XY control of the hydrogel was achieved using microcontact printing, while thickness control was achieved using atom transfer radical polymerization (ATRP). Atomic force microscopy analysis showed that to the ATRP reaction time governed the pattern growth. The temperature dependent swelling ratio was tailored by tuning the mesh size of the hydrogel. While nanopatterns exhibited a broad lower critical solution temperature (LCST) transition, surface roughness showed a sharp LCST transition. Quartz crystal microbalance with dissipation showed rapid response behavior of the thin films, which makes them applicable as functional components in biomedical devices. The easy synthesis, relative biocompatibility, inertness, and easy functionalization of gold nanoparticles (GNPs) have made them useful for various biomedical applications. Although ATRP can be successfully carried out over GNPs, the yield of stable solution based GNPs for biomedical applications prove to be low. As an alternative approach, a novel method of ISOlating, FUnctionalizing, and REleasing nanoparticles (ISOFURE) was proposed. Biodegradable poly(beta-amino ester) hydrogels were used to synthesize ISOFURE-GNP composites. ATRP was performed inside the composite, and the

Bench-scale synthesis of nanoscale materials

NASA Technical Reports Server (NTRS)

Buehler, M. F.; Darab, J. G.; Matson, D. W.; Linehan, J. C.

1994-01-01

A novel flow-through hydrothermal method used to synthesize nanoscale powders is introduced by Pacific Northwest Laboratory. The process, Rapid Thermal Decomposition of precursors in Solution (RTDS), uniquely combines high-pressure and high-temperature conditions to rapidly form nanoscale particles. The RTDS process was initially demonstrated on a laboratory scale and was subsequently scaled up to accommodate production rates attractive to industry. The process is able to produce a wide variety of metal oxides and oxyhydroxides. The powders are characterized by scanning and transmission electron microscopic methods, surface-area measurements, and x-ray diffraction. Typical crystallite sizes are less than 20 nanometers, with BET surface areas ranging from 100 to 400 sq m/g. A description of the RTDS process is presented along with powder characterization results. In addition, data on the sintering of nanoscale ZrO2 produced by RTDS are included.

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

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

NASA Astrophysics Data System (ADS)

Riba, Olga; Barnes, Robert J.; Scott, Thomas B.; Gardner, Murray N.; Jackman, Simon A.; Thompson, Ian P.

2011-10-01

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m2/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity 30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H2 on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m2/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.

Nanoscale volcanoes: accretion of matter at ion-sculpted nanopores.

PubMed

Mitsui, Toshiyuki; Stein, Derek; Kim, Young-Rok; Hoogerheide, David; Golovchenko, J A

2006-01-27

We demonstrate the formation of nanoscale volcano-like structures induced by ion-beam irradiation of nanoscale pores in freestanding silicon nitride membranes. Accreted matter is delivered to the volcanoes from micrometer distances along the surface. Volcano formation accompanies nanopore shrinking and depends on geometrical factors and the presence of a conducting layer on the membrane's back surface. We argue that surface electric fields play an important role in accounting for the experimental observations.

Friction laws at the nanoscale.

PubMed

Mo, Yifei; Turner, Kevin T; Szlufarska, Izabela

2009-02-26

Macroscopic laws of friction do not generally apply to nanoscale contacts. Although continuum mechanics models have been predicted to break down at the nanoscale, they continue to be applied for lack of a better theory. An understanding of how friction force depends on applied load and contact area at these scales is essential for the design of miniaturized devices with optimal mechanical performance. Here we use large-scale molecular dynamics simulations with realistic force fields to establish friction laws in dry nanoscale contacts. We show that friction force depends linearly on the number of atoms that chemically interact across the contact. By defining the contact area as being proportional to this number of interacting atoms, we show that the macroscopically observed linear relationship between friction force and contact area can be extended to the nanoscale. Our model predicts that as the adhesion between the contacting surfaces is reduced, a transition takes place from nonlinear to linear dependence of friction force on load. This transition is consistent with the results of several nanoscale friction experiments. We demonstrate that the breakdown of continuum mechanics can be understood as a result of the rough (multi-asperity) nature of the contact, and show that roughness theories of friction can be applied at the nanoscale.

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.

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

DTIC Science & Technology

1988-09-01

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

Nanoscale Surface Plasmonics Sensor With Nanofluidic Control

NASA Technical Reports Server (NTRS)

Wei, Jianjun; Singhal, Sameer; Waldeck, David H.; Kofke, Matthew

2013-01-01

Conventional quantitative protein assays of bodily fluids typically involve multiple steps to obtain desired measurements. Such methods are not well suited for fast and accurate assay measurements in austere environments such as spaceflight and in the aftermath of disasters. Consequently, there is a need for a protein assay technology capable of routinely monitoring proteins in austere environments. For example, there is an immediate need for a urine protein assay to assess astronaut renal health during spaceflight. The disclosed nanoscale surface plasmonics sensor provides a core detection method that can be integrated to a lab-on-chip device that satisfies the unmet need for such a protein assay technology. Assays based upon combinations of nanoholes, nanorings, and nanoslits with transmission surface plasmon resonance (SPR) are used for assays requiring extreme sensitivity, and are capable of detecting specific analytes at concentrations as low as picomole to femtomole level in well-controlled environments. The device operates in a transmission mode configuration in which light is directed at one planar surface of the array, which functions as an optical aperture. The incident light induces surface plasmon light transmission from the opposite surface of the array. The presence of a target analyte is detected by changes in the spectrum of light transmitted by the array when a target analyte induces a change in the refractive index of the fluid within the nanochannels. This occurs, for example, when a target analyte binds to a receptor fixed to the walls of the nanochannels in the array. Independent fluid handling capability for individual nanoarrays on a nanofluidic chip containing a plurality of nanochannel arrays allows each array to be used to sense a different target analyte and/or for paired arrays to analyze control and test samples simultaneously in parallel. The present invention incorporates transmission mode nanoplasmonics and nanofluidics into a single

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Dynamic structural disorder in supported nanoscale catalysts

NASA Astrophysics Data System (ADS)

Rehr, J. J.; Vila, F. D.

2014-04-01

We investigate the origin and physical effects of "dynamic structural disorder" (DSD) in supported nano-scale catalysts. DSD refers to the intrinsic fluctuating, inhomogeneous structure of such nano-scale systems. In contrast to bulk materials, nano-scale systems exhibit substantial fluctuations in structure, charge, temperature, and other quantities, as well as large surface effects. The DSD is driven largely by the stochastic librational motion of the center of mass and fluxional bonding at the nanoparticle surface due to thermal coupling with the substrate. Our approach for calculating and understanding DSD is based on a combination of real-time density functional theory/molecular dynamics simulations, transient coupled-oscillator models, and statistical mechanics. This approach treats thermal and dynamic effects over multiple time-scales, and includes bond-stretching and -bending vibrations, and transient tethering to the substrate at longer ps time-scales. Potential effects on the catalytic properties of these clusters are briefly explored. Model calculations of molecule-cluster interactions and molecular dissociation reaction paths are presented in which the reactant molecules are adsorbed on the surface of dynamically sampled clusters. This model suggests that DSD can affect both the prefactors and distribution of energy barriers in reaction rates, and thus can significantly affect catalytic activity at the nano-scale.

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

PubMed Central

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Engineering single-molecule, nanoscale, and microscale bio-functional materials via click chemistry

NASA Astrophysics Data System (ADS)

Daniele, Michael Angelo-Anthony

To expand the design envelope and supplement the materials library available to biomaterials scientists, the copper(I)-catalyzed azide-alkyne cycloaddition (CuCAAC) was explored as a route to design, synthesize and characterize bio-functional small-molecules, nanoparticles, and microfibers. In each engineered system, the use of click chemistry provided facile, bio-orthogonal control for materials synthesis; moreover, the results provided a methodology and more complete, fundamental understanding of the use of click chemistry as a tool for the synergy of biotechnology, polymer and materials science. Fluorophores with well-defined photophysical characteristics (ranging from UV to NIR fluorescence) were used as building blocks for small-molecule, fluorescent biosensors. Fluorophores were paired to exhibit fluorescence resonant energy transfer (FRET) and used to probe the metabolic activity of carbazole 1,9a-dioxygenase (CARDO). The FRET pair exhibited a significant variation in PL response with exposure to the lysate of Pseudomonas resinovorans CA10, an organism which can degrade variants of both the donor and acceptor fluorophores. Nanoparticle systems were modified via CuCAAC chemistry to carry affinity tags for CARDO and were subsequently utilized for affinity based bioseparation of CARDO from crude cell lysate. The enzymes were baited with an azide-modified carbazolyl-moiety attached to a poly(propargyl acrylate) nanoparticle. Magnetic nanocluster systems were also modified via CuCAAC chemistry to carry fluorescent imaging tags. The iron-oxide nanoclusters were coated with poly(acrylic acid-co-propargyl acrylate) to provide a clickable surface. Ultimately, alternate Cu-free click chemistries were utilized to produce biohybrid microfibers. The biohybrid microfibers were synthesized under benign photopolymerization conditions inside a microchannel, allowing the encapsulation of viable bacteria. By adjusting pre-polymer solutions and laminar flow rates within the

Nanoscale lubrication of ionic surfaces controlled via a strong electric field

DOE PAGES

Strelcov, Evgheni; Bocharova, Vera; Sumpter, Bobby G.; ...

2015-01-27

Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip andmore » salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. Lastly, the demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.« less

Understanding of the Formation of Micro/Nanoscale Structures on Metal Surfaces by Ultrafast Pulse Laser Processing

NASA Astrophysics Data System (ADS)

Peng, Edwin

In the recent decades, there has been much interest in functionalized surfaces produced by ultrafast laser processing. Using pulse lasers with nanosecond to femtosecond time scale, a wide range of micro/nanoscale structures can be produced on virtually all metal surfaces. These surface structures create special optoelectronic, wetting, and tribological properties with a diverse range of potential applications. The formation mechanisms of these surface structures, especially microscale, mound-like structures, are not fully understood. There has been wide study of ultrafast laser processing of metals. Yet, the proposed formation models present in current literature often lack sufficient experimental verification. Specifically, many studies are limited to surface characterization, e.g. scanning electron microscopy of the surfaces of these micro/nanoscale structures. Valuable insight into the physical processes responsible for formation can be obtained if standard material science characterization methods are performed across the entire mound. In our study, we examined mound-like structures formed on three metal alloys. Using cross section and 3D slice and view operations by a dual beam scanning electron microscope-focused ion beam, the interior microstructures of these mounds are revealed. Taking advantage of amorphous phase formation during laser processing of Ni60Nb40, we verified the fluence-dependent formation model: mounds formed at low fluence are primarily the result of ablation while mounds formed at high fluence are formed by both ablation and rapid resolidification by hydrodynamical fluid flow. For the first time, we revealed the cross section of a wide variety of mound-like structures on titanium surfaces. The increased contribution to mound formation by fluid flow with increasing fluence was observed. Finally, a 3D scanning electron microscopy technique was applied for mounds produced on silver surface by delayed-pulse laser processing. The interior

Endocytosis of Nanoscale Systems for Cancer Treatments.

PubMed

Chen, Kai; Li, Xue; Zhu, Hongyan; Gong, Qiyong; Luo, Kui

2017-04-28

Advances of nanoscale systems for cancer treatment have been involved in enabling highly regulated site-specific localization to sub cellular organelles hidden beneath cell membranes. Thus far, the cellular entry of these nanoscale systems has been not fully understood. Endocytosisis a form of active transport in which cell transports elected extracellular molecules (such as proteins, viruses, micro-organisms and nanoscale systems) are allowed into cell interiors by engulfing them in an energy-dependent process. This process appears at the plasma membrane surface and contains internalization of the cell membrane as well as the membrane proteins and lipids of cell. There are multiform pathways of endocytosis for nanoscale systems. Further comprehension for the mechanisms of endocytosis is achieved with a combination of efficient genetic manipulations, cell dynamic imaging, and chemical endocytosis inhibitors. This review provides an account of various endocytic pathways, itemizes current methods to study endocytosis of nanoscale systems, discusses some factors associated with cellular uptake for nanoscale systems and introduces the trafficking behavior for nanoscale systems with active targeting. An insight into the endocytosis mechanism is urgent and significant for developing safe and efficient nanoscale systems for cancer diagnosis and therapy. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

The surface science of nanocrystals

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Development of a Tip-Enhanced Near-Field Optical Microscope for Nanoscale Interrogation of Surface Chemistry and Plasmonic Phenomena

NASA Astrophysics Data System (ADS)

Heilman, Alexander Lee

Optical microscopy and spectroscopy are invaluable tools for the physical and chemical characterization of materials and surfaces in a wide range of scientific disciplines. However, the application of conventional optical methods in the study of nanomaterials is inherently limited by diffraction. Tip-enhanced near-field optical microscopy (TENOM) is a hybrid technique that marries optical spectroscopy with scanning probe microscopy to overcome the spatial resolution limit imposed by diffraction. By coupling optical energy into the plasmonic modes of a sharp metal probe tip, a strong, localized optical field is generated near the tip's apex and is used to enhance spectroscopic emissions within a sub-diffraction-limited volume. In this thesis, we describe the design, construction, validation, and application of a custom TENOM instrument with a unique attenuated total reflectance (ATR)-geometry excitation/detection system. The specific goals of this work were: (i) to develop a versatile TENOM instrument capable of investigating a variety of optical phenomena at the nanoscale, (ii) to use the instrument to demonstrate chemical interrogation of surfaces with sub-diffraction-limited spatial resolution (i.e., at super resolution), (iii) to apply the instrument to study plasmonic phenomena that influence spectroscopic enhancement in TENOM measurements, and (iv) to leverage resulting insights to develop systematic improvements that expand the ultimate capabilities of near-field optical interrogation techniques. The TENOM instrument described herein is comprised of three main components: an atomic force microscope (AFM), a side-on confocal Raman microscope, and a novel ATR excitation/detection system. The design of each component is discussed along with the results of relevant validation experiments, which were performed to rigorously assess each component's performance. Finite-difference time-domain (FDTD) optical simulations were also developed and used extensively to

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

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

NASA Astrophysics Data System (ADS)

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

2007-03-01

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

Modeling the acid-base surface chemistry of montmorillonite.

PubMed

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

2007-08-15

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

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

DOE PAGES

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

2016-12-08

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

Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

PubMed Central

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

2016-01-01

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

A nanoporous titanium surface promotes the maturation of focal adhesions and formation of filopodia with distinctive nanoscale protrusions by osteogenic cells.

PubMed

Guadarrama Bello, Dainelys; Fouillen, Aurélien; Badia, Antonella; Nanci, Antonio

2017-09-15

While topography is a key determinant of the cellular response to biomaterials, the mechanisms implicated in the cell-surface interactions are complex and still not fully elucidated. In this context, we have examined the effect of nanoscale topography on the formation of filopodia, focal adhesions, and gene expression of proteins associated with cell adhesion and sensing. Commercially pure titanium discs were treated by oxidative nanopatterning with a solution of H 2 SO 4 /H 2 O 2 50:50 (v/v). Scanning electron microscopy and atomic force microscopy characterizations showed that this facile chemical treatment efficiently creates a unique nanoporous surface with a root-mean-square roughness of 11.5nm and pore diameter of 20±5nm. Osteogenic cells were cultured on polished (control) and nanotextured discs for periods of 6, 24, and 72h. Immunofluorescence analysis revealed increases in the adhesion formation per cell area, focal adhesion length, and maturity on the nanoporous surface. Gene expression for various focal adhesion markers, including paxillin and talin, and different integrins (e.g. α1, β1, and α5) was also significantly increased. Scanning electron microscopy revealed the presence of more filopodia on cells grown on the nanoporous surface. These cell extensions displayed abundant and distinctive nanoscale lateral protrusions of 10-15nm diameter that molded the nanopore walls. Together the increase in the focal adhesions and abundance of filopodia and associated protrusions could contribute to strengthening the adhesive interaction of cells with the surface, and thereby, alter the nanoscale biomechanical relationships that trigger cellular cascades that regulate cell behavior. Oxidative patterning was exploited to create a unique three-dimensional network of nanopores on titanium surfaces. Our study illustrates how a facile chemical treatment can be advantageously used to modulate cellular behavior. The nanoscale lateral protrusions on filopodia

Enhanced cell attachment and hemocompatibility of titanium by nanoscale surface modification through severe plastic integration of magnesium-rich islands and porosification.

PubMed

Rezaei, Masoud; Tamjid, Elnaz; Dinari, Ali

2017-10-11

Besides the wide applications of titanium and its alloys for orthopedic and biomedical implants, the biocompatible nature of titanium has emerged various surface modification techniques to enhance its bioactivity and osteointegration with living tissues. In this work, we present a new procedure for nanoscale surface modification of titanium implants by integration of magnesium-rich islands combined with controlled formation of pores and refinement of the surface grain structure. Through severe plastic deformation of the titanium surface with fine magnesium hydride powder, Mg-rich islands with varying sizes ranging from 100 nm to 1000 nm can be integrated inside a thin surface layer (100-500 µm) of the implant. Selective etching of the surface forms a fine structure of surface pores which their average size varies in the range of 200-500 nm depending on the processing condition. In vitro biocompatibility and hemocompatibility assays show that the Mg-rich islands and the induced surface pores significantly enhance cell attachment and biocompatibility without an adverse effect on the cell viability. Therefore, severe plastic integration of Mg-rich islands on titanium surface accompanying with porosification is a new and promising procedure with high potential for nanoscale modification of biomedical implants.

Nanoscale chemical mapping of laser-solubilized silk

NASA Astrophysics Data System (ADS)

Ryu, Meguya; Kobayashi, Hanae; Balčytis, Armandas; Wang, Xuewen; Vongsvivut, Jitraporn; Li, Jingliang; Urayama, Norio; Mizeikis, Vygantas; Tobin, Mark; Juodkazis, Saulius; Morikawa, Junko

2017-11-01

A water soluble amorphous form of silk was made by ultra-short laser pulse irradiation and detected by nanoscale IR mapping. An optical absorption-induced nanoscale surface expansion was probed to yield the spectral response of silk at IR molecular fingerprinting wavelengths with a high  ˜ 20 nm spatial resolution defined by the tip of the probe. Silk microtomed sections of 1-5 μm in thickness were prepared for nanoscale spectroscopy and a laser was used to induce amorphisation. Comparison of silk absorbance measurements carried out by table-top and synchrotron Fourier transform IR spectroscopy proved that chemical imaging obtained at high spatial resolution and specificity (able to discriminate between amorphous and crystalline silk) is reliably achieved by nanoscale IR. Differences in absorbance and spectral line-shapes of the bands are related to the different sensitivity of the applied methods to real and imaginary parts of permittivity. A nanoscale material characterization by combining synchrotron IR radiation and nano-IR is discussed.

Operando chemistry of catalyst surfaces during catalysis.

PubMed

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

2017-04-03

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

Effect of Micro- and Nanoscale Topography on the Adhesion of Bacterial Cells to Solid Surfaces

PubMed Central

Hsu, Lillian C.; Fang, Jean; Borca-Tasciuc, Diana A.; Worobo, Randy W.

2013-01-01

Attachment and biofilm formation by bacterial pathogens on surfaces in natural, industrial, and hospital settings lead to infections and illnesses and even death. Minimizing bacterial attachment to surfaces using controlled topography could reduce the spreading of pathogens and, thus, the incidence of illnesses and subsequent human and financial losses. In this context, the attachment of key microorganisms, including Escherichia coli, Listeria innocua, and Pseudomonas fluorescens, to silica and alumina surfaces with micron and nanoscale topography was investigated. The results suggest that orientation of the attached cells occurs preferentially such as to maximize their contact area with the surface. Moreover, the bacterial cells exhibited different morphologies, including different number and size of cellular appendages, depending on the topographical details of the surface to which they attached. This suggests that bacteria may utilize different mechanisms of attachment in response to surface topography. These results are important for the design of novel microbe-repellant materials. PMID:23416997

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

PubMed

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

2016-03-14

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

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

PubMed Central

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

2016-01-01

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

Impact of Wide-Ranging Nanoscale Chemistry on Band Structure at Cu(In, Ga)Se 2 Grain Boundaries

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

Stokes, Adam; Al-Jassim, Mowafak; Diercks, David

The relative chemistry from grain interiors to grain boundaries help explain why grain boundaries may be beneficial, detrimental or benign towards device performance. 3D Nanoscale chemical analysis extracted from atom probe tomography (APT) (10’s of parts-per-million chemical sensitivity and sub-nanometer spatial resolution) of twenty grain boundaries in a high-efficiency Cu(In, Ga)Se 2 solar cell shows the matrix and alkali concentrations are wide-ranging. The concentration profiles are then related to band structure which provide a unique insight into grain boundary electrical performance. Fluctuating Cu, In and Ga concentrations result in a wide distribution of potential barriers at the valence band maximummore » (VBM) (-10 to -160 meV) and the conduction band minimum (CBM) (-20 to -70 meV). Furthermore, Na and K segregation is not correlated to hampering donors, (In, Ga) Cu and V Se, contrary to what has been previously reported. In addition, Na and K are predicted to be n-type dopants at grain boundaries. An overall band structure at grain boundaries is presented.« less

Impact of Wide-Ranging Nanoscale Chemistry on Band Structure at Cu(In, Ga)Se 2 Grain Boundaries

DOE PAGES

Stokes, Adam; Al-Jassim, Mowafak; Diercks, David; ...

2017-10-26

The relative chemistry from grain interiors to grain boundaries help explain why grain boundaries may be beneficial, detrimental or benign towards device performance. 3D Nanoscale chemical analysis extracted from atom probe tomography (APT) (10’s of parts-per-million chemical sensitivity and sub-nanometer spatial resolution) of twenty grain boundaries in a high-efficiency Cu(In, Ga)Se 2 solar cell shows the matrix and alkali concentrations are wide-ranging. The concentration profiles are then related to band structure which provide a unique insight into grain boundary electrical performance. Fluctuating Cu, In and Ga concentrations result in a wide distribution of potential barriers at the valence band maximummore » (VBM) (-10 to -160 meV) and the conduction band minimum (CBM) (-20 to -70 meV). Furthermore, Na and K segregation is not correlated to hampering donors, (In, Ga) Cu and V Se, contrary to what has been previously reported. In addition, Na and K are predicted to be n-type dopants at grain boundaries. An overall band structure at grain boundaries is presented.« less

Molecular insight into nanoscale water films dewetting on modified silica surfaces.

PubMed

Zhang, Jun; Li, Wen; Yan, Youguo; Wang, Yefei; Liu, Bing; Shen, Yue; Chen, Haixiang; Liu, Liang

2015-01-07

In this work, molecular dynamics simulations are adopted to investigate the microscopic dewetting mechanism of nanoscale water films on methylated silica surfaces. The simulation results show that the dewetting process is divided into two stages: the appearance of dry patches and the quick contraction of the water film. First, the appearance of dry patches is due to the fluctuation in the film thickness originating from capillary wave instability. Second, for the fast contraction of water film, the unsaturated electrostatic and hydrogen bond interactions among water molecules are the driving forces, which induce the quick contraction of the water film. Finally, the effect of film thickness on water films dewetting is studied. Research results suggest that upon increasing the water film thickness from 6 to 8 Å, the final dewetting patterns experience separate droplets and striation-shaped structures, respectively. But upon further increasing the water film thickness, the water film is stable and there are no dry patches. The microscopic dewetting behaviors of water films on methylated silica surfaces discussed here are helpful in understanding many phenomena in scientific and industrial processes better.

Grain Surface Chemistry and the Composition of Interstellar Ices

NASA Technical Reports Server (NTRS)

Tielens, A. G. G. M.

2006-01-01

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

Fabrication of meso- and nano-scale structures on surfaces of chalcogenide semiconductors by surface hydrodynamic interference patterning

NASA Astrophysics Data System (ADS)

Bilanych, V.; Komanicky, V.; Lacková, M.; Feher, A.; Kuzma, V.; Rizak, V.

2015-10-01

We observe the change of surface relief on amorphous Ge-As-Se thin films after irradiation with an electron beam. The beam softens the glass and induces various topological surface changes in the irradiated area. The film relief change depends on the film thickness, deposited charge, and film composition. Various structures are formed: Gausian-like cones, extremely sharp Taylor cones, deep craters, and craters with large spires grown on the side. Our investigation shows that these effects can be at least partially a result of electro-hydrodynamic material flow, but the observed phenomena are likely more complex. When we irradiated structural patterns formed by the electron beam with a red laser beam, we could not only fully relax the produced patterns, but also form very complex and intricate superstructures. These organized meso- and nano-scale structures are formed by a combination of photo-induced structural relaxation, light interference on structures fabricated by the e-beam, and photo-induced material flow.

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

PubMed

Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

2016-07-08

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

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

NASA Astrophysics Data System (ADS)

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

2008-08-01

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

A general lithography-free method of microscale/nanoscale fabrication and patterning on Si and Ge surfaces

PubMed Central

2012-01-01

Here, we introduce and give an overview of a general lithography-free method to fabricate silicide and germanide micro-/nanostructures on Si and Ge surfaces through metal-vapor-initiated endoepitaxial growth. Excellent controls on shape and orientation are achieved by adjusting the substrate orientation and growth parameters. Furthermore, micro-/nanoscale pits with controlled morphologies can also be successfully fabricated on Si and Ge surfaces by taking advantage of the sublimation of silicides/germanides. The aim of this brief report is to illustrate the concept of lithography-free synthesis and patterning on surfaces of elemental semiconductors, and the differences and the challenges associated with the Si and the Ge surfaces will be discussed. Our results suggest that this low-cost bottom-up approach is promising for applications in functional nanodevices. PMID:22315969

Nanoscale Structure at Mineral-Fluid Interfaces

NASA Astrophysics Data System (ADS)

Sturchio, N. C.; Sturchio, N. C.; Fenter, P.; Cheng, L.; Park, C.; Zhang, Z.; Zhang, Z.; Nagy, K. L.; Schlegel, M. L.

2001-12-01

The nature of nanoparticles and their role in the natural environment is currently a subject of renewed interest. The high surface area (and surface area-to-volume ratio) of nanoparticles exerts a widespread influence on geochemical reactions and transport processes. A thorough understanding of the nanoscale world remains largely hypothetical, however, because of the challenges associated with characterizing nanoscale structures and processes. Recent insights gained from high-resolution synchrotron x-ray reflectivity measurements at the solid-fluid interfaces of macroscopic (i.e., mm-scale) mineral particles may provide relevant guidelines for expected nanoparticle surface structures. For example, at calcite-water and barite-water interfaces, undercoordinated surface cations bond with water species of variable protonation, and modest relaxations (to several hundredths of a nanometer) affect the outermost unit cells [1,2]. Undercoordinated tetrahedral ions at aluminosilicate surfaces also bond with water species, whereas interstitial or interlayer alkali or alkaline earth ions at the surface may readily exchange with hydronium or other ions; modest relaxations also affect the outermost unit cells [3,4]. Modulation of liquid water structure out to about one nanometer has been observed at the (001) cleavage surface of muscovite in deionized water, and may be present at other mineral-fluid interfaces [4]. Dissolution mechanisms at the orthoclase-water interface have been clarified by combining x-ray reflectivity and scanning force microscopy measurements [5]. Further progress in understanding nanoscale structures and processes at macroscopic mineral-water interfaces is likely to benefit nanoparticle studies. [1] Fenter et al. (2000) Geochim. Cosmochim. Acta 64, 1221-1228. [2] Fenter et al. (2001) J. Phys. Chem. B 105(34), 8112-8119. [3] Fenter et al. (2000) Geochim. Cosmochim. Acta 64, 3663-3673. [4] Cheng et al. (2001) Phys. Rev. Lett., (in press). [5] Teng et al

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

PubMed

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

2010-05-07

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

Study of nanoscale structural biology using advanced particle beam microscopy

NASA Astrophysics Data System (ADS)

Boseman, Adam J.

This work investigates developmental and structural biology at the nanoscale using current advancements in particle beam microscopy. Typically the examination of micro- and nanoscale features is performed using scanning electron microscopy (SEM), but in order to decrease surface charging, and increase resolution, an obscuring conductive layer is applied to the sample surface. As magnification increases, this layer begins to limit the ability to identify nanoscale surface structures. A new technology, Helium Ion Microscopy (HIM), is used to examine uncoated surface structures on the cuticle of wild type and mutant fruit flies. Corneal nanostructures observed with HIM are further investigated by FIB/SEM to provide detailed three dimensional information about internal events occurring during early structural development. These techniques are also used to reconstruct a mosquito germarium in order to characterize unknown events in early oogenesis. Findings from these studies, and many more like them, will soon unravel many of the mysteries surrounding the world of developmental biology.

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with

Adsorption energy as a metric for wettability at the nanoscale

PubMed Central

Giro, Ronaldo; Bryant, Peter W.; Engel, Michael; Neumann, Rodrigo F.; Steiner, Mathias B.

2017-01-01

Wettability is the affinity of a liquid for a solid surface. For energetic reasons, macroscopic drops of liquid form nearly spherical caps. The degree of wettability is then captured by the contact angle where the liquid-vapor interface meets the solid-liquid interface. As droplet volumes shrink to the scale of attoliters, however, surface interactions become significant, and droplets assume distorted shapes. In this regime, the contact angle becomes ambiguous, and a scalable metric for quantifying wettability is needed, especially given the emergence of technologies exploiting liquid-solid interactions at the nanoscale. Here we combine nanoscale experiments with molecular-level simulation to study the breakdown of spherical droplet shapes at small length scales. We demonstrate how measured droplet topographies increasingly reveal non-spherical features as volumes shrink. Ultimately, the nanoscale droplets flatten out to form layer-like molecular assemblies at the solid surface. For the lack of an identifiable contact angle at small scales, we introduce a droplet’s adsorption energy density as a new metric for a liquid’s affinity for a surface. We discover that extrapolating the macroscopic idealization of a drop to the nanoscale, though it does not geometrically resemble a realistic droplet, can nonetheless recover its adsorption energy if line tension is included. PMID:28397869

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.

The mechanical analysis of thermo-magneto-electric laminated composites in nanoscale with the consideration of surface and flexoelectric effects

NASA Astrophysics Data System (ADS)

Shi, Shuanhu; Li, Peng; Jin, Feng

2018-01-01

A theoretical thermo-magneto-electric (TME) bilayer model is established based on the Hamilton principle, in which both surface effect and flexoelectricity are all taken into account. The governing equations are proposed with the aid of the nonlinear constitutive relations of giant magnetostrictive materials. These equations are general, which can be applied to analyze the coupled extensional, shear and bending deformations at both macroscale and nanoscale. As a specific example, the coupled extensional and bending motion of a slender beam suffering from external magnetic field and thermal variation is investigated, in which the Miller-Shenoy coefficient, magneto-electric (ME) effect, strain gradient and displacement are discussed in detail. After the necessary verification, a critical thickness of the TME model is proposed, below which the surface effect exhibits a remarkable influence on the mechanical behaviors and can not be ignored. It is revealed that the surface effect, flexoelectric effect and temperature increment are beneficial for the enhancement of the induced electric field. This study can provide theoretical basis for the design of nanoscale laminates, especially for the performance evaluation of ME composites under complex environment.

Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

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

He, Ting

2016-03-01

Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinarymore » collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering

Symmetry Breaking by Surface Blocking: Synthesis of Bimorphic Silver Nanoparticles, Nanoscale Fishes and Apples.

PubMed

Cathcart, Nicole; Kitaev, Vladimir

2016-09-08

A powerful approach to augment the diversity of well-defined metal nanoparticle (MNP) morphologies, essential for MNP advanced applications, is symmetry breaking combined with seeded growth. Utilizing this approach enabled the formation of bimorphic silver nanoparticles (bi-AgNPs) consisting of two shapes linked by one regrowth point. Bi-AgNPs were formed by using an adsorbing polymer, poly(acrylic acid), PAA, to block the surface of a decahedral AgNP seed and restricting growth of new silver to a single nucleation point. First, we have realized 2-D growth of platelets attached to decahedra producing nanoscale shapes reminiscent of apples, fishes, mushrooms and kites. 1-D bimorphic growth of rods (with chloride) and 3-D bimorphic growth of cubes and bipyramids (with bromide) were achieved by using halides to induce preferential (100) stabilization over (111) of platelets. Furthermore, the universality of the formation of bimorphic nanoparticles was demonstrated by using different seeds. Bi-AgNPs exhibit strong SERS enhancement due to regular cavities at the necks. Overall, the reported approach to symmetry breaking and bimorphic nanoparticle growth offers a powerful methodology for nanoscale shape design.

Symmetry Breaking by Surface Blocking: Synthesis of Bimorphic Silver Nanoparticles, Nanoscale Fishes and Apples

NASA Astrophysics Data System (ADS)

Cathcart, Nicole; Kitaev, Vladimir

2016-09-01

A powerful approach to augment the diversity of well-defined metal nanoparticle (MNP) morphologies, essential for MNP advanced applications, is symmetry breaking combined with seeded growth. Utilizing this approach enabled the formation of bimorphic silver nanoparticles (bi-AgNPs) consisting of two shapes linked by one regrowth point. Bi-AgNPs were formed by using an adsorbing polymer, poly(acrylic acid), PAA, to block the surface of a decahedral AgNP seed and restricting growth of new silver to a single nucleation point. First, we have realized 2-D growth of platelets attached to decahedra producing nanoscale shapes reminiscent of apples, fishes, mushrooms and kites. 1-D bimorphic growth of rods (with chloride) and 3-D bimorphic growth of cubes and bipyramids (with bromide) were achieved by using halides to induce preferential (100) stabilization over (111) of platelets. Furthermore, the universality of the formation of bimorphic nanoparticles was demonstrated by using different seeds. Bi-AgNPs exhibit strong SERS enhancement due to regular cavities at the necks. Overall, the reported approach to symmetry breaking and bimorphic nanoparticle growth offers a powerful methodology for nanoscale shape design.

Nanoscale topographic pattern formation on Kr{sup +}-bombarded germanium surfaces

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

Perkinson, Joy C.; Madi, Charbel S.; Aziz, Michael J.

2013-03-15

The nanoscale pattern formation of Ge surfaces uniformly irradiated by Kr{sup +} ions was studied in a low-contamination environment at ion energies of 250 and 500 eV and at angles of 0 Degree-Sign through 80 Degree-Sign . The authors present a phase diagram of domains of pattern formation occurring as these two control parameters are varied. The results are insensitive to ion energy over the range covered by the experiments. Flat surfaces are stable from normal incidence up to an incidence angle of {theta} = 55 Degree-Sign from normal. At higher angles, the surface is linearly unstable to the formationmore » of parallel-mode ripples, in which the wave vector is parallel to the projection of the ion beam on the surface. For {theta} {>=} 75 Degree-Sign the authors observe perpendicular-mode ripples, in which the wave vector is perpendicular to the ion beam. This behavior is qualitatively similar to those of Madi et al. for Ar{sup +}-irradiated Si but is inconsistent with those of Ziberi et al. for Kr{sup +}-irradiated Ge. The existence of a window of stability is qualitatively inconsistent with a theory based on sputter erosion [R. M. Bradley and J. M. Harper, J. Vac. Sci. Technol. A 6, 2390 (1988)] and qualitatively consistent with a model of ion impact-induced mass redistribution [G. Carter and V. Vishnyakov, Phys. Rev. B 54, 17647 (1996)] as well as a crater function theory incorporating both effects [S. A. Norris et al., Nat. Commun. 2, 276 (2011)]. The critical transition angle between stable and rippled surfaces occurs 10 Degree-Sign -15 Degree-Sign above the value of 45 Degree-Sign predicted by the mass redistribution model.« less

Density functional theory in surface chemistry and catalysis

PubMed Central

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

2011-01-01

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

Development of a Detailed Surface Chemistry Framework in DSMC

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Nanoscale electron transport at the surface of a topological insulator.

PubMed

Bauer, Sebastian; Bobisch, Christian A

2016-04-21

The use of three-dimensional topological insulators for disruptive technologies critically depends on the dissipationless transport of electrons at the surface, because of the suppression of backscattering at defects. However, in real devices, defects are unavoidable and scattering at angles other than 180° is allowed for such materials. Until now, this has been studied indirectly by bulk measurements and by the analysis of the local density of states in close vicinity to defect sites. Here, we directly measure the nanoscale voltage drop caused by the scattering at step edges, which occurs if a lateral current flows along a three-dimensional topological insulator. The experiments were performed using scanning tunnelling potentiometry for thin Bi2Se3 films. So far, the observed voltage drops are small because of large contributions of the bulk to the electronic transport. However, for the use of ideal topological insulating thin films in devices, these contributions would play a significant role.

Nanoscale electron transport at the surface of a topological insulator

NASA Astrophysics Data System (ADS)

Bauer, Sebastian; Bobisch, Christian A.

2016-04-01

The use of three-dimensional topological insulators for disruptive technologies critically depends on the dissipationless transport of electrons at the surface, because of the suppression of backscattering at defects. However, in real devices, defects are unavoidable and scattering at angles other than 180° is allowed for such materials. Until now, this has been studied indirectly by bulk measurements and by the analysis of the local density of states in close vicinity to defect sites. Here, we directly measure the nanoscale voltage drop caused by the scattering at step edges, which occurs if a lateral current flows along a three-dimensional topological insulator. The experiments were performed using scanning tunnelling potentiometry for thin Bi2Se3 films. So far, the observed voltage drops are small because of large contributions of the bulk to the electronic transport. However, for the use of ideal topological insulating thin films in devices, these contributions would play a significant role.

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

PubMed

Scully, John R

2015-01-01

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

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Mechanical writing of n-type conductive layers on the SrTiO3 surface in nanoscale

PubMed Central

Wang, Yuhang; Zhao, Kehan; Shi, Xiaolan; Li, Geng; Xie, Guanlin; Lai, Xubo; Ni, Jun; Zhang, Liuwan

2015-01-01

The fabrication and control of the conductive surface and interface on insulating SrTiO3 bulk provide a pathway for oxide electronics. The controllable manipulation of local doping concentration in semiconductors is an important step for nano-electronics. Here we show that conductive patterns can be written on bare SrTiO3 surface by controllable doping in nanoscale using the mechanical interactions of atomic force microscopy tip without applying external electric field. The conductivity of the layer is n-type, oxygen sensitive, and can be effectively tuned by the gate voltage. Hence, our findings have potential applications in oxide nano-circuits and oxygen sensors. PMID:26042679

EDITORIAL: Nanoscale metrology Nanoscale metrology

NASA Astrophysics Data System (ADS)

Picotto, G. B.; Koenders, L.; Wilkening, G.

2009-08-01

Instrumentation and measurement techniques at the nanoscale play a crucial role not only in extending our knowledge of the properties of matter and processes in nanosciences, but also in addressing new measurement needs in process control and quality assurance in industry. Micro- and nanotechnologies are now facing a growing demand for quantitative measurements to support the reliability, safety and competitiveness of products and services. Quantitative measurements presuppose reliable and stable instruments and measurement procedures as well as suitable calibration artefacts to ensure the quality of measurements and traceability to standards. This special issue of Measurement Science and Technology presents selected contributions from the Nanoscale 2008 seminar held at the Istituto Nazionale di Ricerca Metrologica (INRIM), Torino, in September 2008. This was the 4th Seminar on Nanoscale Calibration Standards and Methods and the 8th Seminar on Quantitative Microscopy (the first being held in 1995). The seminar was jointly organized by the Nanometrology Group within EUROMET (The European Collaboration in Measurement Standards), the German Nanotechnology Competence Centre 'Ultraprecise Surface Figuring' (CC-UPOB), the Physikalisch-Technische Bundesanstalt (PTB) and INRIM. A special event during the seminar was the 'knighting' of Günter Wilkening from PTB, Braunschweig, Germany, as the 1st Knight of Dimensional Nanometrology. Günter Wilkening received the NanoKnight Award for his outstanding work in the field of dimensional nanometrology over the last 20 years. The contributions in this special issue deal with the developments and improvements of instrumentation and measurement methods for scanning force microscopy (SFM), electron and optical microscopy, high-resolution interferometry, calibration of instruments and new standards, new facilities and applications including critical dimension (CD) measurements on small and medium structures and nanoparticle

Nanoscale surface modifications of medically relevant metals: state-of-the art and perspectives.

PubMed

Variola, Fabio; Brunski, John B; Orsini, Giovanna; Tambasco de Oliveira, Paulo; Wazen, Rima; Nanci, Antonio

2011-02-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently adopted to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. This review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately, the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, indeed, of all biomaterials.

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

NASA Astrophysics Data System (ADS)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox

Chemically stable and mechanically durable superamphiphobic aluminum surface with a micro/nanoscale binary structure.

PubMed

Peng, Shan; Yang, Xiaojun; Tian, Dong; Deng, Wenli

2014-09-10

We developed a simple fabrication method to prepare a superamphiphobic aluminum surface. On the basis of a low-energy surface and the combination of micro- and nanoscale roughness, the resultant surface became super-repellent toward a wide range of liquids with surface tensions of 25.3-72.1 mN m(-1). The applied approach involved (1) the formation of an irregular microplateau structure on an aluminum surface, (2) the fabrication of a nanoplatelet structure, and (3) fluorination treatment. The chemical stability and mechanical durability of the superamphiphobic surface were evaluated in detail. The results demonstrated that the surface presented an excellent chemical stability toward cool corrosive liquids (HCl/NaOH solutions, 25 °C) and 98% concentrated sulfuric acid, hot liquids (water, HCl/NaOH solutions, 30-100 °C), solvent immersion, high temperature, and a long-term period. More importantly, the surface also exhibited robust mechanical durability and could withstand multiple-fold, finger-touch, intensive scratching by a sharp blade, ultrasonication treatment, boiling treatment in water and coffee, repeated peeling by adhesive tape, and even multiple abrasion tests under 500 g of force without losing superamphiphobicity. The as-prepared superamphiphobic surface was also demonstrated to have excellent corrosion resistance. This work provides a simple, cost-effective, and highly efficient method to fabricate a chemically stable and mechanically robust superamphiphobic aluminum surface, which can find important outdoor applications.

Next Steps Forward in Understanding Martian Surface and Subsurface Chemistry

NASA Astrophysics Data System (ADS)

Carrier, Brandi L.

2017-09-01

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

Influence of surface structure and chemistry on water droplet splashing.

PubMed

Koch, Kerstin; Grichnik, Roland

2016-08-06

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

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

NASA Astrophysics Data System (ADS)

Vincent, Abhilash

Due to their therapeutic applications such as radical scavenging, MRI contrast imaging, Photoluminescence imaging, drug delivery, etc., nanoparticles (NPs) have a significant importance in bio-nanotechnology. The reason that prevents the utilizing NPs for drug delivery in medical field is mostly due to their biocompatibility issues (incompatibility can lead to toxicity and cell death). Changes in the surface conditions of NPs often lead to NP cytotoxicity. Investigating the role of NP surface properties (surface charges and surface chemistry) on their interactions with biomolecules (Cells, protein and DNA) could enhance the current understanding of NP cytotoxicity. Hence, it is highly beneficial to the nanotechnology community to bring more attention towards the enhancement of surface properties of NPs to make them more biocompatible and less toxic to biological systems. Surface functionalization of NPs using specific ligand biomolecules have shown to enhance the protein adsorption and cellular uptake through more favorable interaction pathways. Cerium oxide NPs (CNPs also known as nanoceria) are potential antioxidants in cell culture models and understanding the nature of interaction between cerium oxide NPs and biological proteins and cells are important due to their therapeutic application (especially in site specific drug delivery systems). The surface charges and surface chemistry of CNPs play a major role in protein adsorption and cellular uptake. Hence, by tuning the surface charges and by selecting proper functional molecules on the surface, CNPs exhibiting strong adhesion to biological materials can be prepared. By probing the nanoscale interaction forces acting between CNPs and protein molecules using Atomic Force Microscopy (AFM) based force-distance (F-D) spectroscopy, the mechanism of CNP-protein adsorption and CNP cellular uptake can be understood more quantitatively. The work presented in this dissertation is based on the application of AFM in

Ferroelectrics: A pathway to switchable surface chemistry and catalysis

NASA Astrophysics Data System (ADS)

Kakekhani, Arvin; Ismail-Beigi, Sohrab; Altman, Eric I.

2016-08-01

It has been known for more than six decades that ferroelectricity can affect a material's surface physics and chemistry thereby potentially enhancing its catalytic properties. Ferroelectrics are a class of materials with a switchable electrical polarization that can affect surface stoichiometry and electronic structure and thus adsorption energies and modes; e.g., molecular versus dissociative. Therefore, ferroelectrics may be utilized to achieve switchable surface chemistry whereby surface properties are not fixed but can be dynamically controlled by, for example, applying an external electric field or modulating the temperature. Several important examples of applications of ferroelectric and polar materials in photocatalysis and heterogeneous catalysis are discussed. In photocatalysis, the polarization direction can control band bending at water/ferroelectric and ferroelectric/semiconductor interfaces, thereby facilitating charge separation and transfer to the electrolyte and enhancing photocatalytic activity. For gas-surface interactions, available results suggest that using ferroelectrics to support catalytically active transition metals and oxides is another way to enhance catalytic activity. Finally, the possibility of incorporating ferroelectric switching into the catalytic cycle itself is described. In this scenario, a dynamic collaboration of two polarization states can be used to drive reactions that have been historically challenging to achieve on surfaces with fixed chemical properties (e.g., direct NOx decomposition and the selective partial oxidation of methane). These predictions show that dynamic modulation of the polarization can help overcome some of the fundamental limitations on catalytic activity imposed by the Sabatier principle.

A Thermal Diode Based on Nanoscale Thermal Radiation.

PubMed

Fiorino, Anthony; Thompson, Dakotah; Zhu, Linxiao; Mittapally, Rohith; Biehs, Svend-Age; Bezencenet, Odile; El-Bondry, Nadia; Bansropun, Shailendra; Ben-Abdallah, Philippe; Meyhofer, Edgar; Reddy, Pramod

2018-05-23

In this work we demonstrate thermal rectification at the nanoscale between doped Si and VO 2 surfaces. Specifically, we show that the metal-insulator transition of VO 2 makes it possible to achieve large differences in the heat flow between Si and VO 2 when the direction of the temperature gradient is reversed. We further show that this rectification increases at nanoscale separations, with a maximum rectification coefficient exceeding 50% at ∼140 nm gaps and a temperature difference of 70 K. Our modeling indicates that this high rectification coefficient arises due to broadband enhancement of heat transfer between metallic VO 2 and doped Si surfaces, as compared to narrower-band exchange that occurs when VO 2 is in its insulating state. This work demonstrates the feasibility of accomplishing near-field-based rectification of heat, which is a key component for creating nanoscale radiation-based information processing devices and thermal management approaches.

Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials

PubMed Central

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

2004-01-01

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

Learning Quantum Chemistry via a Visual-Conceptual Approach: Students' Bidirectional Textual and Visual Understanding

ERIC Educational Resources Information Center

Dangur, Vered; Avargil, Shirly; Peskin, Uri; Dori, Yehudit Judy

2014-01-01

Most undergraduate chemistry courses and a few high school honors courses, which focus on physical chemistry and quantum mechanics, are highly mathematically-oriented. At the Technion, Israel Institute of Technology, we developed a new module for high school students, titled "Chemistry--From 'the Hole' to 'the Whole': From the Nanoscale to…

Nanoscale Characterization of Carrier Dynamic and Surface Passivation in InGaN/GaN Multiple Quantum Wells on GaN Nanorods.

PubMed

Chen, Weijian; Wen, Xiaoming; Latzel, Michael; Heilmann, Martin; Yang, Jianfeng; Dai, Xi; Huang, Shujuan; Shrestha, Santosh; Patterson, Robert; Christiansen, Silke; Conibeer, Gavin

2016-11-23

Using advanced two-photon excitation confocal microscopy, associated with time-resolved spectroscopy, we characterize InGaN/GaN multiple quantum wells on nanorod heterostructures and demonstrate the passivation effect of a KOH treatment. High-quality InGaN/GaN nanorods were fabricated using nanosphere lithography as a candidate material for light-emitting diode devices. The depth- and time-resolved characterization at the nanoscale provides detailed carrier dynamic analysis helpful for understanding the optical properties. The nanoscale spatially resolved images of InGaN quantum well and defects were acquired simultaneously. We demonstrate that nanorod etching improves light extraction efficiency, and a proper KOH treatment has been found to reduce the surface defects efficiently and enhance the luminescence. The optical characterization techniques provide depth-resolved and time-resolved carrier dynamics with nanoscale spatially resolved mapping, which is crucial for a comprehensive and thorough understanding of nanostructured materials and provides novel insight into the improvement of materials fabrication and applications.

Nanoscale Chemical Processes Affecting Storage Capacities and Seals during Geologic CO2 Sequestration.

PubMed

Jun, Young-Shin; Zhang, Lijie; Min, Yujia; Li, Qingyun

2017-07-18

Geologic CO 2 sequestration (GCS) is a promising strategy to mitigate anthropogenic CO 2 emission to the atmosphere. Suitable geologic storage sites should have a porous reservoir rock zone where injected CO 2 can displace brine and be stored in pores, and an impermeable zone on top of reservoir rocks to hinder upward movement of buoyant CO 2 . The injection wells (steel casings encased in concrete) pass through these geologic zones and lead CO 2 to the desired zones. In subsurface environments, CO 2 is reactive as both a supercritical (sc) phase and aqueous (aq) species. Its nanoscale chemical reactions with geomedia and wellbores are closely related to the safety and efficiency of CO 2 storage. For example, the injection pressure is determined by the wettability and permeability of geomedia, which can be sensitive to nanoscale mineral-fluid interactions; the sealing safety of the injection sites is affected by the opening and closing of fractures in caprocks and the alteration of wellbore integrity caused by nanoscale chemical reactions; and the time scale for CO 2 mineralization is also largely dependent on the chemical reactivities of the reservoir rocks. Therefore, nanoscale chemical processes can influence the hydrogeological and mechanical properties of geomedia, such as their wettability, permeability, mechanical strength, and fracturing. This Account reviews our group's work on nanoscale chemical reactions and their qualitative impacts on seal integrity and storage capacity at GCS sites from four points of view. First, studies on dissolution of feldspar, an important reservoir rock constituent, and subsequent secondary mineral precipitation are discussed, focusing on the effects of feldspar crystallography, cations, and sulfate anions. Second, interfacial reactions between caprock and brine are introduced using model clay minerals, with focuses on the effects of water chemistries (salinity and organic ligands) and water content on mineral dissolution and

Nanoscale wear and kinetic friction between atomically smooth surfaces sliding at high speeds

NASA Astrophysics Data System (ADS)

Rajauria, Sukumar; Canchi, Sripathi V.; Schreck, Erhard; Marchon, Bruno

2015-02-01

The kinetic friction and wear at high sliding speeds is investigated using the head-disk interface of hard disk drives, wherein the head and the disk are less than 10 nm apart and move at sliding speeds of 5-10 m/s relative to each other. While the spacing between the sliding surfaces is of the same order of magnitude as various AFM based fundamental studies on friction, the sliding speed is nearly six orders of magnitude larger, allowing a unique set-up for a systematic study of nanoscale wear at high sliding speeds. In a hard disk drive, the physical contact between the head and the disk leads to friction, wear, and degradation of the head overcoat material (typically diamond like carbon). In this work, strain gauge based friction measurements are performed; the friction coefficient as well as the adhering shear strength at the head-disk interface is extracted; and an experimental set-up for studying friction between high speed sliding surfaces is exemplified.

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

DOE PAGES

Tolbert, Allison K.; Ragauskas, Arthur J.

2016-12-12

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

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

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

Tolbert, Allison K.; Ragauskas, Arthur J.

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

Synthesis of nanoscale copper nitride thin film and modification of the surface under high electronic excitation.

PubMed

Ghosh, S; Tripathi, A; Ganesan, V; Avasthi, D K

2008-05-01

Nanoscale (approximately 90 nm) Copper nitride (Cu3N) films are deposited on borosilicate glass and Si substrates by RF sputtering technique in the reactive environment of nitrogen gas. These films are irradiated with 200 MeV Au15+ ions from Pelletron accelerator in order to modify the surface by high electronic energy deposition of heavy ions. Due to irradiation (i) at incident ion fluence of 1 x 10(12) ions/cm2 enhancement of grains, (ii) at 5 x 10912) ions/cm2 mass transport on the films surface, (iii) at 2 x 10(13) ions/cm2 line-like features on Cu3N/glass and nanometallic structures on Cu3N/Si surface are observed. The surface morphology is examined by atomic force microscope (AFM). All results are explained on the basis of a thermal spike model of ion-solid interaction.

Spatial Manipulation of Heat Flow by Surface Boundaries at the Nanoscale

NASA Astrophysics Data System (ADS)

Malhotra, Abhinav; Maldovan, Martin

The precise manipulation of phonon transport properties is central to controlling thermal transport in semiconductor nanostructures. The physical understanding, prediction, and control of thermal phonon heat spectra and thermal conductivity accumulation functions - which establish the proportion of heat transported by phonons with different frequencies and mean-free-paths - has attracted significant attention in recent years. In this talk, we advance the possibilities of manipulating heat by spatially modulating thermal transport in nanostructures. We show that phonon scattering at interfaces impacts the most preferred physical pathway used by heat energy flow in thermal transport in nanostructures. The role of introducing boundaries with different surface conditions on resultant thermal flux is presented and methodologies to enhance these spatial modulations are discussed. This talk aims to advance the fundamental understanding on the nature of heat transport at nanoscale with potential applications in multiple research areas ranging from energy materials to optoelectronics.

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

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

Not Available

1990-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Surface chemistry and mineralogy. [of planet Mars

NASA Technical Reports Server (NTRS)

Banin, A.; Clark, B. C.; Waenke, H.

1992-01-01

The accumulated knowledge on the chemistry and mineralogy of Martian surface materials is reviewed. Pertinent information obtained by direct analyses of the soil on Mars by the Viking Landers, by remote sensing of Mars from flyby and orbiting spacecraft, by telescopic observations from earth, and through detailed analyses of the SNC meteorites presumed to be Martian rocks are summarized and analyzed. A compositional model for Mars soil, giving selected average elemental concentrations of major and trace elements, is suggested. It is proposed that the fine surface materials on Mars are a multicomponent mixture of weathered and nonweathered minerals. Smectite clays, silicate mineraloids similar to palagonite, and scapolite are suggested as possible major candidate components among the weathered minerals.

Nanoscale relaxation oscillator

DOEpatents

Zettl, Alexander K.; Regan, Brian C.; Aloni, Shaul

2009-04-07

A nanoscale oscillation device is disclosed, wherein two nanoscale droplets are altered in size by mass transport, then contact each other and merge through surface tension. The device may also comprise a channel having an actuator responsive to mechanical oscillation caused by expansion and contraction of the droplets. It further has a structure for delivering atoms between droplets, wherein the droplets are nanoparticles. Provided are a first particle and a second particle on the channel member, both being made of a chargeable material, the second particle contacting the actuator portion; and electrodes connected to the channel member for delivering a potential gradient across the channel and traversing the first and second particles. The particles are spaced apart a specified distance so that atoms from one particle are delivered to the other particle by mass transport in response to the potential (e.g. voltage potential) and the first and second particles are liquid and touch at a predetermined point of growth, thereby causing merging of the second particle into the first particle by surface tension forces and reverse movement of the actuator. In a preferred embodiment, the channel comprises a carbon nanotube and the droplets comprise metal nanoparticles, e.g. indium, which is readily made liquid.

Cold atmospheric plasma (CAP) surface nanomodified 3D printed polylactic acid (PLA) scaffolds for bone regeneration.

PubMed

Wang, Mian; Favi, Pelagie; Cheng, Xiaoqian; Golshan, Negar H; Ziemer, Katherine S; Keidar, Michael; Webster, Thomas J

2016-12-01

Three-dimensional (3D) printing is a new fabrication method for tissue engineering which can precisely control scaffold architecture at the micron-scale. However, scaffolds not only need 3D biocompatible structures that mimic the micron structure of natural tissues, they also require mimicking of the nano-scale extracellular matrix properties of the tissue they intend to replace. In order to achieve this, the objective of the present in vitro study was to use cold atmospheric plasma (CAP) as a quick and inexpensive way to modify the nano-scale roughness and chemical composition of a 3D printed scaffold surface. Water contact angles of a normal 3D printed poly-lactic-acid (PLA) scaffold dramatically dropped after CAP treatment from 70±2° to 24±2°. In addition, the nano-scale surface roughness (Rq) of the untreated 3D PLA scaffolds drastically increased (up to 250%) after 1, 3, and 5min of CAP treatment from 1.20nm to 10.50nm, 22.90nm, and 27.60nm, respectively. X-ray photoelectron spectroscopy (XPS) analysis showed that the ratio of oxygen to carbon significantly increased after CAP treatment, which indicated that the CAP treatment of PLA not only changed nano-scale roughness but also chemistry. Both changes in hydrophilicity and nano-scale roughness demonstrated a very efficient plasma treatment, which in turn significantly promoted both osteoblast (bone forming cells) and mesenchymal stem cell attachment and proliferation. These promising results suggest that CAP surface modification may have potential applications for enhancing 3D printed PLA bone tissue engineering materials (and all 3D printed materials) in a quick and an inexpensive manner and, thus, should be further studied. Three-dimensional (3D) printing is a new fabrication method for tissue engineering which can precisely control scaffold architecture at the micron-scale. Although their success is related to their ability to exactly mimic the structure of natural tissues and control mechanical

Nanoscale surface modifications of medically-relevant metals: state-of-the art and perspectives

PubMed Central

Variola, Fabio; Brunski, John; Orsini, Giovanna; de Oliveira, Paulo Tambasco; Wazen, Rima; Nanci, Antonio

2011-01-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently used to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. Importantly, this review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, as a matter of fact, all biomaterials. PMID:20976359

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

PubMed

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

2017-04-01

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

From surface to intracellular non-invasive nanoscale study of living cells impairments

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

Ewald, Dr. Maxime; Tetard, Laurene; Elie-Caille, Dr. Cecile

Among the enduring challenges in nanoscience, subsurface characterization of live cells holds major stakes. Developments in nanometrology for soft matter thriving on the sensitivity and high resolution benefits of atomic force microscopy have enabled detection of subsurface structures at the nanoscale (1,2,3). However, measurements in liquid environments remain complex (4,5,6,7), in particular in the subsurface domain. Here we introduce liquid-Mode Synthesizing Atomic Force Microscopy (l-MSAFM) to study both the inner structures and the chemically induced intracellular impairments of living cells. Specifically, we visualize the intracellular stress effects of glyphosate on living keratinocytes skin cells. This new approach for living cellmore » nanoscale imaging, l-MSAFM, in their physiological environment or in presence of a chemical stress agent confirmed the loss of inner structures induced by glyphosate. The ability to monitor the cell's inner response to external stimuli, non-destructively and in real time, has the potential to unveil critical nanoscale mechanisms of life science.« less

From surface to intracellular non-invasive nanoscale study of living cells impairments

NASA Astrophysics Data System (ADS)

Ewald, M.; Tetard, L.; Elie-Caille, C.; Nicod, L.; Passian, A.; Bourillot, E.; Lesniewska, E.

2014-07-01

Among the enduring challenges in nanoscience, subsurface characterization of living cells holds major stakes. Developments in nanometrology for soft matter thriving on the sensitivity and high resolution benefits of atomic force microscopy have enabled detection of subsurface structures at the nanoscale. However, measurements in liquid environments remain complex, in particular in the subsurface domain. Here we introduce liquid-mode synthesizing atomic force microscopy (l-MSAFM) to study both the inner structures and the chemically induced intracellular impairments of living cells. Specifically, we visualize the intracellular stress effects of glyphosate on living keratinocytes skin cells. This new approach, l-MSAFM, for nanoscale imaging of living cell in their physiological environment or in presence of a chemical stress agent could resolve the loss of inner structures induced by glyphosate, the main component of a well-known pesticide (RoundUp™). This firsthand ability to monitor the cell’s inner response to external stimuli non-destructively and in liquid, has the potential to unveil critical nanoscale mechanisms of life science.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Pinning of the Contact Line during Evaporation on Heterogeneous Surfaces: Slowdown or Temporary Immobilization? Insights from a Nanoscale Study.

PubMed

Zhang, Jianguo; Müller-Plathe, Florian; Leroy, Frédéric

2015-07-14

The question of the effect of surface heterogeneities on the evaporation of liquid droplets from solid surfaces is addressed through nonequilibrium molecular dynamics simulations. The mechanism behind contact line pinning which is still unclear is discussed in detail on the nanoscale. Model systems with the Lennard-Jones interaction potential were employed to study the evaporation of nanometer-sized cylindrical droplets from a flat surface. The heterogeneity of the surface was modeled through alternating stripes of equal width but two chemical types. The first type leads to a contact angle of 67°, and the other leads to a contact angle of 115°. The stripe width was varied between 2 and 20 liquid-particle diameters. On the surface with the narrowest stripes, evaporation occurred at constant contact angle as if the surface was homogeneous, with a value of the contact angle as predicted by the regular Cassie-Baxter equation. When the width was increased, the contact angle oscillated during evaporation between two boundaries whose values depend on the stripe width. The evaporation behavior was thus found to be a direct signature of the typical size of the surface heterogeneity domains. The contact angle both at equilibrium and during evaporation could be predicted from a local Cassie-Baxter equation in which the surface composition within a distance of seven fluid-particle diameters around the contact line was considered, confirming the local nature of the interactions that drive the wetting behavior of droplets. More importantly, we propose a nanoscale explanation of pinning during evaporation. Pinning should be interpreted as a drastic slowdown of the contact line dynamics rather than a complete immobilization of it during a transition between two contact angle boundaries.

Surface Plasmon-Mediated Nanoscale Localization of Laser-Driven sub-Terahertz Spin Dynamics in Magnetic Dielectrics.

PubMed

Chekhov, Alexander L; Stognij, Alexander I; Satoh, Takuya; Murzina, Tatiana V; Razdolski, Ilya; Stupakiewicz, Andrzej

2018-05-09

We report spatial localization of the effective magnetic field generated via the inverse Faraday effect employing surface plasmon polaritons (SPPs) at Au/garnet interface. Analyzing both numerically and analytically the electric field of the SPPs at this interface, we corroborate our study with a proof-of-concept experiment showing efficient SPP-driven excitation of coherent spin precession with 0.41 THz frequency. We argue that the subdiffractional confinement of the SPP electric field enables strong spatial localization of the SPP-mediated excitation of spin dynamics. We demonstrate two orders of magnitude enhancement of the excitation efficiency at the surface plasmon resonance within a 100 nm layer of a dielectric garnet. Our findings broaden the horizons of ultrafast spin-plasmonics and open pathways toward nonthermal opto-magnetic recording on the nanoscale.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Bio-Organic Nanotechnology: Using Proteins and Synthetic Polymers for Nanoscale Devices

NASA Technical Reports Server (NTRS)

Molnar, Linda K.; Xu, Ting; Trent, Jonathan D.; Russell, Thomas P.

2003-01-01

While the ability of proteins to self-assemble makes them powerful tools in nanotechnology, in biological systems protein-based structures ultimately depend on the context in which they form. We combine the self-assembling properties of synthetic diblock copolymers and proteins to construct intricately ordered, three-dimensional polymer protein structures with the ultimate goal of forming nano-scale devices. This hybrid approach takes advantage of the capabilities of organic polymer chemistry to build ordered structures and the capabilities of genetic engineering to create proteins that are selective for inorganic or organic substrates. Here, microphase-separated block copolymers coupled with genetically engineered heat shock proteins are used to produce nano-scale patterning that maximizes the potential for both increased structural complexity and integrity.

Nano-scale processes behind ion-beam cancer therapy

NASA Astrophysics Data System (ADS)

Surdutovich, Eugene; Garcia, Gustavo; Mason, Nigel; Solov'yov, Andrey V.

2016-04-01

This topical issue collates a series of papers based on new data reported at the third Nano-IBCT Conference of the COST Action MP1002: Nanoscale Insights into Ion Beam Cancer Therapy, held in Boppard, Germany, from October 27th to October 31st, 2014. The Nano-IBCT COST Action was launched in December 2010 and brought together more than 300 experts from different disciplines (physics, chemistry, biology) with specialists in radiation damage of biological matter from hadron-therapy centres, and medical institutions. This meeting followed the first and the second conferences of the Action held in October 2011 in Caen, France and in May 2013 in Sopot, Poland respectively. This conference series provided a focus for the European research community and has highlighted the pioneering research into the fundamental processes underpinning ion beam cancer therapy. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey V. Solov'yov, Nigel Mason, Gustavo Garcia and Eugene Surdutovich.

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2015-09-04

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

Chemistry of the surface and lower atmosphere of Venus

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

Surface chemistry of gold nanorods: origin of cell membrane damage and cytotoxicity

NASA Astrophysics Data System (ADS)

Wang, Liming; Jiang, Xiumei; Ji, Yinglu; Bai, Ru; Zhao, Yuliang; Wu, Xiaochun; Chen, Chunying

2013-08-01

We investigated how surface chemistry influences the interaction between gold nanorods (AuNRs) and cell membranes and the subsequent cytotoxicity arising from them in a serum-free cell culture system. Our results showed that the AuNRs coated with cetyl trimethylammonium bromide (CTAB) molecules can generate defects in the cell membrane and induce cell death, mainly due to the unique bilayer structure of CTAB molecules on the surface of the rods rather than their charge. Compared to CTAB-capped nanorods, positively charged polyelectrolyte-coated, i.e. poly(diallyldimethyl ammonium chloride) (PDDAC), AuNRs show improved biocompatibility towards cells. Thus, the present results indicate that the nature of surface molecules, especially their packing structures on the surface of AuNRs rather than surface charge, play a more crucial role in determining cytotoxicity. These findings about interfacial interactions could also explain the effects of internalized AuNRs on the structures or functions of organelles. This study will help understanding of the toxic nature of AuNRs and guide rational design of the surface chemistry of AuNRs for good biocompatibility in pharmaceutical therapy.

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.

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

PubMed

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

2015-12-06

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

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

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

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

2015-09-15

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

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

PubMed Central

Syverud, Kristin

2014-01-01

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

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

DTIC Science & Technology

2015-12-21

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

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

PubMed

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

2015-03-26

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

Surface Plasmon-Mediated Nanoscale Localization of Laser-Driven sub-Terahertz Spin Dynamics in Magnetic Dielectrics

NASA Astrophysics Data System (ADS)

Chekhov, Alexander L.; Stognij, Alexander I.; Satoh, Takuya; Murzina, Tatiana V.; Razdolski, Ilya; Stupakiewicz, Andrzej

2018-05-01

Ultrafast all-optical control of spins with femtosecond laser pulses is one of the hot topics at the crossroads of photonics and magnetism with a direct impact on future magnetic recording. Unveiling light-assisted recording mechanisms for an increase of the bit density beyond the diffraction limit without excessive heating of the recording medium is an open challenge. Here we show that surface plasmon-polaritons in hybrid metal-dielectric structures can provide spatial confinement of the inverse Faraday effect, mediating the excitation of localized coherent spin precession with 0.41 THz frequency. We demonstrate a two orders of magnitude enhancement of the excitation efficiency at the surface plasmon resonance within the 100 nm layer in dielectric garnet. Our findings broaden the horizons of ultrafast spin-plasmonics and open pathways towards non-thermal opto-magnetic recording at the nano-scale.

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.

Superhydrophobic surfaces

DOEpatents

Wang, Evelyn N; McCarthy, Matthew; Enright, Ryan; Culver, James N; Gerasopoulos, Konstantinos; Ghodssi, Reza

2015-03-24

Surfaces having a hierarchical structure--having features of both microscale and nanoscale dimensions--can exhibit superhydrophobic properties and advantageous condensation and heat transfer properties. The hierarchical surfaces can be fabricated using biological nanostructures, such as viruses as a self-assembled nanoscale template.

Tip-enhanced ablation and ionization mass spectrometry for nanoscale chemical analysis

PubMed Central

Liang, Zhisen; Zhang, Shudi; Li, Xiaoping; Wang, Tongtong; Huang, Yaping; Hang, Wei; Yang, Zhilin; Li, Jianfeng; Tian, Zhongqun

2017-01-01

Spectroscopic methods with nanoscale lateral resolution are becoming essential in the fields of physics, chemistry, geology, biology, and materials science. However, the lateral resolution of laser-based mass spectrometry imaging (MSI) techniques has so far been limited to the microscale. This report presents the development of tip-enhanced ablation and ionization time-of-flight mass spectrometry (TEAI-TOFMS), using a shell-isolated apertureless silver tip. The TEAI-TOFMS results indicate the capability and reproducibility of the system for generating nanosized craters and for acquiring the corresponding mass spectral signals. Multi-elemental analysis of nine inorganic salt residues and MSI of a potassium salt residue pattern at a 50-nm lateral resolution were achieved. These results demonstrate the opportunity for the distribution of chemical compositions at the nanoscale to be visualized. PMID:29226250

Nanoscale Structure and Interaction of Compact Assemblies of Carbon Nano-Materials

NASA Astrophysics Data System (ADS)

Timsina, Raju; Qiu, Xiangyun

Carbon-based nano-materials (CNM) are a diverse family of multi-functional materials under research and development world wide. Our work is further motivated by the predictive power of the physical understanding of the underlying structure-interaction-function relationships. Here we present results form recent studies of the condensed phases of several model CNMs in complexation with biologically derived molecules. Specifically, we employ X-ray diffraction (XRD) to determine nanoscale structures and use the osmotic stress method to quantify their interactions. The systems under investigation are dsDNA-dispersed carbon nanotubes (dsDNA-CNT), bile-salt-dispersed carbon nanotubes, and surfactant-assisted assemblies of graphene oxides. We found that salt and molecular crowding are both effective in condensing CNMs but the resultant structures show disparate phase behaviors. The molecular interactions driving the condensation/assembly sensitively depend on the nature of CNM complex surface chemistry and range from hydrophobic to electrostatic to entropic forces.

On the origin of enhanced sensitivity in nanoscale FET-based biosensors

PubMed Central

Shoorideh, Kaveh; Chui, Chi On

2014-01-01

Electrostatic counter ion screening is a phenomenon that is detrimental to the sensitivity of charge detection in electrolytic environments, such as in field-effect transistor-based biosensors. Using simple analytical arguments, we show that electrostatic screening is weaker in the vicinity of concave curved surfaces, and stronger in the vicinity of convex surfaces. We use this insight to show, using numerical simulations, that the enhanced sensitivity observed in nanoscale biosensors is due to binding of biomolecules in concave corners where screening is reduced. We show that the traditional argument, that increased surface area-to-volume ratio for nanoscale sensors is responsible for their increased sensitivity, is incorrect. PMID:24706861

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

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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

PubMed

Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

2017-10-01

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

Mixed electrochemical–ferroelectric states in nanoscale ferroelectrics

DOE PAGES

Yang, Sang Mo; Morozovska, Anna N.; Kumar, Rajeev; ...

2017-05-01

Ferroelectricity on the nanoscale has been the subject of much fascination in condensed-matter physics for over half a century. In recent years, multiple reports claiming ferroelectricity in ultrathin ferroelectric films based on the formation of remnant polarization states, local electromechanical hysteresis loops, and pressure-induced switching were made. But, similar phenomena were reported for traditionally non-ferroelectric materials, creating a significant level of uncertainty in the field. We show that in nanoscale systems the ferroelectric state is fundamentally inseparable from the electrochemical state of the surface, leading to the emergence of a mixed electrochemical–ferroelectric state. We explore the nature, thermodynamics, and thicknessmore » evolution of such states, and demonstrate the experimental pathway to establish its presence. Our analysis reconciles multiple prior studies, provides guidelines for studies of ferroelectric materials on the nanoscale, and establishes the design paradigm for new generations of ferroelectric-based devices.« less

Nanoscale thermal transport. II. 2003-2012

NASA Astrophysics Data System (ADS)

Cahill, David G.; Braun, Paul V.; Chen, Gang; Clarke, David R.; Fan, Shanhui; Goodson, Kenneth E.; Keblinski, Pawel; King, William P.; Mahan, Gerald D.; Majumdar, Arun; Maris, Humphrey J.; Phillpot, Simon R.; Pop, Eric; Shi, Li

2014-03-01

A diverse spectrum of technology drivers such as improved thermal barriers, higher efficiency thermoelectric energy conversion, phase-change memory, heat-assisted magnetic recording, thermal management of nanoscale electronics, and nanoparticles for thermal medical therapies are motivating studies of the applied physics of thermal transport at the nanoscale. This review emphasizes developments in experiment, theory, and computation in the past ten years and summarizes the present status of the field. Interfaces become increasingly important on small length scales. Research during the past decade has extended studies of interfaces between simple metals and inorganic crystals to interfaces with molecular materials and liquids with systematic control of interface chemistry and physics. At separations on the order of ˜ 1 nm , the science of radiative transport through nanoscale gaps overlaps with thermal conduction by the coupling of electronic and vibrational excitations across weakly bonded or rough interfaces between materials. Major advances in the physics of phonons include first principles calculation of the phonon lifetimes of simple crystals and application of the predicted scattering rates in parameter-free calculations of the thermal conductivity. Progress in the control of thermal transport at the nanoscale is critical to continued advances in the density of information that can be stored in phase change memory devices and new generations of magnetic storage that will use highly localized heat sources to reduce the coercivity of magnetic media. Ultralow thermal conductivity—thermal conductivity below the conventionally predicted minimum thermal conductivity—has been observed in nanolaminates and disordered crystals with strong anisotropy. Advances in metrology by time-domain thermoreflectance have made measurements of the thermal conductivity of a thin layer with micron-scale spatial resolution relatively routine. Scanning thermal microscopy and thermal

Global transcriptomic analysis of model human cell lines exposed to surface-modified gold nanoparticles: the effect of surface chemistry

NASA Astrophysics Data System (ADS)

Grzincic, E. M.; Yang, J. A.; Drnevich, J.; Falagan-Lotsch, P.; Murphy, C. J.

2015-01-01

Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how Au NPs and their surface coatings may impact cellular gene expression. The gene expression of two model human cell lines, human dermal fibroblasts (HDF) and prostate cancer cells (PC3) was interrogated by microarray analysis of over 14 000 human genes. The cell lines were exposed to four differently functionalized Au NPs: citrate, poly(allylamine hydrochloride) (PAH), and lipid coatings combined with alkanethiols or PAH. Gene functional annotation categories and weighted gene correlation network analysis were used in order to connect gene expression changes to common cellular functions and to elucidate expression patterns between Au NP samples. Coated Au NPs affect genes implicated in proliferation, angiogenesis, and metabolism in HDF cells, and inflammation, angiogenesis, proliferation apoptosis regulation, survival and invasion in PC3 cells. Subtle changes in surface chemistry, such as the initial net charge, lability of the ligand, and underlying layers greatly influence the degree of expression change and the type of cellular pathway affected.Gold nanoparticles (Au NPs) are attractive for biomedical applications not only for their remarkable physical properties, but also for the ease of which their surface chemistry can be manipulated. Many applications involve functionalization of the Au NP surface in order to improve biocompatibility, attach targeting ligands or carry drugs. However, changes in cells exposed to Au NPs of different surface chemistries have been observed, and little is known about how

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

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

PubMed

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

2014-06-01

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

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

PubMed

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

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

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

PubMed

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

2017-03-15

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

Indium-tin-oxide nanowhiskers crystalline silicon photovoltaics combining micro- and nano-scale surface textures

NASA Astrophysics Data System (ADS)

Chang, C. H.; Hsu, M. H.; Chang, W. L.; Sun, W. C.; Yu, Peichen

2011-02-01

In this work, we present a solution that employs combined micro- and nano-scale surface textures to increase light harvesting in the near infrared for crystalline silicon photovoltaics, and discuss the associated antireflection and scattering mechanisms. The combined surface textures are achieved by uniformly depositing a layer of indium-tin-oxide nanowhiskers on passivated, micro-grooved silicon solar cells using electron-beam evaporation. The nanowhiskers facilitate optical transmission in the near-infrared, which is optically equivalent to a stack of two dielectric thin-films with step- and graded- refractive index profiles. The ITO nanowhiskers provide broadband anti-reflective properties (R<5%) in the wavelength range of 350-1100nm. In comparison with conventional Si solar cell, the combined surface texture solar cell shows higher external quantum efficiency (EQE) in the range of 700-1100nm. Moreover, the ITO nano-whisker coating Si solar cell shows a high total efficiency increase of 1.1% (from 16.08% to17.18%). Furthermore, the nano-whiskers also provide strong forward scattering for ultraviolet and visible light, favorable in thin-wafer silicon photovoltaics to increase the optical absorption path.

Nanoscale β-nuclear magnetic resonance depth imaging of topological insulators

PubMed Central

Koumoulis, Dimitrios; Morris, Gerald D.; He, Liang; Kou, Xufeng; King, Danny; Wang, Dong; Hossain, Masrur D.; Wang, Kang L.; Fiete, Gregory A.; Kanatzidis, Mercouri G.; Bouchard, Louis-S.

2015-01-01

Considerable evidence suggests that variations in the properties of topological insulators (TIs) at the nanoscale and at interfaces can strongly affect the physics of topological materials. Therefore, a detailed understanding of surface states and interface coupling is crucial to the search for and applications of new topological phases of matter. Currently, no methods can provide depth profiling near surfaces or at interfaces of topologically inequivalent materials. Such a method could advance the study of interactions. Herein, we present a noninvasive depth-profiling technique based on β-detected NMR (β-NMR) spectroscopy of radioactive 8Li+ ions that can provide “one-dimensional imaging” in films of fixed thickness and generates nanoscale views of the electronic wavefunctions and magnetic order at topological surfaces and interfaces. By mapping the 8Li nuclear resonance near the surface and 10-nm deep into the bulk of pure and Cr-doped bismuth antimony telluride films, we provide signatures related to the TI properties and their topological nontrivial characteristics that affect the electron–nuclear hyperfine field, the metallic shift, and magnetic order. These nanoscale variations in β-NMR parameters reflect the unconventional properties of the topological materials under study, and understanding the role of heterogeneities is expected to lead to the discovery of novel phenomena involving quantum materials. PMID:26124141

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

PubMed

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

2016-10-01

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

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

PubMed Central

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

1981-01-01

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

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

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

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

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

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

DOE PAGES

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

2017-12-18

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

Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

PubMed

Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

2013-05-21

Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

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

PubMed

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

2018-03-20

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be

EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles.

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

NASA Astrophysics Data System (ADS)

Yonata, B.; Nasrudin, H.

2018-01-01

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

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

PubMed

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

2016-09-28

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

Nanoscale perspective: Materials designs and understandings in lithium metal anodes

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

Lin, Dingchang; Liu, Yayuan; Pei, Allen

Li metal chemistry is a promising alternative with a much higher energy density than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technology from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies onmore » nanoscale Li nucleation/deposition. Lastly, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technology and inspires more research in the future.« less

Nanoscale perspective: Materials designs and understandings in lithium metal anodes

DOE PAGES

Lin, Dingchang; Liu, Yayuan; Pei, Allen; ...

2017-05-19

Li metal chemistry is a promising alternative with a much higher energy density than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technology from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies onmore » nanoscale Li nucleation/deposition. Lastly, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technology and inspires more research in the future.« less

Adhesion-dependent negative friction coefficient on chemically modified graphite at the nanoscale

NASA Astrophysics Data System (ADS)

Deng, Zhao; Smolyanitsky, Alex; Li, Qunyang; Feng, Xi-Qiao; Cannara, Rachel J.

2012-12-01

From the early tribological studies of Leonardo da Vinci to Amontons’ law, friction has been shown to increase with increasing normal load. This trend continues to hold at the nanoscale, where friction can vary nonlinearly with normal load. Here we present nanoscale friction force microscopy (FFM) experiments for a nanoscale probe tip sliding on a chemically modified graphite surface in an atomic force microscope (AFM). Our results demonstrate that, when adhesion between the AFM tip and surface is enhanced relative to the exfoliation energy of graphite, friction can increase as the load decreases under tip retraction. This leads to the emergence of an effectively negative coefficient of friction in the low-load regime. We show that the magnitude of this coefficient depends on the ratio of tip-sample adhesion to the exfoliation energy of graphite. Through both atomistic- and continuum-based simulations, we attribute this unusual phenomenon to a reversible partial delamination of the topmost atomic layers, which then mimic few- to single-layer graphene. Lifting of these layers with the AFM tip leads to greater deformability of the surface with decreasing applied load. This discovery suggests that the lamellar nature of graphite yields nanoscale tribological properties outside the predictive capacity of existing continuum mechanical models.

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

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

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

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

The Role of Membrane Curvature in Nanoscale Topography-Induced Intracellular Signaling.

PubMed

Lou, Hsin-Ya; Zhao, Wenting; Zeng, Yongpeng; Cui, Bianxiao

2018-05-15

Over the past decade, there has been growing interest in developing biosensors and devices with nanoscale and vertical topography. Vertical nanostructures induce spontaneous cell engulfment, which enhances the cell-probe coupling efficiency and the sensitivity of biosensors. Although local membranes in contact with the nanostructures are found to be fully fluidic for lipid and membrane protein diffusions, cells appear to actively sense and respond to the surface topography presented by vertical nanostructures. For future development of biodevices, it is important to understand how cells interact with these nanostructures and how their presence modulates cellular function and activities. How cells recognize nanoscale surface topography has been an area of active research for two decades before the recent biosensor works. Extensive studies show that surface topographies in the range of tens to hundreds of nanometers can significantly affect cell functions, behaviors, and ultimately the cell fate. For example, titanium implants having rough surfaces are better for osteoblast attachment and host-implant integration than those with smooth surfaces. At the cellular level, nanoscale surface topography has been shown by a large number of studies to modulate cell attachment, activity, and differentiation. However, a mechanistic understanding of how cells interact and respond to nanoscale topographic features is still lacking. In this Account, we focus on some recent studies that support a new mechanism that local membrane curvature induced by nanoscale topography directly acts as a biochemical signal to induce intracellular signaling, which we refer to as the curvature hypothesis. The curvature hypothesis proposes that some intracellular proteins can recognize membrane curvatures of a certain range at the cell-to-material interface. These proteins then recruit and activate downstream components to modulate cell signaling and behavior. We discuss current technologies

Understanding and exploiting nanoscale surface heterogeneity for particle and cell manipulation

NASA Astrophysics Data System (ADS)

Kalasin, Surachate

This thesis explores the impact of surface heterogeneities on colloidal interactions and translates concepts to biointerfacial systems, for instance, microfluidic and biomedical devices. The thesis advances a model system, originally put forth by Kozlova: Tunable electrostatic surface heterogeneity is produced by adsorbing small amounts of cationic polyelectrolyte on a silica flat. The resulting positive electrostatic patches possess a density that is tuned from a saturated carpet down to average spacings on the order of a few hundred nanometers. At these length-scales, multiple adhesive elements (from tens to thousands) are present in the area of contact between a particle and a surface, a distinguishing feature of the thesis. Much of the literature addressing surface "heterogeneity" engineers surfaces with micron-scale features, almost always larger than the contact area between a particle and a second surface. With a nanoscale heterogeneity model, this thesis reports and quantitatively explains particle interaction behavior not typical of homogeneous interfaces. This includes (1) an adhesion threshold, a minimum average surface density of cationic patches needed for particle capture, (previously observed by Kozlova); (2) a crossover, from salt-destabilized to salt-stabilized interactions between heterogeneous surfaces with net-negative charge; (3) a shift of the adhesion threshold with shear, reducing adhesion; (4) a crossover from shear-enhanced to shear-hindered particle adhesion; (5) a range of surface compositions and processing parameters that sustain particle rolling; and (6) conditions where particles arrest immediately on contact. Through variations in ionic strength and particle size, the particle-surface contact area is systematically varied relative to the heterogeneity lengthscale. This provides a semi-quantitative explanation for the shifting of the adhesion threshold, in terms of the statistical probability of a particle being able to find a

Surface modification of 316L stainless steel with magnetron sputtered TiN/VN nanoscale multilayers for bio implant applications.

PubMed

Subramanian, B; Ananthakumar, R; Kobayashi, Akira; Jayachandran, M

2012-02-01

Nanoscale multilayered TiN/VN coatings were developed by reactive dc magnetron sputtering on 316L stainless steel substrates. The coatings showed a polycrystalline cubic structure with (111) preferential growth. XPS analysis indicated the presence of peaks corresponding to Ti2p, V2p, N1s, O1s, and C1s. Raman spectra exhibited the characteristic peaks in the acoustic range of 160-320 cm(-1) and in the optic range between 480 and 695 cm(-1). Columnar structure of the coatings was observed from TEM analysis. The number of adherent platelets on the surface of the TiN/VN multilayer, VN, TiN single layer coating exhibit fewer aggregation and pseudopodium than on substrates. The wear resistance of the multilayer coatings increases obviously as a result of their high hardness. Tafel plots in simulated bodily fluid showed lower corrosion rate for the TiN/VN nanoscale multilayer coatings compared to single layer and bare 316L SS substrate.

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

NASA Astrophysics Data System (ADS)

Blechle, Joshua M.

Part I of this dissertation focuses on investigations of nitrogen oxide plasma systems. With increasing concerns over the environmental presence of NxOy species, there is growing interest in utilizing plasma-assisted conversion techniques. Advances, however, have been limited because of the lack of knowledge regarding the fundamental chemistry of these plasma systems. Understanding the kinetics and thermodynamics of processes in these systems is vital to realizing their potential in a range of applications. Unraveling the complex chemical nature of these systems, however, presents numerous challenges. As such, this work serves as a foundational step in the diagnostics and assessment of these NxOy plasmas. The partitioning of energy within the plasma system is essential to unraveling these complications as it provides insight into both gas and surface reactivity. To obtain this information, techniques such as optical emission spectroscopy (OES), broadband absorption spectroscopy (BAS), and laser induced fluorescence (LIF) were utilized to determine species energetics (vibrational, rotational, translational temperatures). These temperature data provide mechanistic insight and establish the relationships between system parameters and energetic outcomes. Additionally, these data are also correlated to surface reactivity data collected with the Imaging of Radicals Interacting with Surfaces (IRIS) technique. IRIS data demonstrate the relationship between internal temperatures of radicals and their observed surface scatter coefficients (S), the latter of which is directly related to surface reactivity (R) [R = 1-S]. Furthermore, time-resolved (TR) spectroscopic techniques, specifically TR-OES, revealed kinetic trends in NO and N2 formation from a range of precursors (NO, N2O, N2/O2). By examining the rate constants associated with the generation and destruction of various plasma species we can investigate possible mechanistic implications. All told, such data provides

Surface chemistry and morphology in single particle optical imaging

NASA Astrophysics Data System (ADS)

Ekiz-Kanik, Fulya; Sevenler, Derin Deniz; Ünlü, Neşe Lortlar; Chiari, Marcella; Ünlü, M. Selim

2017-05-01

Biological nanoparticles such as viruses and exosomes are important biomarkers for a range of medical conditions, from infectious diseases to cancer. Biological sensors that detect whole viruses and exosomes with high specificity, yet without additional labeling, are promising because they reduce the complexity of sample preparation and may improve measurement quality by retaining information about nanoscale physical structure of the bio-nanoparticle (BNP). Towards this end, a variety of BNP biosensor technologies have been developed, several of which are capable of enumerating the precise number of detected viruses or exosomes and analyzing physical properties of each individual particle. Optical imaging techniques are promising candidates among broad range of label-free nanoparticle detectors. These imaging BNP sensors detect the binding of single nanoparticles on a flat surface functionalized with a specific capture molecule or an array of multiplexed capture probes. The functionalization step confers all molecular specificity for the sensor's target but can introduce an unforeseen problem; a rough and inhomogeneous surface coating can be a source of noise, as these sensors detect small local changes in optical refractive index. In this paper, we review several optical technologies for label-free BNP detectors with a focus on imaging systems. We compare the surface-imaging methods including dark-field, surface plasmon resonance imaging and interference reflectance imaging. We discuss the importance of ensuring consistently uniform and smooth surface coatings of capture molecules for these types of biosensors and finally summarize several methods that have been developed towards addressing this challenge.

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

ERIC Educational Resources Information Center

Kontogeorgis, Georgios M.; Vigild, Martin E.

2009-01-01

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

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

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

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

Designing nanoscale constructs from atomic thin sheets of graphene, boron nitride and gold nanoparticles for advanced material applications

NASA Astrophysics Data System (ADS)

Jasuja, Kabeer

2011-12-01

Nanoscale materials invite immense interest from diverse scientific disciplines as these provide access to precisely understand the physical world at their most fundamental atomic level. In concert with this aim of enhancing our understanding of the fundamental behavior at nanoscale, this dissertation presents research on three nanomaterials: Gold nanoparticles (GNPs), Graphene and ultra-thin Boron Nitride sheets (UTBNSs). The three-fold goals which drive this research are: incorporating mobility in nanoparticle based single-electron junction constructs, developing effective strategies to functionalize graphene with nano-forms of metal, and exfoliating ultrathin sheets of Boron Nitride. Gold nanoparticle based electronic constructs can achieve a new degree of operational freedom if nanoscale mobility is incorporated in their design. We achieved such a nano-electromechanical construct by incorporating elastic polymer molecules between GNPs to form 2-dimensional (2-D) molecular junctions which show a nanoscale reversible motion on applying macro scale forces. This GNP-polymer assembly works like a molecular spring opening avenues to maneuver nano components and store energy at nano-scale. Graphene is the first isolated nanomaterial that displays single-atom thickness. It exhibits quantum confinement that enables it to possess a unique combination of fascinating electronic, optical, and mechanical properties. Modifying the surface of graphene is extremely significant to enable its incorporation into applications of interest. We demonstrated the ability of chemically modified graphene sheets to act as GNP stabilizing templates in solution, and utilized this to process GNP composites of graphene. We discovered that GNPs synthesized by chemical or microwave reduction stabilize on graphene-oxide sheets to form snow-flake morphologies and bare-surfaces respectively. These hybrid nano constructs were extensively studied to understand the effect and nature of GNPs

Tin doped indium oxide anodes with artificially controlled nano-scale roughness using segregated Ag nanoparticles for organic solar cells

NASA Astrophysics Data System (ADS)

Kim, Hyo-Joong; Ko, Eun-Hye; Noh, Yong-Jin; Na, Seok-In; Kim, Han-Ki

2016-09-01

Nano-scale surface roughness in transparent ITO films was artificially formed by sputtering a mixed Ag and ITO layer and wet etching of segregated Ag nanoparticles from the surface of the ITO film. Effective removal of self-segregated Ag particles from the grain boundaries and surface of the crystalline ITO film led to a change in only the nano-scale surface morphology of ITO film without changes in the sheet resistance and optical transmittance. A nano-scale rough surface of the ITO film led to an increase in contact area between the hole transport layer and the ITO anode, and eventually increased the hole extraction efficiency in the organic solar cells (OSCs). The heterojunction OSCs fabricated on the ITO anode with a nano-scale surface roughness exhibited a higher power conversion efficiency of 3.320%, than that (2.938%) of OSCs made with the reference ITO/glass. The results here introduce a new method to improve the performance of OSCs by simply modifying the surface morphology of the ITO anodes.

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

PubMed

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

2017-01-31

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

Ultralow nanoscale wear through atom-by-atom attrition in silicon-containing diamond-like carbon

NASA Astrophysics Data System (ADS)

Bhaskaran, Harish; Gotsmann, Bernd; Sebastian, Abu; Drechsler, Ute; Lantz, Mark A.; Despont, Michel; Jaroenapibal, Papot; Carpick, Robert W.; Chen, Yun; Sridharan, Kumar

2010-03-01

Understanding friction and wear at the nanoscale is important for many applications that involve nanoscale components sliding on a surface, such as nanolithography, nanometrology and nanomanufacturing. Defects, cracks and other phenomena that influence material strength and wear at macroscopic scales are less important at the nanoscale, which is why nanowires can, for example, show higher strengths than bulk samples. The contact area between the materials must also be described differently at the nanoscale. Diamond-like carbon is routinely used as a surface coating in applications that require low friction and wear because it is resistant to wear at the macroscale, but there has been considerable debate about the wear mechanisms of diamond-like carbon at the nanoscale because it is difficult to fabricate diamond-like carbon structures with nanoscale fidelity. Here, we demonstrate the batch fabrication of ultrasharp diamond-like carbon tips that contain significant amounts of silicon on silicon microcantilevers for use in atomic force microscopy. This material is known to possess low friction in humid conditions, and we find that, at the nanoscale, it is three orders of magnitude more wear-resistant than silicon under ambient conditions. A wear rate of one atom per micrometre of sliding on SiO2 is demonstrated. We find that the classical wear law of Archard does not hold at the nanoscale; instead, atom-by-atom attrition dominates the wear mechanisms at these length scales. We estimate that the effective energy barrier for the removal of a single atom is ~1 eV, with an effective activation volume of ~1 × 10-28 m.

Nanoscale deicing by molecular dynamics simulation.

PubMed

Xiao, Senbo; He, Jianying; Zhang, Zhiliang

2016-08-14

Deicing is important to human activities in low-temperature circumstances, and is critical for combating the damage caused by excessive accumulation of ice. The aim of creating anti-icing materials, surfaces and applications relies on the understanding of fundamental nanoscale ice adhesion mechanics. Here in this study, we employ all-atom modeling and molecular dynamics simulation to investigate ice adhesion. We apply force to detach and shear nano-sized ice cubes for probing the determinants of atomistic adhesion mechanics, and at the same time investigate the mechanical effect of a sandwiched aqueous water layer between ice and substrates. We observe that high interfacial energy restricts ice mobility and increases both ice detaching and shearing stresses. We quantify up to a 60% decrease in ice adhesion strength by an aqueous water layer, and provide atomistic details that support previous experimental studies. Our results contribute quantitative comparison of nanoscale adhesion strength of ice on hydrophobic and hydrophilic surfaces, and supply for the first time theoretical references for understanding the mechanics at the atomistic origins of macroscale ice adhesion.

Nonlinear dynamics of nanoscale systems

NASA Astrophysics Data System (ADS)

Hodas, Nathan Oken

This work builds theoretical tools to better understand nanoscale systems, and it ex- plores experimental techniques to probe nanoscale dynamics using nonlinear optical microscopy. In both the theory and experiment, this work harnesses nonlinearity to explore new boundaries in the ongoing attempts to understand the amazing world that is much smaller than we can see. In particular, the first part of this work proves the upper-bounds on the number and quality of oscillations when the sys- tem in question is homogeneously driven and has discrete states, a common way of describing nanoscale motors and chemical systems, although it has application to networked systems in general. The consequences of this limit are explored in the context of chemical clocks and limit cycles. This leads to the analysis of sponta- neous oscillations in GFPmut2, where we postulate that the oscillations must be due to coordinated rearrangement of the beta-barrel. Next, we utilize nonlinear optics to probe the constituent structures of zebrafish muscle. By comparing experimental observations with computational models, we show how second harmonic generation differs from fluorescence for confocal imaging. We use the wavelength dependence of the second harmonic generation conversion efficiency to extract information about the microscopic organization of muscle fibers, using the coherent nature of second ix harmonic generation as an analytical probe. Finally, existing experiments have used a related technique, sum-frequency generation, to directly probe the dynamics of free OH bonds at the water-vapor boundary. Using molecular dynamic simulations of the water surface and by designating surface-sensitive free OH bonds on the water surface, many aspects of the sum-frequency generation measurements were calcu- lated and compared with those inferred from experiment. The method utilizes results available from independent IR and Raman experiments to obtain some of the needed quantities, rather than

A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles.

PubMed

Kim, Hyejung; Kim, Min Gyu; Jeong, Hu Young; Nam, Haisol; Cho, Jaephil

2015-03-11

Structural degradation of Ni-rich cathode materials (LiNi(x)M(1-x)O2; M = Mn, Co, and Al; x > 0.5) during cycling at both high voltage (>4.3 V) and high temperature (>50 °C) led to the continuous generation of microcracks in a secondary particle that consisted of aggregated micrometer-sized primary particles. These microcracks caused deterioration of the electrochemical properties by disconnecting the electrical pathway between the primary particles and creating thermal instability owing to oxygen evolution during phase transformation. Here, we report a new concept to overcome those problems of the Ni-rich cathode material via nanoscale surface treatment of the primary particles. The resultant primary particles' surfaces had a higher cobalt content and a cation-mixing phase (Fm3̅m) with nanoscale thickness in the LiNi0.6Co0.2Mn0.2O2 cathode, leading to mitigation of the microcracks by suppressing the structural change from a layered to rock-salt phase. Furthermore, the higher oxidation state of Mn(4+) at the surface minimized the oxygen evolution at high temperatures. This approach resulted in improved structural and thermal stability in the severe cycling-test environment at 60 °C between 3.0 and 4.45 V and at elevated temperatures, showing a rate capability that was comparable to that of the pristine sample.

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

PubMed Central

2016-01-01

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

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

PubMed

Williams, David; Viti, Serena

2013-07-13

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

Nanoscale Ge fin etching using F- and Cl-based etchants for Ge-based multi-gate devices

NASA Astrophysics Data System (ADS)

Zhang, Bingxin; An, Xia; Li, Ming; Hao, Peilin; Zhang, Xing; Huang, Ru

2018-04-01

In this paper, nanoscale germanium (Ge) fin etching with inductively coupled plasma equipment with SF6/CHF3/Ar and Cl2/BCl3/Ar gas mixes are experimentally demonstrated. The impact of the gas ratio on etching induced Ge surface flatness, etch rate and sidewall steepness are comprehensively investigated and compared for these two kinds of etchants and the optimized gas ratio is provided. By using silicon oxide as a hard mask, nanoscale Ge fin with a flat surface and sharp sidewall is experimentally illustrated, which indicates great potential for use in nanoscale Ge-based multi-gate MOSFETs.

Ultrafast Chemistry under Nonequilibrium Conditions and the Shock to Deflagration Transition at the Nanoscale

DOE PAGES

Wood, Mitchell A.; Cherukara, Mathew J.; Kober, Edward M.; ...

2015-06-13

We use molecular dynamics simulations to describe the chemical reactions following shock-induced collapse of cylindrical pores in the high-energy density material RDX. For shocks with particle velocities of 2 km/s we find that the collapse of a 40 nm diameter pore leads to a deflagration wave. Molecular collisions during the collapse lead to ultrafast, multistep chemical reactions that occur under nonequilibrium conditions. WE found that exothermic products formed during these first few picoseconds prevent the nanoscale hotspot from quenching. Within 30 ps, a local deflagration wave develops. It propagates at 0.25 km/s and consists of an ultrathin reaction zone ofmore » only ~5 nm, thus involving large temperature and composition gradients. Contrary to the assumptions in current models, a static thermal hotspot matching the dynamical one in size and thermodynamic conditions fails to produce a deflagration wave indicating the importance of nonequilibrium loading in the criticality of nanoscale hot spots. These results provide insight into the initiation of reactive decomposition.« less

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

ERIC Educational Resources Information Center

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

2008-01-01

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

Spectrally resolved chromatic confocal interferometry for one-shot nano-scale surface profilometry with several tens of micrometric depth range

NASA Astrophysics Data System (ADS)

Chen, Liang-Chia; Chen, Yi-Shiuan; Chang, Yi-Wei; Lin, Shyh-Tsong; Yeh, Sheng Lih

2013-01-01

In this research, new nano-scale measurement methodology based on spectrally-resolved chromatic confocal interferometry (SRCCI) was successfully developed by employing integration of chromatic confocal sectioning and spectrally-resolve white light interferometry (SRWLI) for microscopic three dimensional surface profilometry. The proposed chromatic confocal method (CCM) using a broad band while light in combination with a specially designed chromatic dispersion objective is capable of simultaneously acquiring multiple images at a large range of object depths to perform surface 3-D reconstruction by single image shot without vertical scanning and correspondingly achieving a high measurement depth range up to hundreds of micrometers. A Linnik-type interferometric configuration based on spectrally resolved white light interferometry is developed and integrated with the CCM to simultaneously achieve nanoscale axis resolution for the detection point. The white-light interferograms acquired at the exit plane of the spectrometer possess a continuous variation of wavelength along the chromaticity axis, in which the light intensity reaches to its peak when the optical path difference equals to zero between two optical arms. To examine the measurement accuracy of the developed system, a pre-calibrated accurate step height target with a total step height of 10.10 μm was measured. The experimental result shows that the maximum measurement error was verified to be less than 0.3% of the overall measuring height.

Plasmonic Nanostructures for Nano-Scale Bio-Sensing

PubMed Central

Chung, Taerin; Lee, Seung-Yeol; Song, Eui Young; Chun, Honggu; Lee, Byoungho

2011-01-01

The optical properties of various nanostructures have been widely adopted for biological detection, from DNA sequencing to nano-scale single molecule biological function measurements. In particular, by employing localized surface plasmon resonance (LSPR), we can expect distinguished sensing performance with high sensitivity and resolution. This indicates that nano-scale detections can be realized by using the shift of resonance wavelength of LSPR in response to the refractive index change. In this paper, we overview various plasmonic nanostructures as potential sensing components. The qualitative descriptions of plasmonic nanostructures are supported by the physical phenomena such as plasmonic hybridization and Fano resonance. We present guidelines for designing specific nanostructures with regard to wavelength range and target sensing materials. PMID:22346679

A Theoretical Review on Interfacial Thermal Transport at the Nanoscale.

PubMed

Zhang, Ping; Yuan, Peng; Jiang, Xiong; Zhai, Siping; Zeng, Jianhua; Xian, Yaoqi; Qin, Hongbo; Yang, Daoguo

2018-01-01

With the development of energy science and electronic technology, interfacial thermal transport has become a key issue for nanoelectronics, nanocomposites, energy transmission, and conservation, etc. The application of thermal interfacial materials and other physical methods can reliably improve the contact between joined surfaces and enhance interfacial thermal transport at the macroscale. With the growing importance of thermal management in micro/nanoscale devices, controlling and tuning the interfacial thermal resistance (ITR) at the nanoscale is an urgent task. This Review examines nanoscale interfacial thermal transport mainly from a theoretical perspective. Traditional theoretical models, multiscale models, and atomistic methodologies for predicting ITR are introduced. Based on the analysis and summary of the factors that influence ITR, new methods to control and reduce ITR at the nanoscale are described in detail. Furthermore, the challenges facing interfacial thermal management and the further progress required in this field are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioadhesion of mussels and geckos: Molecular mechanics, surface chemistry, and nanoadhesives

NASA Astrophysics Data System (ADS)

Lee, Haeshin

The adhesive strategies of living creatures are diverse, ranging from temporary to permanent adhesions with various functions such as locomotion, self-defense, communication, colony formation, and so on. The classic example of temporary adhesion is the gecko, which is known for its ability to walk along vertical and even inverted surfaces; this remarkable adhesion arises from the interfacial weak interactions of van der Waals and capillary forces. In contrast, a celerbrated example of permanent adhesion is found in marine mussels which secrete protein adhesives that function in aqueous environments without mechanical failure against turbulent conditions on the seashore. In addition, mussel adhesives stick to virtually all inorganic and organic surfaces. However, most commonly used man-made adhesives lack such unique adhesion properties compared to their natural counterparts. For example, many commercial adhesives quickly lose their adhesive strength when exposed to solvents, particularly water. The first part of this thesis focused on adhesion mechanics of mussels at a single-molecule level, in which the adhesive molecule showed surprisingly strong yet reversible adhesion on inorganic surfaces but exhibited irreversible covalent bond formation on organic surfaces. Strong and reversible adhesion on mucin surfaces was found, indicating potential application for drug delivery via mucus layers. Next, inspired by the mussel's versatile adhesion on a wide variety of material surfaces, a material-independent surface modification chemistry called 'polydopamine coating' is described. This concept was subsequently adapted to develop a surface-independent polymeric primer for layer-by-layer assembly of multifunctional coatings. Finally, a new bio-hybrid adhesive 'geckel' was developed by the functional combination of adhesion strategies of geckos and mussels. The new bio-inspired adhesive and material-independent surface chemistry can revolutionize the research areas such as

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.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

Genotoxic capacity of Cd/Se semiconductor quantum dots with differing surface chemistries

PubMed Central

Manshian, Bella B.; Soenen, Stefaan J.; Brown, Andy; Hondow, Nicole; Wills, John; Jenkins, Gareth J. S.; Doak, Shareen H.

2016-01-01

Quantum dots (QD) have unique electronic and optical properties promoting biotechnological advances. However, our understanding of the toxicological structure–activity relationships remains limited. This study aimed to determine the biological impact of varying nanomaterial surface chemistry by assessing the interaction of QD with either a negative (carboxyl), neutral (hexadecylamine; HDA) or positive (amine) polymer coating with human lymphoblastoid TK6 cells. Following QD physico-chemical characterisation, cellular uptake was quantified by optical and electron microscopy. Cytotoxicity was evaluated and genotoxicity was characterised using the micronucleus assay (gross chromosomal damage) and the HPRT forward mutation assay (point mutagenicity). Cellular damage mechanisms were also explored, focusing on oxidative stress and mitochondrial damage. Cell uptake, cytotoxicity and genotoxicity were found to be dependent on QD surface chemistry. Carboxyl-QD demonstrated the smallest agglomerate size and greatest cellular uptake, which correlated with a dose dependent increase in cytotoxicity and genotoxicity. Amine-QD induced minimal cellular damage, while HDA-QD promoted substantial induction of cell death and genotoxicity. However, HDA-QD were not internalised by the cells and the damage they caused was most likely due to free cadmium release caused by QD dissolution. Oxidative stress and induced mitochondrial reactive oxygen species were only partially associated with cytotoxicity and genotoxicity induced by the QD, hence were not the only mechanisms of importance. Colloidal stability, nanoparticle (NP) surface chemistry, cellular uptake levels and the intrinsic characteristics of the NPs are therefore critical parameters impacting genotoxicity induced by QD. PMID:26275419

Reverse micelle synthesis of nanoscale metal containing catalysts

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

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

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

DTIC Science & Technology

1988-06-30

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

Ferroionic states: coupling between surface electrochemical and bulk ferroelectric functionalities on the nanoscale.

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

Ferroelectricity on the nanoscale has remained a subject of much fascination in condensed matter physics for the last several decades. It is well-recognized that stability of the ferroelectric state necessitates effective polarization screening, and hence screening mechanism and screening charge dynamics become strongly coupled to ferroelectric phase stability and domain behavior. Previously, the role of the screening charge in macroscopic ferroelectrics was observed in phenomena such as potential retention above Curie temperature, back switching of ferroelectric domains, and chaos and intermittency during domain switching. In the last several years, multiple reports claiming ferroelectricity in ultrathin ferroelectrics based on formation of remanent polarization states, local hysteresis loops, and pressure induced switching were made. However, similar phenomena were reported for traditionally non-ferroelectric materials, creating significant level of uncertainty in the field. We pose that in the nanoscale systems, the ferroelectric state is fundamentally inseparable from electrochemical state of the surface, leading to emergence of coupled electrochemical-ferroelectric states. I will present the results of experimental and theoretical work exploring the basic mechanisms of emergence of these coupled states including the basic theory and phase-field formulation for domain evolution. I further discuss the thermodynamics and thickness evolution of this state, and demonstrate the experimental pathway to establish its presence based on spectroscopic version of piezoresponse force microscopy. Finally, the role of chemical screening on domain dynamics is explored using phase-field modelling. This analysis reconciles multiple prior studies, and set forward the predictive pathways for new generations of ferroelectric devices and applications. This research was sponsored by the Division of Materials Sciences and Engineering, BES, DOE, and was conducted at the Center for

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.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Elementary photocatalytic chemistry on TiO2 surfaces.

PubMed

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

2016-07-07

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

Complementary Imaging of Silver Nanoparticle Interactions with Green Algae: Dark-Field Microscopy, Electron Microscopy, and Nanoscale Secondary Ion Mass Spectrometry.

PubMed

Sekine, Ryo; Moore, Katie L; Matzke, Marianne; Vallotton, Pascal; Jiang, Haibo; Hughes, Gareth M; Kirby, Jason K; Donner, Erica; Grovenor, Chris R M; Svendsen, Claus; Lombi, Enzo

2017-11-28

Increasing consumer use of engineered nanomaterials has led to significantly increased efforts to understand their potential impact on the environment and living organisms. Currently, no individual technique can provide all the necessary information such as their size, distribution, and chemistry in complex biological systems. Consequently, there is a need to develop complementary instrumental imaging approaches that provide enhanced understanding of these "bio-nano" interactions to overcome the limitations of individual techniques. Here we used a multimodal imaging approach incorporating dark-field light microscopy, high-resolution electron microscopy, and nanoscale secondary ion mass spectrometry (NanoSIMS). The aim was to gain insight into the bio-nano interactions of surface-functionalized silver nanoparticles (Ag-NPs) with the green algae Raphidocelis subcapitata, by combining the fidelity, spatial resolution, and elemental identification offered by the three techniques, respectively. Each technique revealed that Ag-NPs interact with the green algae with a dependence on the size (10 nm vs 60 nm) and surface functionality (tannic acid vs branched polyethylenimine, bPEI) of the NPs. Dark-field light microscopy revealed the presence of strong light scatterers on the algal cell surface, and SEM imaging confirmed their nanoparticulate nature and localization at nanoscale resolution. NanoSIMS imaging confirmed their chemical identity as Ag, with the majority of signal concentrated at the cell surface. Furthermore, SEM and NanoSIMS provided evidence of 10 nm bPEI Ag-NP internalization at higher concentrations (40 μg/L), correlating with the highest toxicity observed from these NPs. This multimodal approach thus demonstrated an effective approach to complement dose-response studies in nano-(eco)-toxicological investigations.

Contributions of nanoscale roughness to anomalous colloid retention and stability behavior

USDA-ARS?s Scientific Manuscript database

All natural surfaces exhibit nanoscale roughness (NR) and chemical heterogeneity (CH) to some extent. Expressions were developed to determine the mean interaction energy between a colloid and a solid-water interface (SWI), as well as for colloid-colloid interactions, when both surfaces contain binar...

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.

Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

NASA Astrophysics Data System (ADS)

Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

2016-04-01

Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

Probing physical properties at the nanoscale using atomic force microscopy

NASA Astrophysics Data System (ADS)

Ditzler, Lindsay Rachel

Techniques that measure physical properties at the nanoscale with high sensitivity are significantly limited considering the number of new nanomaterials being developed. The development of atomic force microscopy (AFM) has lead to significant advancements in the ability to characterize physical properties of materials in all areas of science: chemistry, physics, engineering, and biology have made great scientific strides do to the versatility of the AFM. AFM is used for quantification of many physical properties such as morphology, electrical, mechanical, magnetic, electrochemical, binding interactions, and protein folding. This work examines the electrical and mechanical properties of materials applicable to the field of nano-electronics. As electronic devices are miniaturized the demand for materials with unique electrical properties, which can be developed and exploited, has increased. For example, discussed in this work, a derivative of tetrathiafulvalene, which exhibits a unique loss of conductivity upon compression of the self-assembled monolayer could be developed into a molecular switch. This work also compares tunable organic (tetraphenylethylene tetracarboxylic acid and bis(pyridine)s assemblies) and metal-organic (Silver-stilbizole coordination compounds) crystals which show high electrical conductivity. The electrical properties of these materials vary depending on their composition allowing for the development of compositionally tunable functional materials. Additional work was done to investigate the effects of molecular environment on redox active 11-ferroceneyl-1 undecanethiol (Fc) molecules. The redox process of mixed monolayers of Fc and decanethiol was measured using conductive probe atomic force microscopy and force spectroscopy. As the concentration of Fc increased large, variations in the force were observed. Using these variations the number of oxidized molecules in the monolayer was determined. AFM is additionally capable of investigating

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

DOE PAGES

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

2017-04-27

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

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

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

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

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

Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

NASA Technical Reports Server (NTRS)

Cooper, Paul D.; Cooper, John F.; Sittler, Edward C.; Burger, Matthew H.; Sturner, Steven J.; Rymer, Abigail M.

2008-01-01

The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

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

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

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

Saltwater icephobicity: Influence of surface chemistry on saltwater icing

PubMed Central

Carpenter, Katherine; Bahadur, Vaibhav

2015-01-01

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

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

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

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

DOE PAGES

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.; ...

2016-09-01

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be

Modeling of nanoscale liquid mixture transport by density functional hydrodynamics

NASA Astrophysics Data System (ADS)

Dinariev, Oleg Yu.; Evseev, Nikolay V.

2017-06-01

Modeling of multiphase compositional hydrodynamics at nanoscale is performed by means of density functional hydrodynamics (DFH). DFH is the method based on density functional theory and continuum mechanics. This method has been developed by the authors over 20 years and used for modeling in various multiphase hydrodynamic applications. In this paper, DFH was further extended to encompass phenomena inherent in liquids at nanoscale. The new DFH extension is based on the introduction of external potentials for chemical components. These potentials are localized in the vicinity of solid surfaces and take account of the van der Waals forces. A set of numerical examples, including disjoining pressure, film precursors, anomalous rheology, liquid in contact with heterogeneous surface, capillary condensation, and forward and reverse osmosis, is presented to demonstrate modeling capabilities.

Nanoscale roughness contact in a slider-disk interface.

PubMed

Hua, Wei; Liu, Bo; Yu, Shengkai; Zhou, Weidong

2009-07-15

The nanoscale roughness contact between molecularly smooth surfaces of a slider-disk interface in a hard disk drive is analyzed, and the lubricant behavior at very high shear rate is presented. A new contact model is developed to study the nanoscale roughness contact behavior by classifying various forms of contact into slider-lubricant contact, slider-disk elastic contact and plastic contact. The contact pressure and the contact probabilities of the three types of contact are investigated. The new contact model is employed to explain and provide insight to an interesting experimental result found in a thermal protrusion slider. The protrusion budget for head surfing in the lubricant, which is the ideal state for contact recording, is also discussed.

Nanoscale multiple gaseous layers on a hydrophobic surface.

PubMed

Zhang, Lijuan; Zhang, Xuehua; Fan, Chunhai; Zhang, Yi; Hu, Jun

2009-08-18

The nanoscale gas state at the interfaces of liquids (water, acid, and salt solutions) and highly oriented pyrolytic graphite (HOPG) was investigated via tapping-mode atomic force microscopy (AFM). For the first time, we report that the interfacial gases could form bilayers and trilayers, i.e., on the top of a flat gas layer, there are one or two more gas layers. The formation of these gas layers could be induced by a local supersaturation of gases, which can be achieved by (1) temperature difference between the liquids and the HOPG substrates or (2) exchange ethanol with water. Furthermore, we found that the gas layers were less stable than spherical bubbles. They could transform to bubbles with time or under the perturbation of the AFM tip.

Surface microstructure and chemistry of polyimide by single pulse ablation of picosecond laser

NASA Astrophysics Data System (ADS)

Du, Qifeng; Chen, Ting; Liu, Jianguo; Zeng, Xiaoyan

2018-03-01

Polyimide (PI) surface was ablated by the single pulse of picosecond laser, and the effects of laser wavelength (λ= 355 nm and 1064 nm) and fluence on surface microstructure and chemistry were explored. Scanning electron microscopy (SEM) analysis found that different surface microstructures, i.e., the concave of concentric ring and the convex of porous circular disk, were generated by 355 nm and 1064 nm picosecond laser ablation, respectively. X-ray photoelectron spectroscopy (XPS) characterization indicated that due to the high peak energy density of picosecond laser, oxygen and nitrogen from the ambient were incorporated into the PI surface mainly in the form of Cdbnd O and Csbnd Nsbnd C groups. Thus, both of the O/C and N/C atomic content ratios increased, but the increase caused by 1064 nm wavelength laser was larger. It inferred that the differences of PI surface microstructures and chemistry resulted from different laser parameters were related to different laser-matter interaction effects. For 355 nm picosecond laser, no obvious thermal features were observed and the probable ablation process of PI was mainly governed by photochemical effect; while for 1064 nm picosecond laser, obvious thermal feature appeared and photothermal effect was thought to be dominant.

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

NASA Astrophysics Data System (ADS)

Adib, Kaveh

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

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

PubMed

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

2014-07-09

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

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

PubMed

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

2013-06-01

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

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

PubMed

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

2015-12-01

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

Fundamentals of Nanoscale Polymer–Protein Interactions and Potential Contributions to Solid-State Nanobioarrays

PubMed Central

2015-01-01

Protein adsorption onto polymer surfaces is a very complex, ubiquitous, and integrated process, impacting essential areas of food processing and packaging, health devices, diagnostic tools, and medical products. The nature of protein–surface interactions is becoming much more complicated with continuous efforts toward miniaturization, especially for the development of highly compact protein detection and diagnostic devices. A large body of literature reports on protein adsorption from the perspective of ensemble-averaged behavior on macroscopic, chemically homogeneous, polymeric surfaces. However, protein–surface interactions governing the nanoscale size regime may not be effectively inferred from their macroscopic and microscopic characteristics. Recently, research efforts have been made to produce periodically arranged, nanoscopic protein patterns on diblock copolymer surfaces solely through self-assembly. Intriguing protein adsorption phenomena are directly probed on the individual biomolecule level for a fundamental understanding of protein adsorption on nanoscale surfaces exhibiting varying degrees of chemical heterogeneity. Insight gained from protein assembly on diblock copolymers can be effectively used to control the surface density, conformation, orientation, and biofunctionality of prebound proteins in highly miniaturized applications, now approaching the nanoscale. This feature article will highlight recent experimental and theoretical advances made on these fronts while focusing on single-biomolecule-level investigations of protein adsorption behavior combined with surface chemical heterogeneity on the length scale commensurate with a single protein. This article will also address advantages and challenges of the self-assembly-driven patterning technology used to produce protein nanoarrays and its implications for ultrahigh density, functional, and quantifiable protein detection in a highly miniaturized format. PMID:24456577

Fundamentals of nanoscale polymer-protein interactions and potential contributions to solid-state nanobioarrays.

PubMed

Hahm, Jong-in

2014-08-26

Protein adsorption onto polymer surfaces is a very complex, ubiquitous, and integrated process, impacting essential areas of food processing and packaging, health devices, diagnostic tools, and medical products. The nature of protein-surface interactions is becoming much more complicated with continuous efforts toward miniaturization, especially for the development of highly compact protein detection and diagnostic devices. A large body of literature reports on protein adsorption from the perspective of ensemble-averaged behavior on macroscopic, chemically homogeneous, polymeric surfaces. However, protein-surface interactions governing the nanoscale size regime may not be effectively inferred from their macroscopic and microscopic characteristics. Recently, research efforts have been made to produce periodically arranged, nanoscopic protein patterns on diblock copolymer surfaces solely through self-assembly. Intriguing protein adsorption phenomena are directly probed on the individual biomolecule level for a fundamental understanding of protein adsorption on nanoscale surfaces exhibiting varying degrees of chemical heterogeneity. Insight gained from protein assembly on diblock copolymers can be effectively used to control the surface density, conformation, orientation, and biofunctionality of prebound proteins in highly miniaturized applications, now approaching the nanoscale. This feature article will highlight recent experimental and theoretical advances made on these fronts while focusing on single-biomolecule-level investigations of protein adsorption behavior combined with surface chemical heterogeneity on the length scale commensurate with a single protein. This article will also address advantages and challenges of the self-assembly-driven patterning technology used to produce protein nanoarrays and its implications for ultrahigh density, functional, and quantifiable protein detection in a highly miniaturized format.

Ground- and Surface-Water Chemistry of Handcart Gulch, Park County, Colorado, 2003-2006

USGS Publications Warehouse

Verplanck, Philip L.; Manning, Andrew H.; Kimball, Briant A.; McCleskey, R. Blaine; Runkel, Robert L.; Caine, Jonathan S.; Adams, Monique; Gemery-Hill, Pamela A.; Fey, David L.

2008-01-01

As part of a multidisciplinary project to determine the processes that control ground-water chemistry and flow in mineralized alpine environments, ground- and surface-water samples from Handcart Gulch, Colorado were collected for analysis of inorganic solutes and water and dissolved sulfate stable isotopes in selected samples. The primary aim of this study was to document variations in ground-water chemistry in Handcart Gulch and to identify changes in water chemistry along the receiving stream of Handcart Gulch. Water analyses are reported for ground-water samples collected from 12 wells in Handcart Gulch, Colorado. Samples were collected between August 2003 and October 2005. Water analyses for surface-water samples are reported for 50 samples collected from Handcart Gulch and its inflows during a low-flow tracer injection on August 6, 2003. In addition, water analyses are reported for three other Handcart Gulch stream samples collected in September 2005 and March 2006. Reported analyses include field parameters (pH, specific conductance, temperature, dissolved oxygen, and Eh), major and trace constituents, oxygen and hydrogen isotopic composition of water and oxygen and sulfur isotopic composition of dissolved sulfate. Ground-water samples from this study are Ca-SO4 type and range in pH from 2.5 to 6.8. Most of the samples (75 percent) have pH values between 3.3 and 4.3. Surface water samples are also Ca-SO4 type and have a narrower range in pH (2.7?4.0). Ground- and surface-water samples vary from relatively dilute (specific conductance of 68 ?S/cm) to concentrated (specific conductance of 2,000 ?S/cm).

The nanoscale organization of the B lymphocyte membrane☆

PubMed Central

Maity, Palash Chandra; Yang, Jianying; Klaesener, Kathrin; Reth, Michael

2015-01-01

The fluid mosaic model of Singer and Nicolson correctly predicted that the plasma membrane (PM) forms a lipid bi-layer containing many integral trans-membrane proteins. This model also suggested that most of these proteins were randomly dispersed and freely diffusing moieties. Initially, this view of a dynamic and rather unorganized membrane was supported by early observations of the cell surfaces using the light microscope. However, recent studies on the PM below the diffraction limit of visible light (~ 250 nm) revealed that, at nanoscale dimensions, membranes are highly organized and compartmentalized structures. Lymphocytes are particularly useful to study this nanoscale membrane organization because they grow as single cells and are not permanently engaged in cell:cell contacts within a tissue that can influence membrane organization. In this review, we describe the methods that can be used to better study the protein:protein interaction and nanoscale organization of lymphocyte membrane proteins, with a focus on the B cell antigen receptor (BCR). Furthermore, we discuss the factors that may generate and maintain these membrane structures. PMID:25450974

Wettability of natural root mucilage studied by atomic force microscopy and contact angle: Links between nanoscale and macroscale surface properties

NASA Astrophysics Data System (ADS)

Kaltenbach, Robin; Diehl, Dörte; Schaumann, Gabriele E.

2017-04-01

Organic coatings are considered as main cause of soil water repellency (SWR). This phenomenon plays a crucial role in the rhizosphere, at the interface of plant water uptake and soil hydraulics. Still, there is little knowledge about the nanoscale properties of natural soil compounds such as root-mucilage and its mechanistic effect on wettability. In this study, dried films of natural root-mucilage from Sorghum (Sorghum sp., MOENCH) on glass substrates were studied in order to explore experimental and evaluation methods that allow to link between macroscopic wettability and nano-/microscopic surface properties in this model soil system. SWR was assessed by optical contact angle (CA) measurements. The nanostructure of topography and adhesion forces of the mucilage surfaces was revealed by atomic force microscopy (AFM) measurements in ambient air, using PeakForce Quantitative Nanomechanical Mapping (PFQNM). Undiluted mucilage formed hydrophobic films on the substrate with CA > 90° and rather homogeneous nanostructure. Contact angles showed reduced water repellency of surfaces, when concentration of mucilage was decreased by dilution. AFM height and adhesion images displayed incomplete mucilage surface coverage for diluted samples. Hole-like structures in the film frequently exhibited increased adhesion forces. Spatial analysis of the AFM data via variograms enabled a numerical description of such 'adhesion holes'. The use of geostatistical approaches in AFM studies of the complex surface structure of soil compounds was considered meaningful in view of the need of comprehensive analysis of large AFM image data sets that exceed the capability of comparative visual inspection. Furthermore, force curves measured with the AFM showed increased break-free distances and pull-off forces inside the observed 'adhesion holes', indicating enhanced capillary forces due to adsorbed water films at hydrophilic domains for ambient RH (40 ± 2 %). This offers the possibility of

Bacterial resistance of self-assembled surfaces using PPOm-b-PSBMAn zwitterionic copolymer - concomitant effects of surface topography and surface chemistry on attachment of live bacteria.

PubMed

Hsiao, Sheng-Wen; Venault, Antoine; Yang, Hui-Shan; Chang, Yung

2014-06-01

Three well-defined diblock copolymers made of poly(sulfobetaine methacrylate) (poly(SBMA)) and poly(propylene oxide) (PPO) groups were synthesized by atom transfer radical polymerization (ATRP) method. They were physically adsorbed onto three types of surfaces having different topography, including smooth flat surface, convex surface, and indented surface. Chemical state of surfaces was characterized by XPS while the various topographies were examined by SEM and AFM. Hydrophilicity of surfaces was dependent on both the surface chemistry and the surface topography, suggesting that orientation of copolymer brushes can be tuned in the design of surfaces aimed at resisting bacterial attachment. Escherichia coli, Staphylococcus epidermidis, Streptococcus mutans and Escherichia coli with green fluorescent protein (E. coli GFP) were used in bacterial tests to assess the resistance to bacterial attachment of poly(SBMA)-covered surfaces. Results highlighted a drastic improvement of resistance to bacterial adhesion with the increasing of poly(SBMA) to PPO ratio, as well as an important effect of surface topography. The chemical effect was directly related to the length of the hydrophilic moieties. When longer, more water could be entrapped, leading to improved anti-bacterial properties. The physical effect impacted on the orientation of the copolymer brushes, as well as on the surface contact area available. Convex surfaces as well as indented surfaces wafer presented the best resistance to bacterial adhesion. Indeed, bacterial attachment was more importantly reduced on these surfaces compared with smooth surfaces. It was explained by the non-orthogonal orientation of copolymer brushes, resulting in a more efficient surface coverage of zwitterionic molecules. This work suggests that not only the control of surface chemistry is essential in the preparation of surfaces resisting bacterial attachment, but also the control of surface topography and orientation of antifouling

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

PubMed

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

2013-05-18

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

Absence of molecular slip on ultraclean and SAM-coated surfaces

NASA Astrophysics Data System (ADS)

Pye, Justin; Wood, Clay; Burton, Justin

2016-11-01

The liquid/solid boundary condition is a complex problem that is becoming increasingly important for the development of nanoscale fluidic devices. Many groups have now measured slip near an interface at nanoscale dimensions using a variety of experimental techniques. In simple systems, large slip lengths are generally measured for non-wetting liquid/solid combinations, but many conflicting measurements and interpretations remain. We have developed a novel pseudo-differential technique using a quartz crystal microbalance (QCM) to measure slip lengths on various surfaces. A drop of one liquid is grown on the QCM in the presence of a second, ambient liquid. We have isolated any anomalous boundary effects such as interfacial slip by choosing two liquids which have identical bulk effects on the QCM frequency and dissipation in the presence of no-slip. Slip lengths are -less than 2 nm- for water (relative to undecane) on all surfaces measured, including plasma cleaned gold, SiO2, and two different self assembled monolayers (SAMs), regardless of contact angle. We also find that surface cleanliness is crucial to accurately measure slip lengths. Additionally, clean glass substrates appear to have a significant adsorbed water layer and SAM surfaces show excess dissipation, possibly associated with contact line motion. In addition to investigating other liquid pairs, future work will include extending this technique to surfaces with independently controllable chemistry and roughness, both of which are known to strongly affect interfacial hydrodynamics.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

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

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

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

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

2015-02-02

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

Gridded global surface ozone metrics for atmospheric chemistry model evaluation

NASA Astrophysics Data System (ADS)

Sofen, E. D.; Bowdalo, D.; Evans, M. J.; Apadula, F.; Bonasoni, P.; Cupeiro, M.; Ellul, R.; Galbally, I. E.; Girgzdiene, R.; Luppo, S.; Mimouni, M.; Nahas, A. C.; Saliba, M.; Tørseth, K.

2016-02-01

The concentration of ozone at the Earth's surface is measured at many locations across the globe for the purposes of air quality monitoring and atmospheric chemistry research. We have brought together all publicly available surface ozone observations from online databases from the modern era to build a consistent data set for the evaluation of chemical transport and chemistry-climate (Earth System) models for projects such as the Chemistry-Climate Model Initiative and Aer-Chem-MIP. From a total data set of approximately 6600 sites and 500 million hourly observations from 1971-2015, approximately 2200 sites and 200 million hourly observations pass screening as high-quality sites in regionally representative locations that are appropriate for use in global model evaluation. There is generally good data volume since the start of air quality monitoring networks in 1990 through 2013. Ozone observations are biased heavily toward North America and Europe with sparse coverage over the rest of the globe. This data set is made available for the purposes of model evaluation as a set of gridded metrics intended to describe the distribution of ozone concentrations on monthly and annual timescales. Metrics include the moments of the distribution, percentiles, maximum daily 8-hour average (MDA8), sum of means over 35 ppb (daily maximum 8-h; SOMO35), accumulated ozone exposure above a threshold of 40 ppbv (AOT40), and metrics related to air quality regulatory thresholds. Gridded data sets are stored as netCDF-4 files and are available to download from the British Atmospheric Data Centre (doi: 10.5285/08fbe63d-fa6d-4a7a-b952-5932e3ab0452). We provide recommendations to the ozone measurement community regarding improving metadata reporting to simplify ongoing and future efforts in working with ozone data from disparate networks in a consistent manner.

Gridded global surface ozone metrics for atmospheric chemistry model evaluation

NASA Astrophysics Data System (ADS)

Sofen, E. D.; Bowdalo, D.; Evans, M. J.; Apadula, F.; Bonasoni, P.; Cupeiro, M.; Ellul, R.; Galbally, I. E.; Girgzdiene, R.; Luppo, S.; Mimouni, M.; Nahas, A. C.; Saliba, M.; Tørseth, K.; Wmo Gaw, Epa Aqs, Epa Castnet, Capmon, Naps, Airbase, Emep, Eanet Ozone Datasets, All Other Contributors To

2015-07-01

The concentration of ozone at the Earth's surface is measured at many locations across the globe for the purposes of air quality monitoring and atmospheric chemistry research. We have brought together all publicly available surface ozone observations from online databases from the modern era to build a consistent dataset for the evaluation of chemical transport and chemistry-climate (Earth System) models for projects such as the Chemistry-Climate Model Initiative and Aer-Chem-MIP. From a total dataset of approximately 6600 sites and 500 million hourly observations from 1971-2015, approximately 2200 sites and 200 million hourly observations pass screening as high-quality sites in regional background locations that are appropriate for use in global model evaluation. There is generally good data volume since the start of air quality monitoring networks in 1990 through 2013. Ozone observations are biased heavily toward North America and Europe with sparse coverage over the rest of the globe. This dataset is made available for the purposes of model evaluation as a set of gridded metrics intended to describe the distribution of ozone concentrations on monthly and annual timescales. Metrics include the moments of the distribution, percentiles, maximum daily eight-hour average (MDA8), SOMO35, AOT40, and metrics related to air quality regulatory thresholds. Gridded datasets are stored as netCDF-4 files and are available to download from the British Atmospheric Data Centre (doi:10.5285/08fbe63d-fa6d-4a7a-b952-5932e3ab0452). We provide recommendations to the ozone measurement community regarding improving metadata reporting to simplify ongoing and future efforts in working with ozone data from disparate networks in a consistent manner.

Advances in Surface Plasmon Resonance Imaging enable quantitative measurement of laterally heterogeneous coatings of nanoscale thickness

NASA Astrophysics Data System (ADS)

Raegen, Adam; Reiter, Kyle; Clarke, Anthony; Lipkowski, Jacek; Dutcher, John

2013-03-01

The Surface Plasmon Resonance (SPR) phenomenon is routinely exploited to qualitatively probe changes to the optical properties of nanoscale coatings on thin metallic surfaces, for use in probes and sensors. Unfortunately, extracting truly quantitative information is usually limited to a select few cases - uniform absorption/desorption of small biomolecules and films, in which a continuous ``slab'' model is a good approximation. We present advancements in the SPR technique that expand the number of cases for which the technique can provide meaningful results. Use of a custom, angle-scanning SPR imaging system, together with a refined data analysis method, allow for quantitative kinetic measurements of laterally heterogeneous systems. We first demonstrate the directionally heterogeneous nature of the SPR phenomenon using a directionally ordered sample, then show how this allows for the calculation of the average coverage of a heterogeneous sample. Finally, the degradation of cellulose microfibrils and bundles of microfibrils due to the action of cellulolytic enzymes will be presented as an excellent example of the capabilities of the SPR imaging system.

Fluorescent nanoscale zinc(II)-carboxylate coordination polymers for explosive sensing.

PubMed

Zhang, Chengyi; Che, Yanke; Zhang, Zengxing; Yang, Xiaomei; Zang, Ling

2011-02-28

Fluorescent nanoscale coordination polymers with cubic morphology and long range ordered structure were fabricated and exhibited efficient sensing for both nitroaromatic explosive and nitromethane due to large surface area to volume ratio and strong binding affinity to explosive molecules.

In-situ observation of switchable nanoscale topography for y-shaped binary brushes in fluids.

PubMed

Lin, Yen-Hsi; Teng, Jing; Zubarev, Eugene R; Shulha, Hennady; Tsukruk, Vladimir V

2005-03-01

Direct, in-fluid observation of the surface morphology and nanomechanical properties of the mixed brushes composed of Y-shaped binary molecules PS-PAA revealed nanoscale network-like surface topography formed by coexisting stretched soluble PAA arms and collapsed insoluble PS chains in water. Placement of Y-shaped brushes in different fluids resulted in dramatic reorganization ranging from soft repellent layer covered by swollen PS arms in toluene to an adhesive, mixed layer composed of coexisting swollen PAA and collapsed PS arms in water. These binary layers with the overall nanoscale thickness can serve as adaptive nanocoatings with stimuli-responsive properties.

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

DOE PAGES

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

2015-02-23

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

Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy

PubMed Central

Wang, Le; Wang, Haomin; Wagner, Martin; Yan, Yong; Jakob, Devon S.; Xu, Xiaoji G.

2017-01-01

Nondestructive chemical and mechanical measurements of materials with ~10-nm spatial resolution together with topography provide rich information on the compositions and organizations of heterogeneous materials and nanoscale objects. However, multimodal nanoscale correlations are difficult to achieve because of the limitation on spatial resolution of optical microscopy and constraints from instrumental complexities. We report a novel noninvasive spectroscopic scanning probe microscopy method—peak force infrared (PFIR) microscopy—that allows chemical imaging, collection of broadband infrared spectra, and mechanical mapping at a spatial resolution of 10 nm. In our technique, chemical absorption information is directly encoded in the withdraw curve of the peak force tapping cycle after illumination with synchronized infrared laser pulses in a simple apparatus. Nanoscale phase separation in block copolymers and inhomogeneity in CH3NH3PbBr3 perovskite crystals are studied with correlative infrared/mechanical nanoimaging. Furthermore, we show that the PFIR method is sensitive to the presence of surface phonon polaritons in boron nitride nanotubes. PFIR microscopy will provide a powerful analytical tool for explorations at the nanoscale across wide disciplines. PMID:28691096

IMMUNOBLOT ANALYSIS OF PROTEINS ASSOCIATED WITH SELF-ASSEMBLED MONOLAYER SURFACES OF DEFINED CHEMISTRIES

PubMed Central

Cornelius, Rena M.; Shankar, Sucharita P.; Brash, John L.; Babensee, Julia E.

2011-01-01

Intact and fragmented proteins, eluted from self assembled monolayer (SAM) surfaces of alkanethiols of different chemistries (-CH3, -OH, -COOH, -NH2 ), following exposure to human plasma (HP) or human serum (HS), were examined using sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and immunoblotting techniques. The SAM surfaces were incubated for 1 hour with 10% (v/v) sterile-filtered heat-inactivated (h.i.) HS or 1% (v/v) sterile-filtered h.i. HP preparations [both in phosphate buffered saline (PBS)]. Adsorbed proteins were eluted using 10% SDS/2.3% dithioerythritol for characterization of protein profiles. The type of incubating medium may be an important determinant of adsorbed protein profiles, since some variations were observed in eluates from filtered versus control unfiltered h.i. 10% HS or 1% HP. Albumin and apolipoprotein A1 were consistently detected in both filtered h.i 10% HS and 1% HP eluates from all SAM surfaces and from control tissue culture-treated polystyrene (TCPS). Interestingly, Factor H and Factor I, antithrombin, prothrombin, high molecular weight kininogen (HMWK) and IgG were present in eluates from OH, COOH and NH2 SAM surfaces and in eluates from TCPS, but not in eluates from CH3 SAM surfaces, following exposure to filtered h.i. 10% HS. These results suggest that CH3 SAM surfaces were the least pro-inflammatory of all SAM surfaces. Overall, similar trends were observed in the profiles of proteins eluted from surfaces exposed to filtered 10% HS or 1% HP. However the unique profiles of adsorbed proteins on different SAM surface chemistries may be related to their differential interactions with cells, including immune/inflammatory cells. PMID:21509932

Measuring restoration progress using pore- and surface-water chemistry across a chronosequence of formerly afforested blanket bogs.

PubMed

Gaffney, Paul P J; Hancock, Mark H; Taggart, Mark A; Andersen, Roxane

2018-08-01

During the restoration of degraded bogs and other peatlands, both habitat and functional recovery can be closely linked with nutrient cycling, which is reflected in pore- and surface-water chemistry. Several peatland restoration studies have shown that the time required for recovery of target conditions is slow (>10 years); for heavily-impacted, drained and afforested peatlands of northern Scotland, recovery time is unknown. We monitored pore- and surface-water chemistry across a chronosequence of formerly drained, afforested bog restoration sites spanning 0-17 years, using a space-for-time substitution, and compared them with open blanket bog control sites. Our aims were to measure rate of recovery towards bog conditions and to identify the best suite of water chemistry variables to indicate recovery. Our results show progress in recovery towards bog conditions over a 0-17 year period post-restoration. Elements scavenged by trees (Mg, Na, S) completely recovered within that period. Many water chemistry variables were affected by the restoration process itself, but recovered within 11 years, except ammonium (NH 4 + ), Zn and dissolved organic carbon (DOC) which remained elevated (when compared to control bogs) 17 years post restoration. Other variables did not completely recover (water table depth (WTD), pH), exhibiting what we term "legacy" effects of drainage and afforestation. Excess N and a lowered WTD are likely to slow the recovery of bog vegetation including key bog plants such as Sphagnum mosses. Over 17 years, we measured near-complete recovery in the chemistry of surface-water and deep pore-water but limited progress in shallow pore-water. Our results suggest that at least >17 years are required for complete recovery of water chemistry to bog conditions. However, we expect that newer restoration methods including conifer harvesting (stem plus brash) and the blocking of plough furrows (to increase the WTD) are likely to accelerate the restoration process

Nanoscale multireference quantum chemistry: full configuration interaction on graphical processing units.

PubMed

Fales, B Scott; Levine, Benjamin G

2015-10-13

Methods based on a full configuration interaction (FCI) expansion in an active space of orbitals are widely used for modeling chemical phenomena such as bond breaking, multiply excited states, and conical intersections in small-to-medium-sized molecules, but these phenomena occur in systems of all sizes. To scale such calculations up to the nanoscale, we have developed an implementation of FCI in which electron repulsion integral transformation and several of the more expensive steps in σ vector formation are performed on graphical processing unit (GPU) hardware. When applied to a 1.7 × 1.4 × 1.4 nm silicon nanoparticle (Si72H64) described with the polarized, all-electron 6-31G** basis set, our implementation can solve for the ground state of the 16-active-electron/16-active-orbital CASCI Hamiltonian (more than 100,000,000 configurations) in 39 min on a single NVidia K40 GPU.

Effect of Gold Nanorod Surface Chemistry on Cellular Interactions In Vitro

DTIC Science & Technology

2010-09-01

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

Rocket Science at the Nanoscale.

PubMed

Li, Jinxing; Rozen, Isaac; Wang, Joseph

2016-06-28

Autonomous propulsion at the nanoscale represents one of the most challenging and demanding goals in nanotechnology. Over the past decade, numerous important advances in nanotechnology and material science have contributed to the creation of powerful self-propelled micro/nanomotors. In particular, micro- and nanoscale rockets (MNRs) offer impressive capabilities, including remarkable speeds, large cargo-towing forces, precise motion controls, and dynamic self-assembly, which have paved the way for designing multifunctional and intelligent nanoscale machines. These multipurpose nanoscale shuttles can propel and function in complex real-life media, actively transporting and releasing therapeutic payloads and remediation agents for diverse biomedical and environmental applications. This review discusses the challenges of designing efficient MNRs and presents an overview of their propulsion behavior, fabrication methods, potential rocket fuels, navigation strategies, practical applications, and the future prospects of rocket science and technology at the nanoscale.

A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals.

PubMed

Dong, Angang; Ye, Xingchen; Chen, Jun; Kang, Yijin; Gordon, Thomas; Kikkawa, James M; Murray, Christopher B

2011-02-02

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

Perspectives on surface nanobubbles

PubMed Central

Zhang, Xuehua; Lohse, Detlef

2014-01-01

Materials of nanoscale size exhibit properties that macroscopic materials often do not have. The same holds for bubbles on the nanoscale: nanoscale gaseous domains on a solid-liquid interface have surprising properties. These include the shape, the long life time, and even superstability. Such so-called surface nanobubbles may have wide applications. This prospective article covers the basic properties of surface nanobubbles and gives several examples of potential nanobubble applications in nanomaterials and nanodevices. For example, nanobubbles can be used as templates or nanostructures in surface functionalization. The nanobubbles produced in situ in a microfluidic system can even induce an autonomous motion of the nanoparticles on which they form. Their formation also has implications for the fluid transport in narrow channels in which they form. PMID:25379084

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

PubMed

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

2017-11-20

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Single-Molecule Chemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

PubMed

Zrimsek, Alyssa B; Chiang, Naihao; Mattei, Michael; Zaleski, Stephanie; McAnally, Michael O; Chapman, Craig T; Henry, Anne-Isabelle; Schatz, George C; Van Duyne, Richard P

2017-06-14

Single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) have emerged as analytical techniques for characterizing molecular systems in nanoscale environments. SERS and TERS use plasmonically enhanced Raman scattering to characterize the chemical information on single molecules. Additionally, TERS can image single molecules with subnanometer spatial resolution. In this review, we cover the development and history of SERS and TERS, including the concept of SERS hot spots and the plasmonic nanostructures necessary for SM detection, the past and current methodologies for verifying SMSERS, and investigations into understanding the signal heterogeneities observed with SMSERS. Moving on to TERS, we cover tip fabrication and the physical origins of the subnanometer spatial resolution. Then, we highlight recent advances of SMSERS and TERS in fields such as electrochemistry, catalysis, and SM electronics, which all benefit from the vibrational characterization of single molecules. SMSERS and TERS provide new insights on molecular behavior that would otherwise be obscured in an ensemble-averaged measurement.

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

ERIC Educational Resources Information Center

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

2015-01-01

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

Kinetics and Chemistry of Ionization Wave Discharges Propagating Over Dielectric Surfaces

NASA Astrophysics Data System (ADS)

Petrishchev, Vitaly

Experimental studies of near-surface ionization wave electric discharges generated by high peak voltage (20-30 kV), nanosecond duration pulses (full width at half-maximum 50-100 ns) of positive and negative polarity and propagating over dielectric surfaces have been performed. A novel way to sustain diffuse, reproducible, ns pulse surface plasmas at a liquid-vapor interface is demonstrated at buffer gas pressures ranging from 10 to 200 Torr. Generation of surface ionization waves well reproduced shot-to-shot and sustaining diffuse near-surface plasmas is one of the principal advantages of the use of ns pulse discharge waveforms. This makes possible characterization of these plasmas in repetitively pulsed experiments. Numerous applications of these plasmas include low-temperature plasma assisted combustion, plasma fuel reforming, plasma flow control, plasma materials processing, agriculture, biology, and medicine. The objectives of the present work are (i) to demonstrate that surface ionization wave discharge plasmas sustained at a liquid-vapor interface can be used as an experimental platform for studies of near-surface plasma chemical reaction kinetics, at the conditions when the interface acts as a high-yield source of radical species, and (ii) to obtain quantitative insight into dynamics, kinetics and chemistry of surface ionization wave discharges and provide experimental data for validation of kinetic models, to assess their predictive capability. Generation of the initial radical pool may trigger a number of plasma chemical processes leading to formation of a variety of stable product species, depending on the initial composition of the liquid and the buffer gas flow. One of the products formed and detected during surface plasma / liquid water interaction is hydroxyl radical, which is closely relevant to applications of plasmas for biology and medicine. The present work includes detailed studies of surface ionization wave discharges sustained in different

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Direct optical imaging of nanoscale internal organization of polymer films

NASA Astrophysics Data System (ADS)

Suran, Swathi; Varma, Manoj

2018-02-01

Owing to its sensitivity and precise control at the nanoscale, polyelectrolytes have been immensely used to modify surfaces. Polyelectrolyte multilayers are generally water made and are easy to fabricate on any surface by the layer-by-layer (LbL) self-assembly process due to electrostatic interactions. Polyelectrolyte multilayers or PEMs can be assembled to form ultrathin membranes which can have potential applications in water filtration and desalination [1-3]. Hydration in PEMs is a consequence of both the bulk and surface phenomenon [4-7]. Bulk behavior of polymer membranes are well understood. Several techniques including reflectivity and contact angle measurements were used to measure the hydration in the bulk of polymer membranes [4, 8]. On the other hand their internal organization at the molecular level which can have a profound contribution in the transport mechanism, are not understood well. Previously, we engineered a technique, which we refer to as Bright-field Nanoscopy, which allows nanoscale optical imaging using local heterogeneities in a water-soluble germanium (Ge) thin film ( 25 nm thick) deposited on gold [8]. We use this technique to study the water transport in PEMs. It is understood that the surface charge and outer layers of the PEMs play a significant role in water transport through polymers [9-11]. This well-known `odd-even' effect arising on having different surface termination of the PEMs was optically observed with a spatial resolution unlike any other reported previously [12]. In this communication, we report that on increasing the etchant's concentration, one can control the lateral etching of the Ge film. This allowed the visualization of the nanoscale internal organization in the PEMs. Knowledge of the internal structure would allow one to engineer polymer membranes specific to applications such as drug delivering capsules, ion transport membranes and barriers etc. We also demonstrate a mathematical model involving a surface

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

PubMed

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

2012-10-01

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

Micro- and nano-scale damage on the surface of W divertor component during exposure to high heat flux loads with He

NASA Astrophysics Data System (ADS)

Li, C.; Greuner, H.; Zhao, S. X.; Böswirth, B.; Luo, G. N.; Zhou, X.; Jia, Y. Z.; Liu, X.; Liu, W.

2015-11-01

Micro- and nano-scale surface damage on a W divertor component sample exposed to high heat flux loads generated with He atoms has been investigated through SEM, EBSD, AFM and FIB-SEM. The component sample was supplied by the Institute of Plasma Physics, Chinese Academy of Sciences (ASIPP) and AT&M company, China, and the loading experiment was performed in the GLADIS facility at IPP Garching, Germany. Two typical damage structures were observed on the surface: the first one is characterized by obvious blisters and some grooves formed from ruptured blisters, and the other one is a kind of porous structure accompanying with at least ∼25 nm surface material loss. As the grain orientation is further away from <111>, the damage morphology gradually changes from the former structure to the latter. The possible damage mechanism is discussed.

All-Optical Nanoscale Thermometry using Silicon-Vacancy Centers in Diamond

NASA Astrophysics Data System (ADS)

Nguyen, Christian; Evans, Ruffin; Sipahigil, Alp; Bhaskar, Mihir; Sukachev, Denis; Lukin, Mikhail

2017-04-01

Accurate thermometry at the nanoscale is a difficult challenge, but building such a thermometer would be a powerful tool for discovering and understanding new processes in biology, chemistry and physics. Applications include cell-selective treatment of disease, engineering of more efficient integrated circuits, or even the development of new chemical and biological reactions. In this work, we study how the bulk properties of the Silicon Vacancy center (SiV) in diamond depend on temperature, and use them to measure temperature with 100mK accuracy. Using SiVs in 200 nm nanodiamonds, we measure the temperature with 100 nm spatial resolution over a 10 μm area.

Groove micro-structure optical fiber refractive index sensor with nanoscale gold film based on surface plasmon resonance

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Li, Shuguang; Liu, Qiang; Feng, Xinxing; Zhang, Shuhuan; Wang, Yujun; Wu, Junjun

2018-07-01

A groove micro-structure optical fiber refractive index sensor with nanoscale gold film based on surface plasmon resonance (SPR) is proposed and analyzed by the finite element method (FEM). Numerical results show that the average sensitivity is 15,933 nm/refractive index unit (RIU) with the refractive index of analyte ranging from 1.40 to 1.43 and the maximum sensitivity is 28,600 nm/RIU and the resolution of the sensor is 3.50 × 10-8 RIU. The groove micro-structure optical fiber refractive index sensor do some changes on the D-shaped fiber sensor, compared with conventional D-shaped fiber sensor, it has a higher sensitivity and it is easier to produce than the traditional SPR sensor.

Redox Deposition of Nanoscale Metal Oxides on Carbon for Next-Generation Electrochemical Capacitors

DTIC Science & Technology

2013-01-01

Nanoscale Metal Oxides Sassin et al. Redox Deposition Approaches to Nanoscale Coatings of Metal Oxides Manganese Oxides. Permanganate (MnO4 ) is a versa...scalability of the permanganate carbon redox reaction for generating MnOx coatings that store charge.21 The initial study per- formed on planar graphite...the carbon surface from the aqueous permanganate solu- tion (pH∼5),29,35 evidenced by a sharp increase in solution pH and a decrease in solution

Direct manufacturing of ultrathin graphite on three-dimensional nanoscale features

PubMed Central

Pacios, Mercè; Hosseini, Peiman; Fan, Ye; He, Zhengyu; Krause, Oliver; Hutchison, John; Warner, Jamie H.; Bhaskaran, Harish

2016-01-01

There have been many successful attempts to grow high-quality large-area graphene on flat substrates. Doing so at the nanoscale has thus far been plagued by significant scalability problems, particularly because of the need for delicate transfer processes onto predefined features, which are necessarily low-yield processes and which can introduce undesirable residues. Herein we describe a highly scalable, clean and effective, in-situ method that uses thin film deposition techniques to directly grow on a continuous basis ultrathin graphite (uG) on uneven nanoscale surfaces. We then demonstrate that this is possible on a model system of atomic force probe tips of various radii. Further, we characterize the growth characteristics of this technique as well as the film’s superior conduction and lower adhesion at these scales. This sets the stage for such a process to allow the use of highly functional graphite in high-aspect-ratio nanoscale components. PMID:26939862

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

PubMed Central

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-01-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications. PMID:28508866

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

DOE PAGES

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; ...

2017-05-16

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

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

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

NASA Astrophysics Data System (ADS)

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-05-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

Nanoscale Controls on CO2-water-rock Interactions in Saline Reservoirs

NASA Astrophysics Data System (ADS)

Deyoreo, J.; Depaolo, D. J.

2009-12-01

It is becoming increasingly widely recognized that geologic sequestration of CO2, when combined with economical means of capture, may be one of the most effective approaches to reducing net CO2 emissions to the atmosphere over the next century. Injection of CO2 into saline geologic formations involves forcing a buoyant, low-viscosity fluid into a more dense, higher viscosity fluid. The difference in wetting properties of the two fluids, their partial miscibility, the fact that CO2 and H2O form an acid, and the heterogeneity of geologic formations combine to make the flow and transport details fascinating but difficult to fully characterize and predict. A major question is whether the flow of CO2 into subsurface formations, the efficiency of pore space filling, and the trapping efficiency can be not only predicted but controlled over the decades of injection that might be associated with the life of a power plant. The major technological gaps to controlling and ultimately sequestering subsurface CO2 can be traced to far-from-equilibrum processes that originate at the molecular and nanoscale, but are expressed as complex emergent behavior at larger scales. Essential knowledge gaps involve the effects of nanoscale confinement on material properties, flow and chemical reactions, the effects of nanoparticles, mineral surface dynamics, and microbiota on mineral dissolution/precipitation and fluid flow, and the dynamics of fluid-fluid and fluid-mineral interfaces. To address these scientific and technical challenges, the Energy Frontier Research Center recently established, involving collaboration between LBNL, ORNL, MIT, UC Berkeley, UC Davis and LLNL, will attempt to bring new approaches to the study of nanoscale phenomena in fluid-rock systems to bear on the problem of CO2 behavior in saline formations. The stated goal is to use molecular, nanoscale, and pore-network scale approaches to control flow, dissolution, and precipitation in deep subsurface rock formations to

Nanoscale integration is the next frontier for nanotechnology

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

Picraux, Samuel T

2009-01-01

Nanoscale integration of materials and structures is the next critical step to exploit the promise of nanomaterials. Many novel and fascinating properties have been revealed for nanostructured materials. But if nanotechnology is to live up to its promise we must incorporate these nanoscale building blocks into functional systems that connect to the micro- and macroscale world. To do this we will inevitably need to understand and exploit the resulting combined unique properties of these integrated nanosystems. Much science waits to be discovered in the process. Nanoscale integration extends from the synthesis and fabrication of individual nanoscale building blocks, to themore » assembly of these building blocks into composite structures, and finally to the formation of complex functional systems. As illustrated in Figure 1, the building blocks may be homogeneous or heterogeneous, the composite materials may be nanocomposite or patterned structures, and the functional systems will involve additional combinations of materials. Nanoscale integration involves assembling diverse nanoscale materials across length scales to design and achieve new properties and functionality. At each stage size-dependent properties, the influence of surfaces in close proximity, and a multitude of interfaces all come into play. Whether the final system involves coherent electrons in a quantum computing approach, the combined flow of phonons and electrons for a high efficiency thermoelectric micro-generator, or a molecular recognition structure for bio-sensing, the combined effects of size, surface, and interface will be critical. In essence, one wants to combine the novel functions available through nanoscale science to achieve unique multi-functionalities not available in bulk materials. Perhaps the best-known example of integration is that of combining electronic components together into very large scale integrated circuits (VLSI). The integrated circuit has revolutionized electronics

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

DTIC Science & Technology

2015-12-18

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

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

PubMed

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

2018-07-01

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

A nano-scale mirror-like surface of Ti-6Al-4V attained by chemical mechanical polishing

NASA Astrophysics Data System (ADS)

Chenliang, Liang; Weili, Liu; Shasha, Li; Hui, Kong; Zefang, Zhang; Zhitang, Song

2016-05-01

Metal Ti and its alloys have been widely utilized in the fields of aviation, medical science, and micro-electro-mechanical systems, for its excellent specific strength, resistance to corrosion, and biological compatibility. As the application of Ti moves to the micro or nano scale, however, traditional methods of planarization have shown their short slabs. Thus, we introduce the method of chemical mechanical polishing (CMP) to provide a new way for the nano-scale planarization method of Ti alloys. We obtain a mirror-like surface, whose flatness is of nano-scale, via the CMP method. We test the basic mechanical behavior of Ti-6Al-4V (Ti64) in the CMP process, and optimize the composition of CMP slurry. Furthermore, the possible reactions that may take place in the CMP process have been studied by electrochemical methods combined with x-ray photoelectron spectroscopy (XPS). An equivalent circuit has been built to interpret the dynamic of oxidation. Finally, a model has been established to explain the synergy of chemical and mechanical effects in the CMP of Ti-6Al-4V. Project supported by the National Major Scientific and Technological Special Project during the Twelfth Five-year Plan Period of China (Grant No. 2009ZX02030-1), the National Natural Science Foundation of China (Grant No. 51205387), the Support by Science and Technology Commission of Shanghai City, China (Grant No. 11nm0500300), and the Science and Technology Commission of Shanghai City, China (Grant No. 14XD1425300).

Nanoscale Ionic Liquids

DTIC Science & Technology

2006-11-01

Technical Report 11 December 2005 - 30 November 2006 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Nanoscale Ionic Liquids 5b. GRANT NUMBER FA9550-06-1-0012...Title: Nanoscale Ionic Liquids Principal Investigator: Emmanuel P. Giannelis Address: Materials Science and Engineering, Bard Hall, Cornell University...based fluids exhibit high ionic conductivity. The NFs are typically synthesized by grafting a charged, oligomeric corona onto the nanoparticle cores

Perchlorate Formation on Mars Through Surface Radiolysis-Initiated Atmospheric Chemistry: A Potential Mechanism

NASA Technical Reports Server (NTRS)

Wilson, Eric H.; Atreya, Sushil K.; Kaiser, Ralf I.; Mahaffy, Paul R.

2016-01-01

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 x 10(exp 7) molecules/sq cm/s sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

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

PubMed

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

2011-04-01

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

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

Treesearch

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

2003-01-01

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

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

PubMed

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

2018-07-15

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

Surface Chemistry in Cobalt Phosphide-Stabilized Lithium-Sulfur Batteries.

PubMed

Zhong, Yiren; Yin, Lichang; He, Peng; Liu, Wen; Wu, Zishan; Wang, Hailiang

2018-01-31

Chemistry at the cathode/electrolyte interface plays an important role for lithium-sulfur batteries in which stable cycling of the sulfur cathode requires confinement of the lithium polysulfide intermediates and their fast electrochemical conversion on the electrode surface. While many materials have been found to be effective for confining polysulfides, the underlying chemical interactions remain poorly understood. We report a new and general lithium polysulfide-binding mechanism enabled by surface oxidation layers of transition-metal phosphide and chalcogenide materials. We for the first time find that CoP nanoparticles strongly adsorb polysulfides because their natural oxidation (forming Co-O-P-like species) activates the surface Co sites for binding polysulfides via strong Co-S bonding. With a surface oxidation layer capable of confining polysulfides and an inner core suitable for conducting electrons, the CoP nanoparticles are thus a desirable candidate for stabilizing and improving the performance of sulfur cathodes in lithium-sulfur batteries. We demonstrate that sulfur electrodes that hold a high mass loading of 7 mg cm -2 and a high areal capacity of 5.6 mAh cm -2 can be stably cycled for 200 cycles. We further reveal that this new surface oxidation-induced polysulfide-binding scheme applies to a series of transition-metal phosphide and chalcogenide materials and can explain their stabilizing effects for lithium-sulfur batteries.

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.

The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

NASA Technical Reports Server (NTRS)

Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

1994-01-01

Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

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

EPA Science Inventory

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

High-capacity electrode materials for electrochemical energy storage: Role of nanoscale effects

DOE PAGES

Nanda, Jagjit; Martha, Surendra K.; Kalyanaraman, Ramki

2015-06-02

In this review, we summarize the current state-of-the art electrode materials used for high-capacity lithium-ion-based batteries and their significant role towards revolutionizing the electrochemical energy storage landscape in the area of consumer electronics, transportation and grid storage application. We discuss the role of nanoscale effects on the electrochemical performance of high-capacity battery electrode materials. Decrease in the particle size of the primary electrode materials from micron to nanometre size improves the ionic and electronic diffusion rates significantly. Nanometre-thick solid electrolyte (such as lithium phosphorous oxynitride) and oxides (such as Al 2O 3, ZnO, TiO 2 etc.) material coatings also improvemore » the interfacial stability and rate capability of a number of battery chemistries. Finally, we elucidate these effects in terms of different high-capacity battery chemistries based on intercalation and conversion mechanism.« less

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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.

Plasmonic mode converter for controlling optical impedance and nanoscale light-matter interaction.

PubMed

Hung, Yun-Ting; Huang, Chen-Bin; Huang, Jer-Shing

2012-08-27

To enable multiple functions of plasmonic nanocircuits, it is of key importance to control the propagation properties and the modal distribution of the guided optical modes such that their impedance matches to that of nearby quantum systems and desired light-matter interaction can be achieved. Here, we present efficient mode converters for manipulating guided modes on a plasmonic two-wire transmission line. The mode conversion is achieved through varying the path length, wire cross section and the surrounding index of refraction. Instead of pure optical interference, strong near-field coupling of surface plasmons results in great momentum splitting and modal profile variation. We theoretically demonstrate control over nanoantenna radiation and discuss the possibility to enhance nanoscale light-matter interaction. The proposed converter may find applications in surface plasmon amplification, index sensing and enhanced nanoscale spectroscopy.

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

PubMed

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

2014-04-01

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

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

DOE PAGES

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

2016-02-11

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

WATER CHEMISTRY ASSESSMENT METHODS

EPA Science Inventory

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

Exploring Carbon Nanotubes for Nanoscale Devices

NASA Technical Reports Server (NTRS)

Han, Jie; Dai; Anantram; Jaffe; Saini, Subhash (Technical Monitor)

1998-01-01

Carbon nanotubes (CNTs) are shown to promise great opportunities in nanoelectronic devices and nanoelectromechanical systems (NEMS) because of their inherent nanoscale sizes, intrinsic electric conductivities, and seamless hexagonal network architectures. I present our collaborative work with Stanford on exploring CNTs for nanodevices in this talk. The electrical property measurements suggest that metallic tubes are quantum wires. Furthermore, two and three terminal CNT junctions have been observed experimentally. We have proposed and studied CNT-based molecular switches and logic devices for future digital electronics. We also have studied CNTs based NEMS inclusing gears, cantilevers, and scanning probe microscopy tips. We investigate both chemistry and physics based aspects of the CNT NEMS. Our results suggest that CNT have ideal stiffness, vibrational frequencies, Q-factors, geometry-dependent electric conductivities, and the highest chemical and mechanical stabilities for the NEMS. The use of CNT SPM tips for nanolithography is presented for demonstration of the advantages of the CNT NEMS.

Giant plasmonic energy and momentum transfer on the nanoscale

NASA Astrophysics Data System (ADS)

Durach, Maxim

electric fields up to 105--10 6 V/cm. It can serve as a powerful nanoscale source of THz radiation. The giant SPIDER opens up a new field of ultraintense THz nanooptics with wide potential applications in nanotechnology and nanoscience, including microelectronics, nanoplasmonics, and biomedicine. Additionally, the SPIDER is an ultrafast effect whose bandwidth for nanometric wires is 20 THz, which allows for detection of femtosecond pulses on the nanoscale. INDEX WORDS: Nanoplasmonics, Nanoplasmonic renormalization of Coulomb interaction, Surface-plasmon enhanced Forster energy transfer (FRET), Surface-plasmon-induced drag-effect rectification (SPIDER), Nanotechnology, Plasmonics on the nanoscale, Localized surface plasmons (LSPs), Surface plasmon polaritons (SPPs)

Contributions of nanoscale roughness to anomalous colloid retention and stability behavior

USDA-ARS?s Scientific Manuscript database

Expressions were presented to determine the mean interaction energy between a colloid and a solid-water interface (SWI), as well as for colloid-colloid interactions, when both surfaces contain binary nanoscale roughness and chemical heterogeneity. The influence of heterogeneity type, roughness para...

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

PubMed

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

2017-07-14

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

Size Effects in Nanoscale Structural Phenomena

NASA Astrophysics Data System (ADS)

McElhinny, Kyle Matthew

The creation of nanostructures offers the opportunity to modify and tune properties in ways inaccessible in bulk materials. A key component in this development is the introduction of size effects which reduce the physical size, dimensionality, and increase the contribution of surface effects. The size effects strongly modify the structural dynamics in nanoscale systems and leads to changes in the vibrational, electrical, and optical properties. An increased level of understanding and control of nanoscale structural dynamics will enable more precise control over nanomaterial transport properties. My work has shown that 1D spatial confinement through the creation of semiconducting nanomembranes modifies the phonon population and dispersion. X ray thermal diffuse scattering distributions show an excess in intensity for nanomembranes less than 100 nm in thickness, for phonon modes with wavevectors spanning the entire Brillouin zone. This excess intensity indicates the development of new low energy phonon modes or the softening of elastic constants. Furthermore, an additional anisotropy in the phonon dispersion is observed with a symmetry matching the direction of spatial confinement. This work has also extended x ray thermal diffuse scattering for use in studying nanomaterials. In electro- and photoactive monolayers a structural reconfiguration can be produced by external optical stimuli. I have developed an electro and photoactive molecular monolayers on oxide surfaces. Using x ray reflectivity, I have evaluated the organization and reconfiguration of molecular monolayers deposited by Langmuir Blodgett technique. I have designed and probed the reconfiguration of optically reconfigurable monolayers of azobenzene donor molecules on semiconducting surfaces. These monolayers reconfigure through a cooperative switching process leading to the development of large isomeric domains. This work represents an advancement in the interpretation of x ray reflectivity from molecular

Nanoscale live cell imaging using hopping probe ion conductance microscopy

PubMed Central

Novak, Pavel; Li, Chao; Shevchuk, Andrew I.; Stepanyan, Ruben; Caldwell, Matthew; Hughes, Simon; Smart, Trevor G.; Gorelik, Julia; Ostanin, Victor P.; Lab, Max J.; Moss, Guy W. J.; Frolenkov, Gregory I.; Klenerman, David; Korchev, Yuri E.

2009-01-01

We describe a major advance in scanning ion conductance microscopy: a new hopping mode that allows non-contact imaging of the complex surfaces of live cells with resolution better than 20 nm. The effectiveness of this novel technique was demonstrated by imaging networks of cultured rat hippocampal neurons and mechanosensory stereocilia of mouse cochlear hair cells. The technique allows studying nanoscale phenomena on the surface of live cells under physiological conditions. PMID:19252505

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

NASA Astrophysics Data System (ADS)

Kirsch, Paul Daniel

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

Apparatus for producing nanoscale ceramic powders

DOEpatents

Helble, Joseph J.; Moniz, Gary A.; Morse, Theodore F.

1997-02-04

An apparatus provides high temperature and short residence time conditions for the production of nanoscale ceramic powders. The apparatus includes a confinement structure having a multiple inclined surfaces for confining flame located between the surfaces so as to define a flame zone. A burner system employs one or more burners to provide flame to the flame zone. Each burner is located in the flame zone in close proximity to at least one of the inclined surfaces. A delivery system disposed adjacent the flame zone delivers an aerosol, comprising an organic or carbonaceous carrier material and a ceramic precursor, to the flame zone to expose the aerosol to a temperature sufficient to induce combustion of the carrier material and vaporization and nucleation, or diffusion and oxidation, of the ceramic precursor to form pure, crystalline, narrow size distribution, nanophase ceramic particles.

Apparatus for producing nanoscale ceramic powders

DOEpatents

Helble, Joseph J.; Moniz, Gary A.; Morse, Theodore F.

1995-09-05

An apparatus provides high temperature and short residence time conditions for the production of nanoscale ceramic powders. The apparatus includes a confinement structure having a multiple inclined surfaces for confining flame located between the surfaces so as to define a flame zone. A burner system employs one or more burners to provide flame to the flame zone. Each burner is located in the flame zone in close proximity to at least one of the inclined surfaces. A delivery system disposed adjacent the flame zone delivers an aerosol, comprising an organic or carbonaceous carrier material and a ceramic precursor, to the flame zone to expose the aerosol to a temperature sufficient to induce combustion of the carrier material and vaporization and nucleation, or diffusion and oxidation, of the ceramic precursor to form pure, crystalline, narrow size distribution, nanophase ceramic particles.

Investigation on nanoscale processes on the BaF{sub 2}(111) surface in various solutions by frequency modulation atomic force microscopy

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

Kobayashi, Naritaka, E-mail: naritaka@mail.saitama-u.ac.jp; Kawamura, Ryuzo; Yoshikawa, Hiroshi Y.

2016-06-07

In this study, we have directly observed nanoscale processes that occur on BaF{sub 2}(111) surfaces in various solutions using liquid-environment frequency modulation atomic force microscopy (FM-AFM) with a true atomic resolution. In addition, to investigate atomic-scale mechanisms of crystal growth process of BaF{sub 2}, we determined a suitable solution for atomic-resolution FM-AFM imaging of the BaF{sub 2}(111) surface. For undersaturated solutions, the surface is roughened by barium hydroxo complexes in the case of high pH, whereas by dissolution and proton or water molecule adsorption throughout the surface in the case of low pH. On the other hand, for supersaturated solutions,more » the surface shows two-dimensional nucleation and growth (σ = 0.1) and three-dimensional crystal growth with tetrahedral structures (σ = 1), where σ is the degree of supersaturation. The atomic-resolution imaging of the BaF{sub 2}(111) surface has been demonstrated in potassium fluoride (KF) and the supersaturated (σ = 0.1 and 1) solutions, wherein atomically flat terraces are shown at least for about 30 min.« less

Unsupervised data mining in nanoscale x-ray spectro-microscopic study of NdFeB magnet

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

Duan, Xiaoyue; Yang, Feifei; Antono, Erin

Novel developments in X-ray based spectro-microscopic characterization techniques have increased the rate of acquisition of spatially resolved spectroscopic data by several orders of magnitude over what was possible a few years ago. This accelerated data acquisition, with high spatial resolution at nanoscale and sensitivity to subtle differences in chemistry and atomic structure, provides a unique opportunity to investigate hierarchically complex and structurally heterogeneous systems found in functional devices and materials systems. However, handling and analyzing the large volume data generated poses significant challenges. Here we apply an unsupervised data-mining algorithm known as DBSCAN to study a rare-earth element based permanentmore » magnet material, Nd 2Fe 14B. We are able to reduce a large spectro-microscopic dataset of over 300,000 spectra to 3, preserving much of the underlying information. Scientists can easily and quickly analyze in detail three characteristic spectra. Our approach can rapidly provide a concise representation of a large and complex dataset to materials scientists and chemists. For instance, it shows that the surface of common Nd 2Fe 14B magnet is chemically and structurally very different from the bulk, suggesting a possible surface alteration effect possibly due to the corrosion, which could affect the material’s overall properties.« less

Unsupervised data mining in nanoscale x-ray spectro-microscopic study of NdFeB magnet

DOE PAGES

Duan, Xiaoyue; Yang, Feifei; Antono, Erin; ...

2016-09-29

Novel developments in X-ray based spectro-microscopic characterization techniques have increased the rate of acquisition of spatially resolved spectroscopic data by several orders of magnitude over what was possible a few years ago. This accelerated data acquisition, with high spatial resolution at nanoscale and sensitivity to subtle differences in chemistry and atomic structure, provides a unique opportunity to investigate hierarchically complex and structurally heterogeneous systems found in functional devices and materials systems. However, handling and analyzing the large volume data generated poses significant challenges. Here we apply an unsupervised data-mining algorithm known as DBSCAN to study a rare-earth element based permanentmore » magnet material, Nd 2Fe 14B. We are able to reduce a large spectro-microscopic dataset of over 300,000 spectra to 3, preserving much of the underlying information. Scientists can easily and quickly analyze in detail three characteristic spectra. Our approach can rapidly provide a concise representation of a large and complex dataset to materials scientists and chemists. For instance, it shows that the surface of common Nd 2Fe 14B magnet is chemically and structurally very different from the bulk, suggesting a possible surface alteration effect possibly due to the corrosion, which could affect the material’s overall properties.« less

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

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

EPA Science Inventory

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

Maintaining the pluripotency of mouse embryonic stem cells on gold nanoparticle layers with nanoscale but not microscale surface roughness

NASA Astrophysics Data System (ADS)

Lyu, Zhonglin; Wang, Hongwei; Wang, Yanyun; Ding, Kaiguo; Liu, Huan; Yuan, Lin; Shi, Xiujuan; Wang, Mengmeng; Wang, Yanwei; Chen, Hong

2014-05-01

Efficient control of the self-renewal and pluripotency maintenance of embryonic stem cell (ESC) is a prerequisite for translating stem cell technologies to clinical applications. Surface topography is one of the most important factors that regulates cell behaviors. In the present study, micro/nano topographical structures composed of a gold nanoparticle layer (GNPL) with nano-, sub-micro-, and microscale surface roughnesses were used to study the roles of these structures in regulating the behaviors of mouse ESCs (mESCs) under feeder-free conditions. The distinctive results from Oct-4 immunofluorescence staining and quantitative real-time polymerase chain reaction (qPCR) demonstrate that nanoscale and low sub-microscale surface roughnesses (Rq less than 392 nm) are conducive to the long-term maintenance of mESC pluripotency, while high sub-microscale and microscale surface roughnesses (Rq greater than 573 nm) result in a significant loss of mESC pluripotency and a faster undirectional differentiation, particularly in long-term culture. Moreover, the likely signalling cascades engaged in the topological sensing of mESCs were investigated and their role in affecting the maintenance of the long-term cell pluripotency was discussed by analyzing the expression of proteins related to E-cadherin mediated cell-cell adhesions and integrin-mediated focal adhesions (FAs). Additionally, the conclusions from MTT, cell morphology staining and alkaline phosphatase (ALP) activity assays show that the surface roughness can provide a potent regulatory signal for various mESC behaviors, including cell attachment, proliferation and osteoinduction.Efficient control of the self-renewal and pluripotency maintenance of embryonic stem cell (ESC) is a prerequisite for translating stem cell technologies to clinical applications. Surface topography is one of the most important factors that regulates cell behaviors. In the present study, micro/nano topographical structures composed of a gold

An evaluation method for nanoscale wrinkle

NASA Astrophysics Data System (ADS)

Liu, Y. P.; Wang, C. G.; Zhang, L. M.; Tan, H. F.

2016-06-01

In this paper, a spectrum-based wrinkling analysis method via two-dimensional Fourier transformation is proposed aiming to solve the difficulty of nanoscale wrinkle evaluation. It evaluates the wrinkle characteristics including wrinkling wavelength and direction simply using a single wrinkling image. Based on this method, the evaluation results of nanoscale wrinkle characteristics show agreement with the open experimental results within an error of 6%. It is also verified to be appropriate for the macro wrinkle evaluation without scale limitations. The spectrum-based wrinkling analysis is an effective method for nanoscale evaluation, which contributes to reveal the mechanism of nanoscale wrinkling.

Effect of nanostructured surface configuration on evaporation and condensation characteristics of thin film liquid argon in a nano-scale confinement

NASA Astrophysics Data System (ADS)

Kuri, Subrata Kumar; Rakibuzzaman, S. M.; Sabah, Arefiny; Ahmed, Jannat; Hasan, Mohammad Nasim

2017-12-01

Molecular dynamics simulation has been carried out to go through the evaporation and condensation characteristics of thin liquid argon film in nanoscale confinement having nanostructured boundary. Nanoscale confinement under consideration consists of hot and cold parallel platinum plates at the bottom and top end of a model cuboid inside which the fluid domain comprised of liquid argon film at the bottom plate and vapor argon in between liquid argon and upper plate of the confinement. Three different confinement configurations have been considered here: (i) Both platinum plates are flat, (ii) Upper plate consisting of transverse slots and (iii) Both plates consisting of transverse slots. The height of the slots is 1.5 nm. Considering hydrophilic nature of top and bottom plates, two different high temperatures of the hot wall was set and an observation was made. For all the structures, equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. Then the lower wall is set to two different temperatures like 110 K and 250 K for all three models to perform non-equilibrium molecular dynamics (NEMD). Various system characteristics such as atomic distribution, wall heat flux, evaporative mass flux etc. have been obtained and discussed to have a clear understanding of the effect of nanotextured surface on phase change phenomena.

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

PubMed Central

Ghouma, Imen; Limousy, Lionel; Bennici, Simona

2018-01-01

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

Wettability of natural superhydrophobic surfaces.

PubMed

Webb, Hayden K; Crawford, Russell J; Ivanova, Elena P

2014-08-01

Since the description of the 'Lotus Effect' by Barthlott and Neinhuis in 1997, the existence of superhydrophobic surfaces in the natural world has become common knowledge. Superhydrophobicity is associated with a number of possible evolutionary benefits that may be bestowed upon an organism, ranging from the ease of dewetting of their surfaces and therefore prevention of encumbrance by water droplets, self-cleaning and removal of particulates and potential pathogens, and even to antimicrobial activity. The superhydrophobic properties of natural surfaces have been attributed to the presence of hierarchical microscale (>1 μm) and nanoscale (typically below 200 nm) structures on the surface, and as a result, the generation of topographical hierarchy is usually considered of high importance in the fabrication of synthetic superhydrophobic surfaces. When one surveys the breadth of data available on naturally existing superhydrophobic surfaces, however, it can be observed that topographical hierarchy is not present on all naturally superhydrophobic surfaces; in fact, the only universal feature of these surfaces is the presence of a sophisticated nanoscale structure. Additionally, several natural surfaces, e.g. those present on rose petals and gecko feet, display high water contact angles and high adhesion of droplets, due to the pinning effect. These surfaces are not truly superhydrophobic, and lack significant degrees of nanoscale roughness. Here, we discuss the phenomena of superhydrophobicity and pseudo-superhydrophobicity in nature, and present an argument that while hierarchical surface roughness may aid in the stability of the superhydrophobic effect, it is nanoscale surface architecture alone that is the true determinant of superhydrophobicity. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoscale morphological and chemical changes of high voltage lithium-manganese rich NMC composite cathodes with cycling.

PubMed

Yang, Feifei; Liu, Yijin; Martha, Surendra K; Wu, Ziyu; Andrews, Joy C; Ice, Gene E; Pianetta, Piero; Nanda, Jagjit

2014-08-13

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium-manganese rich cathode material of composition Li(1 + x)M(1 - x)O2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼ 30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface.

Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling

PubMed Central

2015-01-01

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium–manganese rich cathode material of composition Li1 + xM1 – xO2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface. PMID:25054780

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.

Nanoplasmonics tuned "click chemistry".

PubMed

Tijunelyte, I; Guenin, E; Lidgi-Guigui, N; Colas, F; Ibrahim, J; Toury, T; Lamy de la Chapelle, M

2016-04-07

Nanoplasmonics is a growing field of optical condensed matter science dedicated to optical phenomena at the nanoscale level in metal systems. Extensive research on noble metallic nanoparticles (NPs) has emerged within the last two decades due to their ability to keep the optical energy concentrated in the vicinity of NPs, in particular, the ability to create optical near-field enhancement followed by heat generation. We have exploited these properties in order to induce a localised "click" reaction in the vicinity of gold nanostructures under unfavourable experimental conditions. We demonstrate that this reaction can be controlled by the plasmonic properties of the nanostructures and we propose two physical mechanisms to interpret the observed plasmonic tuning of the "click" chemistry.

Lithographically Patterned Nanoscale Electrodeposition of Plasmonic, Bimetallic, Semiconductor, Magnetic, and Polymer Nanoring Arrays

PubMed Central

2015-01-01

Large area arrays of magnetic, semiconducting, and insulating nanorings were created by coupling colloidal lithography with nanoscale electrodeposition. This versatile nanoscale fabrication process allows for the independent tuning of the spacing, diameter, and width of the nanorings with typical values of 1.0 μm, 750 nm, and 100 nm, respectively, and was used to form nanorings from a host of materials: Ni, Co, bimetallic Ni/Au, CdSe, and polydopamine. These nanoring arrays have potential applications in memory storage, optical materials, and biosensing. A modified version of this nanoscale electrodeposition process was also used to create arrays of split gold nanorings. The size of the split nanoring opening was controlled by the angle of photoresist exposure during the fabrication process and could be varied from 50% down to 10% of the ring circumference. The large area (cm2 scale) gold split nanoring array surfaces exhibited strong polarization-dependent plasmonic absorption bands for wavelengths from 1 to 5 μm. Plasmonic nanoscale split ring arrays are potentially useful as tunable dichroic materials throughout the infrared and near-infrared spectral regions. PMID:25553204

Kinesin Motor Enzymology: Chemistry, Structure, and Physics of Nanoscale Molecular Machines.

PubMed

Cochran, J C

2015-09-01

Molecular motors are enzymes that convert chemical potential energy into controlled kinetic energy for mechanical work inside cells. Understanding the biophysics of these motors is essential for appreciating life as well as apprehending diseases that arise from motor malfunction. This review focuses on kinesin motor enzymology with special emphasis on the literature that reports the chemistry, structure and physics of several different kinesin superfamily members.

Nanoscale Dewetting Transition in Protein Complex Folding

PubMed Central

Hua, Lan; Huang, Xuhui; Liu, Pu; Zhou, Ruhong; Berne, Bruce J.

2011-01-01

In a previous study, a surprising drying transition was observed to take place inside the nanoscale hydrophobic channel in the tetramer of the protein melittin. The goal of this paper is to determine if there are other protein complexes capable of displaying a dewetting transition during their final stage of folding. We searched the entire protein data bank (PDB) for all possible candidates, including protein tetramers, dimers, and two-domain proteins, and then performed the molecular dynamics (MD) simulations on the top candidates identified by a simple hydrophobic scoring function based on aligned hydrophobic surface areas. Our large scale MD simulations found several more proteins, including three tetramers, six dimers, and two two-domain proteins, which display a nanoscale dewetting transition in their final stage of folding. Even though the scoring function alone is not sufficient (i.e., a high score is necessary but not sufficient) in identifying the dewetting candidates, it does provide useful insights into the features of complex interfaces needed for dewetting. All top candidates have two features in common: (1) large aligned (matched) hydrophobic areas between two corresponding surfaces, and (2) large connected hydrophobic areas on the same surface. We have also studied the effect on dewetting of different water models and different treatments of the long-range electrostatic interactions (cutoff vs PME), and found the dewetting phenomena is fairly robust. This work presents a few proteins other than melittin tetramer for further experimental studies of the role of dewetting in the end stages of protein folding. PMID:17608515

Finding the Connections between a High-School Chemistry Curriculum and Nano-Scale Science and Technology

ERIC Educational Resources Information Center

Blonder, Ron; Sakhnini, Sohair

2017-01-01

The high-school chemistry curriculum is loaded with many important chemical concepts that are taught at the high-school level and it is therefore very difficult to add modern contents to the existing curriculum. However, many studies have underscored the importance of integrating modern chemistry contents such as nanotechnology into a high-school…

Nanoscale semiconducting silicon as a nutritional food additive

NASA Astrophysics Data System (ADS)

Canham, L. T.

2007-05-01

Very high surface area silicon powders can be realized by high energy milling or electrochemical etching techniques. Such nanoscale silicon structures, whilst biodegradable in the human gastrointestinal tract, are shown to be remarkably stable in most foodstuffs and beverages. The potential for using silicon to improve the shelf life and bioavailability of specific nutrients in functional foods is highlighted. Published drug delivery data implies that the nanoentrapment of hydrophobic nutrients will significantly improve their dissolution kinetics, through a combined effect of nanostructuring and solid state modification. Nutrients loaded to date include vitamins, fish oils, lycopene and coenzyme Q10. In addition, there is growing published evidence that optimized release of orthosilicic acid, the biodegradation product of semiconducting silicon in the gut, offers beneficial effects with regard bone health. The utility of nanoscale silicon in the nutritional field shows early promise and is worthy of much further study.

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

ERIC Educational Resources Information Center

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

2012-01-01

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

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

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

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

Center for Nanoscale Science and Technology

National Institute of Standards and Technology Data Gateway

NIST Center for Nanoscale Science and Technology (Program website, free access)   Currently there is no database matching your keyword search, but the NIST Center for Nanoscale Science and Technology website may be of interest. The Center for Nanoscale Science and Technology enables science and industry by providing essential measurement methods, instrumentation, and standards to support all phases of nanotechnology development, from discovery to production.

Controlled surface chemistry of diamond/β-SiC composite films for preferential protein adsorption.

PubMed

Wang, Tao; Handschuh-Wang, Stephan; Yang, Yang; Zhuang, Hao; Schlemper, Christoph; Wesner, Daniel; Schönherr, Holger; Zhang, Wenjun; Jiang, Xin

2014-02-04

Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/β-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/β-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/β-SiC ratio of the composite films shows a continuous change from pure diamond to β-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/β-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on β-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/β-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on β-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/β-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/β-SiC gradient film can be a promising material for biomedical applications which

A nanoscale vacuum-tube diode triggered by few-cycle laser pulses

NASA Astrophysics Data System (ADS)

Higuchi, Takuya; Maisenbacher, Lothar; Liehl, Andreas; Dombi, Péter; Hommelhoff, Peter

2015-02-01

We propose and demonstrate a nanoscale vacuum-tube diode triggered by few-cycle near-infrared laser pulses. It represents an ultrafast electronic device based on light fields, exploiting near-field optical enhancement at surfaces of two metal nanotips. The sharper of the two tips displays a stronger field-enhancement, resulting in larger photoemission yields at its surface. One laser pulse with a peak intensity of 4.7 × 1011 W/cm2 triggers photoemission of ˜16 electrons from the sharper cathode tip, while emission from the blunter anode tip is suppressed by 19 dB to ˜0.2 electrons per pulse. Thus, the laser-triggered current between two tips exhibit a rectifying behavior, in analogy to classical vacuum-tube diodes. According to the kinetic energy of the emitted electrons and the distance between the tips, the total operation time of this laser-triggered nanoscale diode is estimated to be below 1 ps.

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

PubMed

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

2015-08-18

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

Rapid changes in surface water carbonate chemistry during Antarctic sea ice melt

NASA Astrophysics Data System (ADS)

Jones, Elizabeth M.; Bakker, Dorothee C. E.; Venables, Hugh J.; Whitehouse, Michael J.; Korb, Rebecca E.; Watson, Andrew J.

2010-11-01

ABSTRACT The effect of sea ice melt on the carbonate chemistry of surface waters in the Weddell-Scotia Confluence, Southern Ocean, was investigated during January 2008. Contrasting concentrations of dissolved inorganic carbon (DIC), total alkalinity (TA) and the fugacity of carbon dioxide (fCO2) were observed in and around the receding sea ice edge. The precipitation of carbonate minerals such as ikaite (CaCO3.6H2O) in sea ice brine has the net effect of decreasing DIC and TA and increasing the fCO2 in the brine. Deficits in DIC up to 12 +/- 3 μmol kg-1 in the marginal ice zone (MIZ) were consistent with the release of DIC-poor brines to surface waters during sea ice melt. Biological utilization of carbon was the dominant processes and accounted for 41 +/- 1 μmol kg-1 of the summer DIC deficit. The data suggest that the combined effects of biological carbon uptake and the precipitation of carbonates created substantial undersaturation in fCO2 of 95 μatm in the MIZ during summer sea ice melt. Further work is required to improve the understanding of ikaite chemistry in Antarctic sea ice and its importance for the sea ice carbon pump.

Investigation of graphene-based nanoscale radiation sensitive materials

NASA Astrophysics Data System (ADS)

Robinson, Joshua A.; Wetherington, Maxwell; Hughes, Zachary; LaBella, Michael, III; Bresnehan, Michael

2012-06-01

Current state-of-the-art nanotechnology offers multiple benefits for radiation sensing applications. These include the ability to incorporate nano-sized radiation indicators into widely used materials such as paint, corrosion-resistant coatings, and ceramics to create nano-composite materials that can be widely used in everyday life. Additionally, nanotechnology may lead to the development of ultra-low power, flexible detection systems that can be embedded in clothing or other systems. Graphene, a single layer of graphite, exhibits exceptional electronic and structural properties, and is being investigated for high-frequency devices and sensors. Previous work indicates that graphene-oxide (GO) - a derivative of graphene - exhibits luminescent properties that can be tailored based on chemistry; however, exploration of graphene-oxide's ability to provide a sufficient change in luminescent properties when exposed to gamma or neutron radiation has not been carried out. We investigate the mechanisms of radiation-induced chemical modifications and radiation damage induced shifts in luminescence in graphene-oxide materials to provide a fundamental foundation for further development of radiation sensitive detection architectures. Additionally, we investigate the integration of hexagonal boron nitride (hBN) with graphene-based devices to evaluate radiation induced conductivity in nanoscale devices. Importantly, we demonstrate the sensitivity of graphene transport properties to the presence of alpha particles, and discuss the successful integration of hBN with large area graphene electrodes as a means to provide the foundation for large-area nanoscale radiation sensors.

Performance of laser sintered Ti-6Al-4V implants with bone-inspired porosity and micro/nanoscale surface roughness in the rabbit femur

PubMed Central

Cohen, David J.; Cheng, Alice; Sahingur, Kaan; Clohessy, Ryan M.; Hopkins, Louis B.; Boyan, Barbara D.; Schwartz, Zvi

2018-01-01

Long term success of bone-interfacing implants remains a challenge in compromised patients and in areas of low bone quality. While surface roughness at the micro/nanoscale can promote osteogenesis, macro-scale porosity is important for promoting mechanical stability of the implant over time. Currently, machining techniques permit pores to be placed throughout the implant, but the pores are generally uniform in dimension. The advent of laser sintering provides a way to design and manufacture implants with specific porosity and variable dimensions at high resolution. This approach enables production of metal implants that mimic complex geometries found in biology. In this study, we used a rabbit femur model to compare osseointegration of laser sintered solid and porous implants. Ti-6Al-4V implants were laser sintered in a clinically relevant size and shape. One set of implants had a novel porosity based on human trabecular bone; both sets had grit-blasted/acid-etched surfaces. After characterization, implants were inserted transaxially into rabbit femora; mechanical testing, microCT and histomorphometry were conducted 10 weeks postoperatively. There were no differences in pull-out strength or bone-to-implant contact. However, both microCT and histomorphometry showed significantly higher new bone volume for porous compared to solid implants. Bone growth was observed into porous implant pores, especially near apical portions of the implant interfacing with cortical bone. These results show that laser sintered Ti-6Al-4V implants with micro/nanoscale surface roughness and trabecular bone-inspired porosity promote bone growth and may be used as a superior alternative to solid implants for bone-interfacing implants. PMID:28452335

Performance of laser sintered Ti-6Al-4V implants with bone-inspired porosity and micro/nanoscale surface roughness in the rabbit femur.

PubMed

Cohen, David J; Cheng, Alice; Sahingur, Kaan; Clohessy, Ryan M; Hopkins, Louis B; Boyan, Barbara D; Schwartz, Zvi

2017-04-28

Long term success of bone-interfacing implants remains a challenge in compromised patients and in areas of low bone quality. While surface roughness at the micro/nanoscale can promote osteogenesis, macro-scale porosity is important for promoting mechanical stability of the implant over time. Currently, machining techniques permit pores to be placed throughout the implant, but the pores are generally uniform in dimension. The advent of laser sintering provides a way to design and manufacture implants with specific porosity and variable dimensions at high resolution. This approach enables production of metal implants that mimic complex geometries found in biology. In this study, we used a rabbit femur model to compare osseointegration of laser sintered solid and porous implants. Ti-6Al-4V implants were laser sintered in a clinically relevant size and shape. One set of implants had a novel porosity based on human trabecular bone; both sets had grit-blasted/acid-etched surfaces. After characterization, implants were inserted transaxially into rabbit femora; mechanical testing, micro-computed tomography (microCT) and histomorphometry were conducted 10 weeks post-operatively. There were no differences in pull-out strength or bone-to-implant contact. However, both microCT and histomorphometry showed significantly higher new bone volume for porous compared to solid implants. Bone growth was observed into porous implant pores, especially near apical portions of the implant interfacing with cortical bone. These results show that laser sintered Ti-6Al-4V implants with micro/nanoscale surface roughness and trabecular bone-inspired porosity promote bone growth and may be used as a superior alternative to solid implants for bone-interfacing implants.

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

DOE PAGES

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; ...

2017-02-01

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

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

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Reducing bacteria and macrophage density on nanophase hydroxyapatite coated onto titanium surfaces without releasing pharmaceutical agents

NASA Astrophysics Data System (ADS)

Bhardwaj, Garima; Yazici, Hilal; Webster, Thomas J.

2015-04-01

Reducing bacterial density on titanium implant surfaces has been a major concern because of the increasing number of nosocomial infections. Controlling the inflammatory response post implantation has also been an important issue for medical devices due to the detrimental effects of chronic inflammation on device performance. It has recently been demonstrated that manipulating medical device surface properties including chemistry, roughness and wettability can control both infection and inflammation. Here, we synthesized nanophase (that is, materials with one dimension in the nanoscale) hydroxyapatite coatings on titanium to reduce bacterial adhesion and inflammatory responses (as measured by macrophage functions) and compared such results to bare titanium and plasma sprayed hydroxyapatite titanium coated surfaces used clinically today. This approach is a pharmaceutical-free approach to inhibit infection and inflammation due to the detrimental side effects of any drug released in the body. Here, nanophase hydroxyapatite was synthesized in sizes ranging from 110-170 nm and was subsequently coated onto titanium samples using electrophoretic deposition. Results indicated that smaller nanoscale hydroxyapatite features on titanium surfaces alone decreased bacterial attachment in the presence of gram negative (P. aeruginosa), gram positive (S. aureus) and ampicillin resistant gram-negative (E. coli) bacteria as well as were able to control inflammatory responses; properties which should lead to their further investigation for improved medical applications.

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

PubMed

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

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

LiNbO3 surfaces from a microscopic perspective

NASA Astrophysics Data System (ADS)

Sanna, Simone; Gero Schmidt, Wolf

2017-10-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-09-01

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

Dechlorination of disinfection by-product monochloroacetic acid in drinking water by nanoscale palladized iron bimetallic particle.

PubMed

Chen, Chao; Wang, Xiangyu; Chang, Ying; Liu, Huiling

2008-01-01

Nanoscale palladized iron (Pd/Fe) bimetallic particles were prepared by reductive deposition method. The particles were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope (SEM), transmission electron microscope (TEM), and Brunauer-Emmett-Teller-nitrogen (BET-N2) method. Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles contained alpha-Fe0. Detected Pd to Fe ratio by weight (Pd/Fe ratio) was close to theoretical value. Spherical granules with diameter of 47 +/- 11.5 nm connected with one another to form chains and the chains composed nanoscale Pd/Fe bimetallic particles. Specific surface area of particles was 51 m2/g. The factors, such as species of reductants, Pd/Fe ratio, dose of nanoscale Pd/Fe bimetallic particles added into solutions, solution initial pH, and a variety of solvents were studied. Dechlorination effect of monochloroacetic acid by different reductants followed the trend: nanoscale Pd/Fe bimetallic particles of 0.182% Pd/Fe > nanoscale Fe > reductive Fe. When the Pd/Fe ratio was lower than 0.083%, increasing Pd/Fe ratio would increase dechlorination efficiency (DE) of MCAA. When the Pd/Fe ratio was higher than 0.083%, increasing Pd/Fe ratio caused a decrease in DE. Adding more nanoscale Pd/Fe bimetallic particles to solution would enhance DE. The DE of MCAA decreased as initial pH of solution increased.

Atomistic methodologies for material properties of 2D materials at the nanoscale

NASA Astrophysics Data System (ADS)

Zhang, Zhen

Research on two dimensional (2D) materials, such as graphene and MoS2, now involves thousands of researchers worldwide cutting across physics, chemistry, engineering and biology. Due to the extraordinary properties of 2D materials, research extends from fundamental science to novel applications of 2D materials. From an engineering point of view, understanding the material properties of 2D materials under various conditions is crucial for tailoring the electrical and mechanical properties of 2D-material-based devices at the nanoscale. Even at the nanoscale, molecular systems typically consist of a vast number of atoms. Molecular dynamics (MD) simulations enable us to understand the properties of assemblies of molecules in terms of their structure and the microscopic interactions between them. From a continuum approach, mechanical properties and thermal properties, such as strain, stress, and heat capacity, are well defined and experimentally measurable. In MD simulations, material systems are considered to be discrete, and only interatomic potential, interatomic forces, and atom positions are directly obtainable. Besides, most of the fracture mechanics concepts, such as stress intensity factors, are not applicable since there is no singularity in MD simulations. However, energy release rate still remains to be a feasible and crucial physical quantity to characterize the fracture mechanical property of materials at the nanoscale. Therefore, equivalent definition of a physical quantity both in atomic scale and macroscopic scale is necessary in order to understand molecular and continuum scale phenomena concurrently. This work introduces atomistic simulation methodologies, based on interatomic potential and interatomic forces, as a tool to unveil the mechanical properties, thermal properties and fracture mechanical properties of 2D materials at the nanoscale. Among many 2D materials, graphene and MoS2 have attracted intense interest. Therefore, we applied our

Lithography of Polymer Nanostructures on Glass for Teaching Polymer Chemistry and Physics.

PubMed

Sahar-Halbany, Adi; Vance, Jennifer M; Drain, Charles Michael

2011-05-01

As nanolithography becomes increasingly important in technology and daily life, a variety of inexpensive and creative methods toward communicating the concepts underpinning these processes in the classroom are necessary. An experiment is described that uses simple CD-Rs, C-clamps, an oven, and a freezer to provide concrete examples and insights into the chemistry and principles of nanolithography. The experiment also has flexibility, making it suitable for a range of classroom levels from high school to more advanced labs in college. Because CD-Rs are composed of grooves of polycarbonate, the experiment provides a basis for discussions and exploration into the chemistry and physics of polymers on the nanoscale.

Controlled implant/soft tissue interaction by nanoscale surface modifications of 3D porous titanium implants.

PubMed

Rieger, Elisabeth; Dupret-Bories, Agnès; Salou, Laetitia; Metz-Boutigue, Marie-Helene; Layrolle, Pierre; Debry, Christian; Lavalle, Philippe; Vrana, Nihal Engin

2015-06-07

-laden gelatin hydrogels, significantly more cells migrated towards the acid etched beads. In conclusion, the nanoscale surface treatment of 3D porous titanium structures can modulate in vivo integration by the accumulative effect of the surface treatment on several physical factors such as protein adsorption, surface hydrophilicity and surface roughness. The improved protein adsorption capacity of the treated implants can be further exploited by a pre-treatment with autologous serum to render the implant surface more bioactive. Titanium microbeads are a good model system to observe these effects in a 3D microenvironment and provide a better representation of cellular responses in 3D.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

Nanoscale potentiometry.

PubMed

Bakker, Eric; Pretsch, Ernö

2008-01-01

Potentiometric sensors share unique characteristics that set them apart from other electrochemical sensors. Potentiometric nanoelectrodes have been reported and successfully used for many decades, and we review these developments. Current research chiefly focuses on nanoscale films at the outer or the inner side of the membrane, with outer layers for increasing biocompatibility, expanding the sensor response, or improving the limit of detection (LOD). Inner layers are mainly used for stabilizing the response and eliminating inner aqueous contacts or undesired nanoscale layers of water. We also discuss the ultimate detectability of ions with such sensors and the power of coupling the ultra-low LODs of ion-selective electrodes with nanoparticle labels to give attractive bioassays that can compete with state-of-the-art electrochemical detection.

Improving Neural Recording Technology at the Nanoscale

NASA Astrophysics Data System (ADS)

Ferguson, John Eric

Neural recording electrodes are widely used to study normal brain function (e.g., learning, memory, and sensation) and abnormal brain function (e.g., epilepsy, addiction, and depression) and to interface with the nervous system for neuroprosthetics. With a deep understanding of the electrode interface at the nanoscale and the use of novel nanofabrication processes, neural recording electrodes can be designed that surpass previous limits and enable new applications. In this thesis, I will discuss three projects. In the first project, we created an ultralow-impedance electrode coating by controlling the nanoscale texture of electrode surfaces. In the second project, we developed a novel nanowire electrode for long-term intracellular recordings. In the third project, we created a means of wirelessly communicating with ultra-miniature, implantable neural recording devices. The techniques developed for these projects offer significant improvements in the quality of neural recordings. They can also open the door to new types of experiments and medical devices, which can lead to a better understanding of the brain and can enable novel and improved tools for clinical applications.

Hybrid quantum and molecular mechanics embedded cluster models for chemistry on silicon and silicon carbide surfaces

NASA Astrophysics Data System (ADS)

Shoemaker, James Richard

Fabrication of silicon carbide (SiC) semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO2 layer on SiC by oxidation is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics (QM), do not exist because of the huge computational cost of solving Schrodinger's equation for a molecular cluster large enough to represent a surface. Molecular mechanics (MM), which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, but cannot accurately model chemical reactions. A new hybrid QM/MM computational method for surface chemistry was developed and applied to silicon and SiC surfaces. The addition of MM steric constraints was shown to have a large effect on the energetics of O atom adsorption on SiC. Adsorption of O atoms on Si-terminated SiC(111) favors above surface sites, in contrast to Si(111), but favors subsurface adsorption sites on C- terminated SiC(111). This difference, and the energetics of C atom etching via CO2 desorption, can explain the observed poor performance of SiC devices in which insulating layers were grown on C-terminated surfaces.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization.

PubMed

Struzzi, Claudia; Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

2017-01-01

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF 4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization

PubMed Central

Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

2017-01-01

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions. PMID:28904833

Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

NASA Astrophysics Data System (ADS)

Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna; Nowakowska, Maria; Szczubiałka, Krzysztof

2014-12-01

Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2

Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

PubMed Central

Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna M.; Nowakowska, Maria; Szczubiałka, Krzysztof

2015-01-01

Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2. PMID:25629028

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

Modeling of Stiffness and Strength of Bone at Nanoscale.

PubMed

Abueidda, Diab W; Sabet, Fereshteh A; Jasiuk, Iwona M

2017-05-01

Two distinct geometrical models of bone at the nanoscale (collagen fibril and mineral platelets) are analyzed computationally. In the first model (model I), minerals are periodically distributed in a staggered manner in a collagen matrix while in the second model (model II), minerals form continuous layers outside the collagen fibril. Elastic modulus and strength of bone at the nanoscale, represented by these two models under longitudinal tensile loading, are studied using a finite element (FE) software abaqus. The analysis employs a traction-separation law (cohesive surface modeling) at various interfaces in the models to account for interfacial delaminations. Plane stress, plane strain, and axisymmetric versions of the two models are considered. Model II is found to have a higher stiffness than model I for all cases. For strength, the two models alternate the superiority of performance depending on the inputs and assumptions used. For model II, the axisymmetric case gives higher results than the plane stress and plane strain cases while an opposite trend is observed for model I. For axisymmetric case, model II shows greater strength and stiffness compared to model I. The collagen-mineral arrangement of bone at nanoscale forms a basic building block of bone. Thus, knowledge of its mechanical properties is of high scientific and clinical interests.

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

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

DOE PAGES

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

2017-12-06

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

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

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

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

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

Uni-directional liquid spreading on asymmetric nanostructured surfaces

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

The Impact of Nanoparticle Surface Chemistry on Biological Systems

NASA Astrophysics Data System (ADS)

Thorn, Angie Sue Morris

because they are easy to synthesize and their properties (such as size, porosity and surface chemistry) can be fine-tuned. Silica nanoparticles can be found in thousands of commercially available products such as toothpastes, cosmetics and detergents and are currently being developed for biomedical applications such as drug delivery and biomedical imaging. Our findings herein indicate that the surface chemistry of silica nanoparticles can have an effect on lung inflammation after exposure. Specifically, amine-modified silica NPs are considered to be less toxic compared to bare silica nanoparticles. Together, these studies provide insight into the role that material properties have on toxicity and allow for a better understanding of their impact on human and environmental health. The final aim of this thesis was to develop surface-modified nanoparticles for drug delivery applications. For this, biodegradable, polymeric NPs were used due to their inert nature and biocompatibility. Furthermore, polymeric NPs are excellent for loading drugs and using them as drug delivery vehicles. In this work, poly (lactic-co-glycolic acid) (PLGA) NPs were loaded with a therapeutic peptide. These NPs were then coated with chitosan (a mucoadhesive polymer) for the treatment of allergic asthma or coated with a small cationic mitochondrial targeting agent for the treatment of ischemia/reperfusion injury. Taken as a whole, this thesis sheds light on the impact of NPs on human health. First by providing useful toxological data for CuO and silica NPs as well as highlighting the potential of surface-modified polymeric NPs to be used in drug delivery-based applications.

Inflammatory cell response to ultra-thin amorphous and crystalline hydroxyapatite surfaces.

PubMed

Rydén, Louise; Omar, Omar; Johansson, Anna; Jimbo, Ryo; Palmquist, Anders; Thomsen, Peter

2017-01-01

It has been suggested that surface modification with a thin hydroxyapatite (HA) coating enhances the osseointegration of titanium implants. However, there is insufficient information about the biological processes involved in the HA-induced response. This study aimed to investigate the inflammatory cell response to titanium implants with either amorphous or crystalline thin HA. Human mononuclear cells were cultured on titanium discs with a machined surface or with a thin, 0.1 μm, amorphous or crystalline HA coating. Cells were cultured for 24 and 96 h, with and without lipopolysaccharide (LPS) stimulation. The surfaces were characterized with respect to chemistry, phase composition, wettability and topography. Biological analyses included the percentage of implant-adherent cells and the secretion of pro-inflammatory cytokine (TNF-α) and growth factors (BMP-2 and TGF-β1). Crystalline HA revealed a smooth surface, whereas the amorphous HA displayed a porous structure, at nano-scale, and a hydrophobic surface. Higher TNF-α secretion and a higher ratio of adherent cells were demonstrated for the amorphous HA compared with the crystalline HA. TGF-β1 secretion was detected in all groups, but without any difference. No BMP-2 secretion was detected in any of the groups. The addition of LPS resulted in a significant increase in TNF-α in all groups, whereas TGF-β1 was not affected. Taken together, the results show that thin HA coatings with similar micro-roughness but a different phase composition, nano-scale roughness and wettability are associated with different monocyte responses. In the absence of strong inflammatory stimuli, crystalline hydroxyapatite elicits a lower inflammatory response compared with amorphous hydroxyapatite.

Nanoscale MOS devices: device parameter fluctuations and low-frequency noise (Invited Paper)

NASA Astrophysics Data System (ADS)

Wong, Hei; Iwai, Hiroshi; Liou, J. J.

2005-05-01

It is well-known in conventional MOS transistors that the low-frequency noise or flicker noise is mainly contributed by the trapping-detrapping events in the gate oxide and the mobility fluctuation in the surface channel. In nanoscale MOS transistors, the number of trapping-detrapping events becomes less important because of the large direct tunneling current through the ultrathin gate dielectric which reduces the probability of trapping-detrapping and the level of leakage current fluctuation. Other noise sources become more significant in nanoscale devices. The source and drain resistance noises have greater impact on the drain current noise. Significant contribution of the parasitic bipolar transistor noise in ultra-short channel and channel mobility fluctuation to the channel noise are observed. The channel mobility fluctuation in nanoscale devices could be due to the local composition fluctuation of the gate dielectric material which gives rise to the permittivity fluctuation along the channel and results in gigantic channel potential fluctuation. On the other hand, the statistical variations of the device parameters across the wafer would cause the noise measurements less accurate which will be a challenge for the applicability of analytical flicker noise model as a process or device evaluation tool for nanoscale devices. Some measures for circumventing these difficulties are proposed.

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.

Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well.

PubMed

Mille, Caroline; Debarnot, Dominique; Zorzi, Willy; El Moualij, Benaïssa; Coudreuse, Arnaud; Legeay, Gilbert; Quadrio, Isabelle; Perret-Liaudet, Armand; Poncin-Epaillard, Fabienne

2012-04-18

The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic-phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°), negatively charged and smooth inner surface.

Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well

PubMed Central

Mille, Caroline; Debarnot, Dominique; Zorzi, Willy; Moualij, Benaïssa El; Coudreuse, Arnaud; Legeay, Gilbert; Quadrio, Isabelle; Perret-Liaudet, Armand; Poncin-Epaillard, Fabienne

2012-01-01

The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic—phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°), negatively charged and smooth inner surface. PMID:24955533