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Sample records for gold surfaces investigated

  1. Interactions of Bacterial Lipopolysaccharides with Gold Nanorod Surfaces Investigated by Refractometric Sensing.

    PubMed

    Abadeer, Nardine S; Fülöp, Gergő; Chen, Si; Käll, Mikael; Murphy, Catherine J

    2015-11-11

    The interface between nanoparticles and bacterial surfaces is of great interest for applications in nanomedicine and food safety. Here, we demonstrate that interactions between gold nanorods and bacterial surface molecules are governed by the nanoparticle surface coating. Polymer-coated gold nanorod substrates are exposed to lipopolysaccharides extracted from Pseudomonas aeruginosa, Salmonella enterica and Escherichia coli, and attachment is monitored using localized surface plasmon resonance refractometric sensing. The number of lipopolysaccharide molecules attached per nanorod is calculated from the shift in the plasmon maximum, which results from the change in refractive index after analyte binding. Colloidal gold nanorods in water are also incubated with lipopolysaccharides to demonstrate the effect of lipopolysaccharide concentration on plasmon shift, ζ-potential, and association constant. Both gold nanorod surface charge and surface chemistry affect gold nanorod-lipopolysaccharide interactions. In general, anionic lipopolysaccharides was found to attach more effectively to cationic gold nanorods than to neutral or anionic gold nanorods. Some variation in lipopolysaccharide attachment is also observed between the three strains studied, demonstrating the potential complexity of bacteria-nanoparticle interactions.

  2. Electrochemical investigations of 3-(3-thienyl) acrylic acid protected nanoclusters and planar gold surfaces.

    PubMed

    Nirmal, R G; Kavitha, A L; Berchmans, Sheela; Yegnaraman, V

    2007-06-01

    Formation of self assembled monolayers on gold surface by thiols and disulphides is a well known phenomenon and extensive research work has been carried out in this area with envisaged applications in the area of sensors, molecular electronics, lithography, device fabrication using bottom-up approach, etc. Recently, it has been established that thiophene molecules can self assemble on gold surface due to Au-S interactions. 3-(3-thienyl) acrylic acid, a bifunctional ligand is used in this work to form self-assembled monolayers on planar gold surfaces (two dimensional assemblies) and to prepare monolayer protected gold nano clusters (three-dimensional assemblies). The electron transfer blocking properties of the two-dimensional monolayers were evaluated by using standard redox probes like ferrocyanide anions and Ruthenium hexamine cations. The functionalisation of the two-dimensional and three-dimensional assemblies has been carried out with ferrocene carboxylic acid and the functionalised monolayers were characterized by Cyclic voltammetry. The formation of thienyl acrylic acid protected nanoclusters has been verified by TEM and surface plasmon resonance absorption. It has been observed that when thiophene based ligands are used as stabilizers for the formation of metal nanoparticles, they tend to aggregate as a result of pi-pi interactions between adjacent thiophene ligands. In this case it is found that aggregation is prevented. The substituent at the thiophene ring hinders pi-pi interactions. The quantised nature of electrochemical charging of these nanoparticles has been demonstrated by differential pulse voltammetry (DPV), which exhibit peak like features (coulomb's staircase). This work also explores the possibility of using 3-(3-thienyl) acrylic acid as building blocks or spacers on planar and colloidal gold surfaces for potential applications in the field of sensors and devices.

  3. In situ investigation of the mobility of small gold clusters on cleaved MgO surfaces

    NASA Technical Reports Server (NTRS)

    Metois, J. J.; Heinemann, K.; Poppa, H.

    1976-01-01

    The mobility of small clusters of gold (about 10 A in diameter) on electron-beam-cleaved MgO surfaces was studied by in situ transmission electron microscopy under controlled vacuum and temperature conditions. During the first 10 min following a deposition at room temperature, over 10 per cent of the crystallites moved over short distances (about 20 A) discontinuously, with a velocity greater than 150 A/sec. Eighty per cent of the mobility events were characterized by the avoidance of proximity of other crystallites, and this was tentatively explained as the result of repulsive elastic forces between the interacting crystallites.

  4. Piezoelectric crystal impedance analysis for investigating the modification processes of protein, cross-linker, and DNA on gold surface

    NASA Astrophysics Data System (ADS)

    Zhou, Anhong; Xie, Qingji; Li, Ping; Nie, Lihua; Yao, Shouzhuo

    2000-05-01

    The processes of surface modification on gold-coated piezoelectric quartz crystal sensor have been in situ investigated by using the impedance analysis technique. The changes of equivalent circuit parameters were used to interpret the different behaviors of successively modifying protein, cross-linker, and DNA onto a gold electrode surface. It was found that the frequency changes due to protein adsorption might be described as a sum of two exponential functions, compared with a first-order kinetic function exhibited in subsequent binding of cross-linker to protein. The kinetic parameters were fitted to these two cases. It was also shown that the DNA molecules binding to cross-linker gave rise to the changes of the density-viscosity and the dielectric constant, both being linearly related to DNA concentration in the liquid when below 6.0 μg m -1.

  5. Surface-stabilized gold nanocatalysts

    DOEpatents

    Dai, Sheng [Knoxville, TN; Yan, Wenfu [Oak Ridge, TN

    2009-12-08

    A surface-stabilized gold nanocatalyst includes a solid support having stabilizing surfaces for supporting gold nanoparticles, and a plurality of gold nanoparticles having an average particle size of less than 8 nm disposed on the stabilizing surfaces. The surface-stabilized gold nanocatalyst provides enhanced stability, such as at high temperature under oxygen containing environments. In one embodiment, the solid support is a multi-layer support comprising at least a first layer having a second layer providing the stabilizing surfaces disposed thereon, the first and second layer being chemically distinct.

  6. Gold nanodisk array surface plasmon resonance sensor

    NASA Astrophysics Data System (ADS)

    Tian, Xueli

    Surface plasmon resonances in periodic metal nanostructures have been investigated for sensing applications over the last decade. The resonance wavelengths of the nanostructures are usually measured in the transmission or reflection spectrum for chemical and biological sensing. In this thesis, I introduce a nanoscale gap mediated surface plasmon resonance nanodisk array for displacement sensing and a super-period gold nanodisk grating enabled surface plasmon resonance spectrometer sensor. The super-period gold nanodisk grating has a small subwavelength period and a large diffraction grating period. Surface plasmon resonance spectra are measured in the first order diffraction spatial profiles captured by a charge-coupled device (CCD). A surface plasmon resonance sensor for the bovine serum albumin (BSA) protein nanolayer bonding is demonstrated by measuring the surface plasmon resonance shift in the first order diffraction spatial intensity profiles captured by the CCD.

  7. In situ synthesis and surface functionalization of gold nanoparticles with curcumin and their antioxidant properties: an experimental and density functional theory investigation

    NASA Astrophysics Data System (ADS)

    Singh, Dheeraj K.; Jagannathan, Ramya; Khandelwal, Puneet; Abraham, Priya Mary; Poddar, Pankaj

    2013-02-01

    Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl4 using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au3+ ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au3+ ions are reduced to Au0. Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules.Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic

  8. In situ synthesis and surface functionalization of gold nanoparticles with curcumin and their antioxidant properties: an experimental and density functional theory investigation.

    PubMed

    Singh, Dheeraj K; Jagannathan, Ramya; Khandelwal, Puneet; Abraham, Priya Mary; Poddar, Pankaj

    2013-03-07

    Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl(4) using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au(3+) ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au(3+) ions are reduced to Au(0). Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules.

  9. Formation, structure, and orientation of gold silicide on gold surfaces

    NASA Technical Reports Server (NTRS)

    Green, A. K.; Bauer, E.

    1976-01-01

    The formation of gold silicide on Au films evaporated onto Si(111) surfaces is studied by Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED). Surface condition, film thickness, deposition temperature, annealing temperature, and heating rate during annealing are varied. Several oriented crystalline silicide layers are observed.

  10. A case study investigating the occurrence of geosmin and 2-methylisoborneol (MIB) in the surface waters of the Hinze Dam, Gold Coast, Australia.

    PubMed

    Uwins, H K; Teasdale, P; Stratton, H

    2007-01-01

    The Hinze Dam is located in the Gold Coast hinterland and is the primary source of water supply for the Gold Coast region. Sporadic and unpredictable taste and odour events caused by geosmin and 2-methylisoborneol (MIB) are an ongoing problem in the Hinze Dam. To investigate potential ecological and physiological triggers of these events, a 12-month surface-sampling regime was undertaken. Concentrations of geosmin, MIB, nitrogen and phosphorus were measured. Algal and cyanobacterial counts were performed. Water temperature, rainfall and dam capacity were also recorded. The occurrence of geosmin was found to correlate significantly with Anabaena numbers, water temperature and dam capacity. The occurrence of MIB correlated with increasing ammonia. No significant correlations were observed with the other nutrients or physical parameters measured. Overall, this study demonstrated that high concentrations of geosmin detected in dam surface waters was strongly correlated with an increase in numbers of Anabaena spp. These events were most likely triggered by significant rainfall causing a pulse in nutrients into the dam, in conjunction with warmer water temperatures.

  11. Gold-Organic Hybrids: On-Surface Synthesis and Perspectives.

    PubMed

    Zhang, Haiming; Chi, Lifeng

    2016-12-01

    Gold-organic hybrids can be prepared on gold substrates by on-surface dehalogenation of molecular precursors with multiple halogen substituents. Various contact geometries of covalent arylAu bonds are achieved by changing the halogen substituents in the bay or peri regions. Scanning tunneling microscopy/spectroscopy (STM/STS) investigations allow a better understanding of the structure/property relationships in various gold-aryl contacts. Recent progress on the synthesis, large-scale alignment, and STS measurement of gold-organic hybrids is described, ending with an emphasis on potential future applications, e.g., as precursors (intermediates) for the synthesis of graphene nanoribbons (GNRs) on insulating surfaces, and as a model system to investigate the role of covalent arylAu bonds in electron transport through gold-GNR contacts.

  12. Electrically Conductive Polyimide Films Containing Gold Surface

    NASA Technical Reports Server (NTRS)

    Caplan, Maggie L.; Stoakley, Diane M.; St. Clair, Anne K.

    1994-01-01

    Polyimide films exhibiting high thermo-oxidative stability and including electrically conductive surface layers containing gold made by casting process. Many variations of basic process conditions, ingredients, and sequence of operations possible, and not all resulting versions of process yield electrically conductive films. Gold-containing layer formed on film surface during cure. These metallic gold-containing polyimides used in film and coating applications requiring electrical conductivity, high reflectivity, exceptional thermal stability, and/or mechanical integrity. They also find commercial potential in areas ranging from thin films for satellite antennas to decorative coatings and packaging.

  13. Topological states on the gold surface.

    PubMed

    Yan, Binghai; Stadtmüller, Benjamin; Haag, Norman; Jakobs, Sebastian; Seidel, Johannes; Jungkenn, Dominik; Mathias, Stefan; Cinchetti, Mirko; Aeschlimann, Martin; Felser, Claudia

    2015-12-14

    Gold surfaces host special electronic states that have been understood as a prototype of Shockley surface states. These surface states are commonly employed to benchmark the capability of angle-resolved photoemission spectroscopy (ARPES) and scanning tunnelling spectroscopy. Here we show that these Shockley surface states can be reinterpreted as topologically derived surface states (TDSSs) of a topological insulator (TI), a recently discovered quantum state. Based on band structure calculations, the Z2-type invariants of gold can be well-defined to characterize a TI. Further, our ARPES measurement validates TDSSs by detecting the dispersion of unoccupied surface states. The same TDSSs are also recognized on surfaces of other well-known noble metals (for example, silver, copper, platinum and palladium), which shines a new light on these long-known surface states.

  14. Surface-modified gold nanoshells for enhanced cellular uptake.

    PubMed

    Liang, Zhongshi; Liu, Yun; Li, Xiangyang; Wu, Qinge; Yu, Jiahui; Luo, Shufang; Lai, Lihui; Liu, Shunying

    2011-09-15

    Gold nanoshells have shown a great potential for use as agents in a wide variety of biomedical applications, and some of which require the delivery of large numbers of gold nanoshells onto or into the cells. Here, we develop a ready method to enhance the cellular uptake of gold nanoshells by modifying with meso-2,3-dimercaptosuccinic acid (DMSA). The quantifiable technique of inductively coupled plasma atomic emissions spectroscopy (ICP-AES) and transmission electron microscopy (TEM) were used to investigate the cellular uptake of unmodified and DMSA-modified gold nanoshells. Three cell lines (RAW 264.7, A549, and BEL-7402) were involved and the results indicated that the cellular uptake of the DMSA-modified gold nanoshells was obviously enhanced versus the unmodified gold nanoshells. The reason possibly lies in the nonspecific adsorption of serum protein on the DMSA-modified gold nanoshells (DMSA-GNs), which consequently enhanced the cellular uptake. As a continued effort, in vitro experiments with endocytic inhibitors suggested the DMSA-GNs internalized into cells via receptor-mediated endocytosis (RME) pathway. This study has provided a valuable insight into the effects of surface modification on cellular uptake of nanoparticles.

  15. Silicide surface phases on gold

    NASA Technical Reports Server (NTRS)

    Green, A. K.; Bauer, E.

    1981-01-01

    The crystalline silicide layers formed on (111) and (100) surfaces of Au films on various Si single-crystal substrates are studied by LEED and AES in conjunction with sputter-depth profiling as a function of annealing temperature. On the (111) surface, three basic silicide structures are obtained corresponding to layers of various thicknesses as obtained by different preparation conditions. The (100) surface shows only two different structures. None of the structures is compatible with the various bulk silicide structures deduced from X-ray diffraction. Using LEED as a criterion for the presence or absence of silicide on the surface, smaller layer thicknesses are obtained than reported previously on the basis of AES studies.

  16. Immobilization of gold nanoparticles on cell culture surfaces for safe and enhanced gold nanoparticle-mediated laser transfection

    NASA Astrophysics Data System (ADS)

    Kalies, Stefan; Heinemann, Dag; Schomaker, Markus; Gentemann, Lara; Meyer, Heiko; Ripken, Tammo

    2014-07-01

    In comparison to standard transfection methods, gold nanoparticle-mediated laser transfection has proven to be a versatile alternative. This is based on its minor influence on cell viability and its high efficiency, especially for the delivery of small molecules like small interfering RNA. However, in order to transfer it to routine usage, a safety aspect is of major concern: The avoidance of nanoparticle uptake by the cells is desired. The immobilization of the gold nanoparticles on cell culture surfaces can address this issue. In this study, we achieved this by silanization of the appropriate surfaces and the binding of gold nanoparticles to them. Comparable perforation efficiencies to the previous approaches of gold nanoparticle-mediated laser transfection with free gold nanoparticles are demonstrated. The uptake of the immobilized particles by the cells is unlikely. Consequently, these investigations offer the possibility of bringing gold nanoparticle-mediated laser transfection closer to routine usage.

  17. Immobilization of gold nanoparticles on cell culture surfaces for safe and enhanced gold nanoparticle-mediated laser transfection.

    PubMed

    Kalies, Stefan; Heinemann, Dag; Schomaker, Markus; Gentemann, Lara; Meyer, Heiko; Ripken, Tammo

    2014-01-01

    In comparison to standard transfection methods, gold nanoparticle-mediated laser transfection has proven to be a versatile alternative. This is based on its minor influence on cell viability and its high efficiency, especially for the delivery of small molecules like small interfering RNA. However, in order to transfer it to routine usage, a safety aspect is of major concern: The avoidance of nanoparticle uptake by the cells is desired. The immobilization of the gold nanoparticles on cell culture surfaces can address this issue. In this study, we achieved this by silanization of the appropriate surfaces and the binding of gold nanoparticles to them. Comparable perforation efficiencies to the previous approaches of gold nanoparticle-mediated laser transfection with free gold nanoparticles are demonstrated. The uptake of the immobilized particles by the cells is unlikely. Consequently, these investigations offer the possibility of bringing gold nanoparticle-mediated laser transfection closer to routine usage.

  18. Gold surface with gold nitride-a surface enhanced Raman scattering active substrate

    NASA Astrophysics Data System (ADS)

    Brieva, A. C.; Alves, L.; Krishnamurthy, S.; Šiller, L.

    2009-03-01

    The nitration of gold surfaces is a nonpolluting method, which can lead to large scale production of substrates with remarkable properties and applications. We present a topographical study of the nanoscale structure of the gold nitride surfaces produced by radio frequency (rf) nitrogen plasma etching of thin gold films. Atomic force microscopy images taken after rf etching reveal the striking appearance of the cluster assembly with large clusters surrounded by small clusters (7.9±1.4 and 2.3±0.9 nm, respectively) appearing to exhibit an attractive interaction. We discuss the possible mechanism for this attraction based on a colloid model by Messina et al. [Phys. Rev. Lett. 85, 872 (2000)]. This surface exhibits a notable surface enhanced Raman scattering effect demonstrated with L-alanine and rhodamine-6G. The significance of this work is that we found that this SERS active gold nitride surface can be prepared in just one step: by nitrogen plasma etching a thin gold film. Until now most SERS active gold cluster covered surfaces have been prepared in several steps very often requiring complex lithography.

  19. Superlubricity of graphene nanoribbons on gold surfaces.

    PubMed

    Kawai, Shigeki; Benassi, Andrea; Gnecco, Enrico; Söde, Hajo; Pawlak, Rémy; Feng, Xinliang; Müllen, Klaus; Passerone, Daniele; Pignedoli, Carlo A; Ruffieux, Pascal; Fasel, Roman; Meyer, Ernst

    2016-02-26

    The state of vanishing friction known as superlubricity has important applications for energy saving and increasing the lifetime of devices. Superlubricity, as detected with atomic force microscopy, appears when sliding large graphite flakes or gold nanoclusters across surfaces, for example. However, the origin of the behavior is poorly understood because of the lack of a controllable nanocontact. We demonstrated the superlubricity of graphene nanoribbons when sliding on gold with a joint experimental and computational approach. The atomically well-defined contact allows us to trace the origin of superlubricity, unraveling the role played by ribbon size and elasticity, as well as by surface reconstruction. Our results pave the way to the scale-up of superlubricity and thus to the realization of frictionless coatings.

  20. Surface effects and gold-nanostructure surface coating of whispering-gallery microresonators

    NASA Astrophysics Data System (ADS)

    Ganta, Deepak

    Scope and method of study. The purpose of this study is to explore the surface effects of high-quality-factor optical microsphere resonators and thin-film-coated microresonators in various ambient gases. In this work, we present a systematic study of the assembly and characterization of gold nanostructures. We employ a wet-chemical synthesis method for growing gold nanorods and a directed electrochemical method for assembly of gold nanowires. The adhesion methods of gold nanostructures on high-quality-factor optical microsphere resonators are also investigated. Findings and conclusions. A novel method is employed for measuring thermal accommodation coefficients of various gases like nitrogen, helium and ambient air on several coated and uncoated surfaces of fused-silica microresonators, operating at room temperature. This method is further extended to measure the absorption coefficient of a surface film or water layer on a fused-silica microresonator, and provides a novel method to find the water layer desorption and adsorption rates on the surface of a microresonator in the presence of gases like ambient air and nitrogen. We have adapted methods for growing gold nanorods of different aspect ratios (AR), and developed a novel method of growing high-AR (20-400) gold nanowires from low-AR gold nanorods. Various methods were discovered to coat these gold nanostructures and carbon nanotubes on the fused-silica surface. The most successful method involves surface modification with MPMDMS (i.e., silanization) before coating with gold nanorods. These coating methods have made microresonators useful for plasmonic sensing applications.

  1. RAPID COMMUNICATION: Surface vertical deposition for gold nanoparticle film

    NASA Astrophysics Data System (ADS)

    Diao, J. J.; Qiu, F. S.; Chen, G. D.; Reeves, M. E.

    2003-02-01

    In this rapid communication, we present the surface vertical deposition (SVD) method to synthesize the gold nanoparticle films. Under conditions where the surface of the gold nanoparticle suspension descends slowly by evaporation, the gold nanoparticles in the solid-liquid-gas junction of the suspension aggregate together on the substrate by the force of solid and liquid interface. When the surface properties of the substrate and colloidal nanoparticle suspension define for the SVD, the density of gold nanoparticles in the thin film made by SVD only depends on the descending velocity of the suspension surface and on the concentration of the gold nanoparticle suspension.

  2. Unidirectional molecular motor on a gold surface

    NASA Astrophysics Data System (ADS)

    van Delden, Richard A.; Ter Wiel, Matthijs K. J.; Pollard, Michael M.; Vicario, Javier; Koumura, Nagatoshi; Feringa, Ben L.

    2005-10-01

    Molecules capable of mimicking the function of a wide range of mechanical devices have been fabricated, with motors that can induce mechanical movement attracting particular attention. Such molecular motors convert light or chemical energy into directional rotary or linear motion, and are usually prepared and operated in solution. But if they are to be used as nanomachines that can do useful work, it seems essential to construct systems that can function on a surface, like a recently reported linear artificial muscle. Surface-mounted rotors have been realized and limited directionality in their motion predicted. Here we demonstrate that a light-driven molecular motor capable of repetitive unidirectional rotation can be mounted on the surface of gold nanoparticles. The motor design uses a chiral helical alkene with an upper half that serves as a propeller and is connected through a carbon-carbon double bond (the rotation axis) to a lower half that serves as a stator. The stator carries two thiol-functionalized `legs', which then bind the entire motor molecule to a gold surface. NMR spectroscopy reveals that two photo-induced cis-trans isomerizations of the central double bond, each followed by a thermal helix inversion to prevent reverse rotation, induce a full and unidirectional 360° rotation of the propeller with respect to the surface-mounted lower half of the system.

  3. Radiotracer investigation in gold leaching tanks.

    PubMed

    Dagadu, C P K; Akaho, E H K; Danso, K A; Stegowski, Z; Furman, L

    2012-01-01

    Measurement and analysis of residence time distribution (RTD) is a classical method to investigate performance of chemical reactors. In the present investigation, the radioactive tracer technique was used to measure the RTD of aqueous phase in a series of gold leaching tanks at the Damang gold processing plant in Ghana. The objective of the investigation was to measure the effective volume of each tank and validate the design data after recent process intensification or revamping of the plant. I-131 was used as a radioactive tracer and was instantaneously injected into the feed stream of the first tank and monitored at the outlet of different tanks. Both sampling and online measurement methods were used to monitor the tracer concentration. The results of measurements indicated that both the methods provided identical RTD curves. The mean residence time (MRT) and effective volume of each tank was estimated. The tanks-in-series model with exchange between active and stagnant volume was used and found suitable to describe the flow structure of aqueous phase in the tanks. The estimated effective volume of the tanks and high degree of mixing in tanks could validate the design data and confirmed the expectation of the plant engineer after intensification of the process.

  4. Surface chemistry driven actuation in nanoporous gold

    SciTech Connect

    Biener, J; Wittstock, A; Zepeda-Ruiz, L; Biener, M M; Zielasek, V; Kramer, D; Viswanath, R N; Weissmuller, J; Baumer, M; Hamza, A V

    2008-04-14

    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 a mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.

  5. Physiological investigation of gold nanorods toward watermelon.

    PubMed

    Wan, Yujie; Li, Junli; Ren, Hongxuan; Huang, Jin; Yuan, Hong

    2014-08-01

    The objective of the present study was to evaluate the phytotoxicity and oxidant stress of the gold nanorods toward watermelon, and hence give a quantitative risk assessment of both seeds and plants phase. The seed germination, the activity of antioxidant enzymes, and the contents of soluble protein and malondialdehyde (MDA) have been measured while the plant roots were observed by transmission electron microscopy (TEM). It was found that the gold nanorods significantly promoted the root elongation. Furthermore, the results on the enzymes activities of plant indicated that oxidative stress happened in the plant treated with gold nanorods. However, the gold nanorods resulted in the phytotoxicity toward plant especially at high concentration. The TEM images of the plant roots with and without the treatment of gold nanorods showed the significant different size of starch granules. In conclusion, significant physiological changes of plant occurred after treatment with the gold nanorods.

  6. Ultrafast Imaging of Surface Plasmons Propagating on a Gold Surface

    SciTech Connect

    Gong, Yu; Joly, Alan G.; Hu, Dehong; El-Khoury, Patrick Z.; Hess, Wayne P.

    2015-05-13

    We record time-resolved nonlinear photoemission electron microscopy (tr-PEEM) images of propagating surface plasmons (PSPs) launched from a lithographically patterned rectangular trench on a flat gold surface. Our tr-PEEM scheme involves a pair of identical, spatially separated, and interferometrically-locked femtosecond laser pulses. Power dependent PEEM images provide experimental evidence for a sequential coherent nonlinear photoemission process, in which one laser source creates a PSP polarization state through a linear interaction, and the second subsequently probes the prepared state via two photon photoemission. The recorded time-resolved movies of a PSP allow us to directly measure various properties of the surface-bound wave packet, including its carrier wavelength (785 nm) and group velocity (0.95c). In addition, tr-PEEM in concert with finite-difference time domain simulations together allow us to set a lower limit of 75 μm for the decay length of the PSP on a 100 nm thick gold film.

  7. An electrochemical investigation of gold, tin and titanium compounds

    SciTech Connect

    Sawtelle, S.M.

    1992-01-01

    The determination of the electron transfer properties of gold, tin, and titanium compounds using electrochemical and spectroelectrochemical techniques is the focus of this dissertation. The investigations of the gold compounds include the determination of the properties of Au[PR[sub 3

  8. Atomically precise gold nanocrystal molecules with surface plasmon resonance.

    PubMed

    Qian, Huifeng; Zhu, Yan; Jin, Rongchao

    2012-01-17

    Since Faraday's pioneering work on gold colloids, tremendous scientific research on plasmonic gold nanoparticles has been carried out, but no atomically precise Au nanocrystals have been achieved. This work reports the first example of gold nanocrystal molecules. Mass spectrometry analysis has determined its formula to be Au(333)(SR)(79) (R = CH(2)CH(2)Ph). This magic sized nanocrystal molecule exhibits fcc-crystallinity and surface plasmon resonance at approximately 520 nm, hence, a metallic nanomolecule. Simulations have revealed that atomic shell closing largely contributes to the particular robustness of Au(333)(SR)(79), albeit the number of free electrons (i.e., 333 - 79 = 254) is also consistent with electron shell closing based on calculations using a confined free electron model. Guided by the atomic shell closing growth mode, we have also found the next larger size of extraordinarily stability to be Au(~530)(SR)(~100) after a size-focusing selection--which selects the robust size available in the starting polydisperse nanoparticles. This work clearly demonstrates that atomically precise nanocrystal molecules are achievable and that the factor of atomic shell closing contributes to their extraordinary stability compared to other sizes. Overall, this work opens up new opportunities for investigating many fundamental issues of nanocrystals, such as the formation of metallic state, and will have potential impact on condensed matter physics, nanochemistry, and catalysis as well.

  9. Use of cellulose derivatives on gold surfaces for reduced nonspecific adsorption of immunoglobulin G.

    PubMed

    Volden, Sondre; Zhu, Kaizheng; Nyström, Bo; Glomm, Wilhelm R

    2009-09-01

    This study addresses the design of protein-repellent gold surfaces using hydroxyethyl- and ethyl(hydroxyethyl) cellulose (HEC and EHEC) and hydrophobically modified analogues of these polymers (HM-HEC and HM-EHEC). Adsorption behavior of the protein immunoglobulin G (IgG) onto pure gold and gold surfaces coated with cellulose polymers was investigated and described by quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and contact angle measurements (CAM). Surfaces coated with the hydrophobically modified cellulose derivatives were found to significantly outperform a reference poly(ethylene glycol) (PEG) coating, which in turn prevented 90% of non-specific protein adsorption as compared to adsorption onto pure gold. HEC and EHEC prevented around 30% and 60% of the IgG adsorption observed on pure gold, while HM-HEC and HM-EHEC were both found to completely hinder biofouling when deposited on the gold substrates. Adsorption behavior of IgG has been discussed in terms of polymer surface coverage and roughness of the applied surfaces, together with hydrophobic interactions between protein and gold, and also polymer-protein interactions.

  10. Hot electron dynamics and impurity scattering on gold nanoshell surfaces

    NASA Astrophysics Data System (ADS)

    Wolfgang, John Adam

    2000-10-01

    Recent ultrafast pump-probe experiments studying the relaxation rate of an optically excited hot electron distribution on Au/Au2S gold nanoshells indicate that this relaxation rate can be modified by the chemical environment surrounding the shell. This work will begin a theoretical investigation of the effect of chemical adsorbates---solvents and impurities---upon nanoshell hot electron dynamics. The effects of water, polyvinyl alcohol (PVA), sulfur, p-aminobenzoic acid, p-mercaptobenzoic acid and propylamine adsorbates are examined for their electronic interaction with a noble metal surface. p-Aminobenzoic acid is found to have a very large dipole moment when adsorbed to the metal surface, in contrast to p-mercaptobenzoic acid, propylamine and water. This correlates well to the experimentally observed results where nanoshells dispersed in an aqueous soulution with p-aminobenzoic acid display a faster relaxation rate compared to nanoshells dispersed in a pure water, aqueous propylamine or aqueous p-mercaptobenzoic acid environments. This thesis will also introduce a non-equilibrium Green's function approach, based on the formalism developed by Baym and Kadanoff, to model the dynamics of a hot electron distribution. The model will be discussed in terms of a simple potential scattering mechanism, which may in later work be expanded to include more complex electron-electron and electron-phonon interactions. Lastly acoustic oscillation modes are calculated for solid gold spheres and gold-silicon nanoshells. These modes describe an effect of electron-phonon coupling between the hot electron distribution and the nanoshell lattice, whereby the electronic energy is converted into mechanical energy.

  11. Investigation of gold embrittlement in connector solder joints

    NASA Technical Reports Server (NTRS)

    Lane, F. L.

    1972-01-01

    An investigation was performed to determine to what extent typical flight connector solder joints may be embrittled by the presence of gold. In addition to mapping of gold content in connector solder joints by an electron microprobe analyzer, metallographic examinations and mechanical tests (thermal shock, vibration, impact and tensile strength) were also conducted. A description of the specimens and tests, a discussion of the data, and some conclusions are presented.

  12. Tailoring surface plasmon resonance and dipole cavity plasmon modes of scattering cross section spectra on the single solid-gold/gold-shell nanorod

    NASA Astrophysics Data System (ADS)

    Chou Chau, Yuan-Fong; Lim, Chee Ming; Lee, Chuanyo; Huang, Hung Ji; Lin, Chun-Ting; Kumara, N. T. R. N.; Yoong, Voo Nyuk; Chiang, Hai-Pang

    2016-09-01

    Tunable surface plasmon resonance (SPR) and dipole cavity plasmon modes of the scattering cross section (SCS) spectra on the single solid-gold/gold-shell nanorod have been numerically investigated by using the finite element method. Various effects, such as the influence of SCS spectra under x- and y-polarizations on the surface of the single solid-gold/gold-shell nanorod, are discussed in detail. With the single gold-shell nanorod, one can independently tune the relative SCS spectrum width by controlling the rod length and rod diameter, and the surface scattering by varying the shell thickness and polarization direction, as well as the dipole peak energy. These behaviors are consistent with the properties of localized SPRs and offer a way to optically control and produce selected emission wavelengths from the single solid-gold/gold-shell nanorod. The electric field and magnetic distributions provide us a qualitative idea of the geometrical properties of the single solid-gold/gold-shell nanorod on plasmon resonance.

  13. Influence of supported gold particles on the surface reactions of diethylamine on TiO2

    NASA Astrophysics Data System (ADS)

    Sarmiento-Lopez, Adan G.; Berumen-España, Gerardo; Lopez-Serrano, Cesar; Fierro-Gonzalez, Juan C.

    2016-11-01

    The adsorption and reactions of diethylamine on the surfaces of TiO2 and TiO2-supported gold samples were investigated by infrared (IR) spectroscopy and mass spectrometry. IR spectra measured as the samples were treated in flowing diethylamine at room temperature indicate that the amine was preferentially adsorbed molecularly on surface Ti4 + sites. Thermal treatment of the samples with flowing diethylamine led to the formation of ethylene and acetonitrile as dehydrogenation products. The data show that the reactions occurred at lower temperatures in the presence of supported gold samples than on TiO2, and IR spectra recorded under reaction conditions show evidence of amine-derived surface species bonded to gold nanoparticles that could be regarded as reaction intermediates. The results indicate that the gold nanoparticles provide sites for subtraction and recombination of hydrogen atoms from the amine, ensuing its dehydrogenation.

  14. Formation of Gold Microparticles by Ablation with Surface Plasmons

    PubMed Central

    Garner, Quincy; Molian, Pal

    2013-01-01

    The formation of gold microparticles on a silicon substrate through the use of energetic surface plasmons is reported. A laser-assisted plasmonics system was assembled and tested to synthesize gold particles from gold thin film by electrical field enhancement mechanism. A mask containing an array of 200 nm diameter holes with a periodicity of 400 nm was prepared and placed on a silicon substrate. The mask was composed of 60 µm thick porous alumina membrane sputter-coated with 100 nm thin gold film. A Nd:YAG laser with 1064 nm wavelength and 230 µs pulse width (free-running mode) was then passed through the mask at an energy fluence of 0.35 J/cm2. The extraordinary transmission of laser light through alumina/gold micro-hole optical antenna created both extended and localized surface plasmons that caused the gold film at the bottom of the mask to fragment into microparticles and deposit on the silicon substrate that is in direct contact with the mask. The surface plasmon method is simpler, quicker, more energy efficient, and environmentally safer than existing physical and chemical methods, as well as being contamination-free, and can be extended to all types of materials that will in turn allow for new possibilities in the formation of structured surfaces.

  15. Enhanced optical second harmonic generation in hybrid polymer nanoassemblies based on coupled surface plasmon resonance of a gold nanoparticle array

    NASA Astrophysics Data System (ADS)

    Ishifuji, Miki; Mitsuishi, Masaya; Miyashita, Tokuji

    2006-07-01

    Effective utilization of coupled surface plasmon resonance from gold nanoparticles was demonstrated experimentally for optoelectronic applications based on second-order nonlinear optics. Hybrid polymer nanoassemblies were constructed by manipulating gold nanoparticle arrays with nonlinear optical active polymer nanosheets to investigate the second harmonic generation. The gold nanoparticle arrays were assembled on heterodeposited polymer nanosheets. The second harmonic light intensity was enhanced by a factor of 8. The observed enhancement was attributed to coupling of surface plasmons between two adjacent gold nanoparticles, thereby enhancing the surface electromagnetic field around the nanoparticles at the fundamental light wavelength (1064nm).

  16. Triply surface-plasmon resonant four-wave mixing imaging of gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Masia, Francesco; Langbein, Wolfgang; Watson, Peter; Borri, Paola

    2011-03-01

    We have developed a novel multiphoton microscopy technique not relying on (and hence not limited by) fluorescence emission, which exploits the third-order nonlinearity called four-wave mixing of gold nanoparticles in resonance with their surface Plasmon. The coherent, transient and resonant nature of this signal allows its detection free from backgrounds that limit other contrast methods for gold nanoparticles. We show detection of single 10nm gold nanoparticles with low excitation intensities, corresponding to negligible average thermal heating. Owing to the the third-order nonlinearity we measure a transversal and axial resolution of 140nm and 470nm respectively, better than the one-photon diffraction limit. We also show high-contrast imaging of gold-labels down to 5nm size in Golgi structures of HepG2 cells at useful imaging speeds (10 kHz pixel rate). Thermal dissociation of gold nanoparticles from their bonding sites when varying the excitation intensity is also investigated.

  17. Electrical bending actuation of gold-films with nanotextured surfaces

    NASA Astrophysics Data System (ADS)

    Kwan, K. W.; Gao, P.; Martin, C. R.; Ngan, A. H. W.

    2015-01-01

    An actuating material system comprising a gold-film with nanotextured surface was fabricated. Using electroless gold plating onto a substrate of porous anodized aluminum oxide, a thin film of gold with a high density of short gold nanofibers on its surface was made. When one end of such a film was connected to an ion generator, bending was achieved upon electrical charging in air. Experiments showed that the free end of an 8 mm film could be displaced by more than 1.6 mm with a bending strain of 0.08%. In contrast with other types of thin-film artificial muscle materials, the present Au-film did not require any electrolyte to function. With the relatively easy fabrication method, this nanotextured film shows promising actuation behavior in air.

  18. Impedimetric investigation of gold nanoparticles - guanine modified electrode

    SciTech Connect

    Vulcu, A.; Pruneanu, S.; Berghian-Grosan, C.; Olenic, L.; Muresan, L. M.; Barbu-Tudoran, L.

    2013-11-13

    In this paper we report the preparation of a modified electrode with gold nanoparticles and guanine. The colloidal suspension of gold nanoparticles was obtained by Turkevich method and was next analyzed by UV-Vis spectroscopy and Transmission Electron Microscopy (TEM). The gold electrode was modified by self-assembling the gold nanoparticles with guanine, the organic molecule playing also the role of linker. The electrochemical characteristics of the bare and modified electrode were investigated by Electrochemical Impedance Spectroscopy (EIS). A theoretical model was developed based on an electrical equivalent circuit which contain solution resistance (R{sub s}), charge transfer resistance (R{sub ct}), Warburg impedance (Z{sub W}) and double layer capacitance (C{sub dl})

  19. Mercury adsorption to gold nanoparticle and thin film surfaces

    NASA Astrophysics Data System (ADS)

    Morris, Todd Ashley

    Mercury adsorption to gold nanoparticle and thin film surfaces was monitored by spectroscopic techniques. Adsorption of elemental mercury to colloidal gold nanoparticles causes a color change from wine-red to orange that was quantified by UV-Vis absorption spectroscopy. The wavelength of the surface plasmon mode of 5, 12, and 31 nm gold particles blue-shifts 17, 14, and 7.5 nm, respectively, after a saturation exposure of mercury vapor. Colorimetric detection of inorganic mercury was demonstrated by employing 2.5 nm gold nanoparticles. The addition of low microgram quantities of Hg 2+ to these nanoparticles induces a color change from yellow to peach or blue. It is postulated that Hg2+ is reduced to elemental mercury by SCN- before and/or during adsorption to the nanoparticle surface. It has been demonstrated that surface plasmon resonance spectroscopy (SPRS) is sensitive to mercury adsorption to gold and silver surfaces. By monitoring the maximum change in reflectivity as a function of amount of mercury adsorbed to the surface, 50 nm Ag films were shown to be 2--3 times more sensitive than 50 nm Au films and bimetallic 15 nm Au/35 nm Ag films. In addition, a surface coverage of ˜40 ng Hg/cm2 on the gold surface results in a 0.03° decrease in the SPR angle of minimum reflectivity. SPRS was employed to follow Hg exposure to self-assembled monolayers (SAMs) on Au. The data indicate that the hydrophilic or hydrophobic character of the SAM has a significant effect on the efficiency of Hg penetration. Water adsorbed to carboxylic acid end group of the hydrophilic SAMs is believed to slow the penetration of Hg compared to methyl terminated SAMs. Finally, two protocols were followed to remove mercury from gold films: immersion in concentrated nitric acid and thermal annealing up to 200°C. The latter protocol is preferred because it removes all of the adsorbed mercury from the gold surface and does not affect the morphology of the gold surface.

  20. Growth of pentacene on clean and modified gold surfaces

    SciTech Connect

    Kaefer, Daniel; Ruppel, Lars; Witte, Gregor

    2007-02-15

    The growth and evolution of pentacene films on gold substrates have been studied. By combining complementary techniques including scanning tunneling microscopy, atomic force microscopy, scanning electron microscopy, near-edge x-ray-absorption fine structure, and x-ray diffraction, the molecular orientation, crystalline structure, and morphology of the organic films were characterized as a function of film thickness and growth parameters (temperature and rate) for different gold substrates ranging from Au(111) single crystals to polycrystalline gold. Moreover, the influence of precoating the various gold substrates with self-assembled monolayers (SAM's) of organothiols with different chemical terminations has been studied. On bare gold the growth of pentacene films is characterized by a pronounced dewetting while the molecular orientation within the resulting crystalline three-dimensional islands depends distinctly on the roughness and cleanliness of the substrate surface. After completion of the first wetting layer where molecules adopt a planar orientation parallel to the surface the molecules continue to grow in a tilted fashion: on Au(111) the long molecular axis is oriented parallel to the surface while on polycrystalline gold it is upstanding oriented and thus parallels the crystalline orientation of pentacene films grown on SiO{sub 2}. On SAM pretreated gold substrates the formation of a wetting layer is effectively suppressed and pentacene grows in a quasi-layer-by-layer fashion with an upstanding orientation leading to rather smooth films. The latter growth mode is observed independently of the chemical termination of the SAM's and the roughness of the gold substrate. Possible reasons for the different growth mechanism as well as consequences for the assignment of spectroscopic data of thin pentacene film are discussed.

  1. Synthesis and tuning of gold nanorods with surface plasmon resonance

    NASA Astrophysics Data System (ADS)

    Shajari, Daryush; Bahari, Ali; Gill, Pooria; Mohseni, Mojtaba

    2017-02-01

    Gold nanostructures in general and gold nanorods in particular due to their plasmon resonance has been employed for many applications, such as biosensors. For the biosensors uses, gold nanorods remain popular and reproducibility of them is the most important and critical. In the present work we used six different CTAB (Hexadecyltrimethylammonium bromide) products and one BDAC (Benzyldimethylhexadecylammonium chloride) with varying silver nitrate concentration in the seed-mediated growth of gold nanostructures. We synthesized gold nanorods with varying aspect ratio up to 5.5 with a longitudinal surface plasmon resonance peak from 670 to 950 nm. We obtained excellent rod-shape gold nanostructures witch were reliable and reproducible with our method based on common seed-mediated growth. The synthesized nanostructures were characterized by UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD). Here, we report our method in more detail as a user-friendly guide for the production of gold nanorods and tuning of their aspect ratios.

  2. Directional surface enhanced Raman scattering on gold nano-gratings

    NASA Astrophysics Data System (ADS)

    Gillibert, Raymond; Sarkar, Mitradeep; Bryche, Jean-François; Yasukuni, Ryohei; Moreau, Julien; Besbes, Mondher; Barbillon, Grégory; Bartenlian, Bernard; Canva, Michael; Lamy de la Chapelle, Marc

    2016-03-01

    Directional plasmon excitation and surface enhanced Raman scattering (SERS) emission were demonstrated for 1D and 2D gold nanostructure arrays deposited on a flat gold layer. The extinction spectrum of both arrays exhibits intense resonance bands that are redshifted when the incident angle is increased. Systematic extinction analysis of different grating periods revealed that this band can be assigned to a propagated surface plasmon of the flat gold surface that fulfills the Bragg condition of the arrays (Bragg mode). Directional SERS measurements demonstrated that the SERS intensity can be improved by one order of magnitude when the Bragg mode positions are matched with either the excitation or the Raman wavelengths. Hybridized numerical calculations with the finite element method and Fourier modal method also proved the presence of the Bragg mode plasmon and illustrated that the enhanced electric field of the Bragg mode is particularly localized on the nanostructures regardless of their size.

  3. Selective electrochemical gold deposition onto p-Si (1 0 0) surfaces

    NASA Astrophysics Data System (ADS)

    Santinacci, L.; Djenizian, T.; Schwaller, P.; Suter, T.; Etcheberry, A.; Schmuki, P.

    2008-09-01

    In this paper, we report selective electrochemical gold deposition onto p-type Si (1 0 0) into nanoscratches produced through a thin oxide layer using an atomic force microscope. A detailed description of the substrate engraving process is presented. The influence of the main scratching parameters such as the normal applied force, the number of scans and the scanning velocity are investigated as well as the mechanical properties of the substrate. Gold deposition is carried out in a KAu(CN)2 + KCN solution by applying cathodic voltages for various durations. The gold deposition process is investigated by cyclic voltammetry. Reactivity enhancement at the scratched locations was studied by comparing the electrochemical behaviour of intact and engraved surfaces using a micro-electrochemical setup. Selective electrochemical gold deposition is achieved: metallic patterns with a sub-500 nm lateral resolution are obtained demonstrating, therefore, the bearing potential of this patterning technique.

  4. Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

    PubMed

    Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

    2014-05-20

    Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

  5. Surface characterization of immunosensor conjugated with gold nanoparticles based on cyclic voltammetry and X-ray photoelectron spectroscopy.

    PubMed

    Lai, Lee-Jene; Yang, Yaw-Wen; Lin, Yao-Kwang; Huang, Li-Ling; Hsieh, Yi-Heui

    2009-02-01

    This investigation describes the surface characterization of rabbit immunoglobulin G (IgG) conjugated with gold nanoparticles. Goat anti-rabbit immunoglobulin G tagged with 5nm gold nanoparticles was applied to detect the IgG. Then, the autocatalyzed deposition of Au(3+) onto the surface of anti-IgGAu increased the surface area per gold nanoparticle. The immobilization chemistries and the atomic concentrations of Au(4f), P(2p), S(2p), C(1s), N(1s) and O(1s) of the resulting antibody-modified Au electrodes were determined by X-ray photoelectron spectroscopy (XPS). The sulfur that is involved in the cysteamine binding and the enlargement of the gold nanoparticles are identified using cyclic voltammetry. The results reveal that the surface area per gold particle, following the autocatalyzed deposition Au(3+) on the surface of anti-IgGAu, was approximately seven times higher than that before deposition.

  6. Organometallic Chemistry and catalysis on gold metal surfaces

    SciTech Connect

    Angelici, Robert J.

    2007-11-21

    As in transition metal complexes, C{triple_bond}N-R ligands adsorbed on powdered gold undergo attack by amines to give putative diaminocarbene groups on the gold surface. This reaction forms the basis for the discovery of a gold metal-catalyzed reaction of C{triple_bond}N-R, primary amines (R{prime}NH{sub 2}) and O{sub 2} to give carbodiimides (R{prime}-N{double_bond}C{double_bond}N-R). An analogous reaction of C{triple_bond}O, RNH{sub 2}, and O{sub 2} gives isocyanates (R-N{double_bond}C{double_bond}O), which react with additional amine to give urea (RNH){sub 2}C{double_bond}O products. The gold-catalyzed reaction of C{triple_bond}N-R with secondary amines (HNR{prime}{sub 2}) and O{sub 2} gives mixed ureas RNH(CO)NR{prime}{sub 2}. In another type of gold-catalyzed reaction, secondary amines HN(CH{sub 2}R){sub 2} react with O{sub 2} to undergo dehydrogenation to the imine product, RCH{double_bond}N(CH{sub 2}R). Of special interest is the high catalytic activity of gold powder, which is otherwise well-known for its poor catalytic properties.

  7. Charge retention by gold clusters on surfaces prepared using soft landing of mass selected ions.

    PubMed

    Johnson, Grant E; Priest, Thomas; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas phase, and mass selection was employed to isolate a single ionic cluster species (Au(11)L(5)(3+), L = 1,3-bis(diphenylphosphino)propane), which was delivered to surfaces at well-controlled kinetic energies. Using in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS), it is demonstrated that the Au(11)L(5)(3+) cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-perfluorodecanethiol self-assembled monolayer (FSAM) on gold. In contrast, when deposited onto 16-mercaptohexadecanoic acid (COOH-SAM) and 1-dodecanethiol (HSAM) surfaces on gold, the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the FSAM and HSAM surfaces are investigated using in situ Fourier transform ion cyclotron resonance (FT-ICR) SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the FSAM surface while an almost instantaneous neutralization takes place on the surface of the HSAM. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto carefully selected substrates.

  8. Analytical performance of molecular beacons on surface immobilized gold nanoparticles of varying size and density.

    PubMed

    Uddayasankar, Uvaraj; Krull, Ulrich J

    2013-11-25

    The high quenching efficiency of metal nanoparticles has facilitated its use as quenchers in molecular beacons. To optimize this system, a good understanding of the many factors that influence molecular beacon performance is required. In this study, molecular beacon performance was evaluated as a function of gold nanoparticle size and its immobilization characteristics. Gold nanoparticles of 4 nm, 15 nm and 87 nm diameter, were immobilized onto glass slides. Each size regime offered distinctive optical properties for fluorescence quenching of molecular dyes that were conjugated to oligonucleotides that were immobilized to the gold nanoparticles. Rigid double stranded DNA was used as a model to place fluorophores at different distances from the gold nanoparticles. The effect of particle size and also the immobilization density of nanoparticles was evaluated. The 4 nm and 87 nm gold nanoparticles offered the highest sensitivity in terms of the change in fluorescence intensity as a function of distance (3-fold improvement for Cy5). The optical properties of the molecular fluorophore was of significance, with Cy5 offering higher contrast ratios than Cy3 due to the red-shifted emission spectrum relative to the plasmon peak. A high density of gold nanoparticles reduced contrast ratios, indicating preference for a monolayer of immobilized nanoparticles when considering analytical performance. Molecular beacon probes were then used in place of the double stranded oligonucleotides. There was a strong dependence of molecular beacon performance on the length of a linker used for attachment to the nanoparticle surface. The optimal optical performance was obtained with 4 nm gold nanoparticles that were immobilized as monolayers of low density (5.7×10(11)particles cm(-2)) on glass surfaces. These nanoparticle surfaces offered a 2-fold improvement in analytical performance of the molecular beacons when compared to other nanoparticle sizes investigated. The principles developed

  9. Surface Nucleation in the Freezing of Gold Nanoparticles

    NASA Astrophysics Data System (ADS)

    Mendez-Villuendas, Eduardo; Bowles, Richard K.

    2007-05-01

    We use molecular simulation to calculate the nucleation free energy barrier for the freezing of a 456 atom gold cluster over a range of temperatures. The results show that the embryo of the solid cluster grows at the vapor-surface interface for all temperatures studied and that the usual classical nucleation model, with the embryo growing in the core of the cluster, is unable to predict the shape of the free energy barrier. We use a simple partial wetting model that treats the crystal as a lens-shaped nucleus at the liquid-vapor interface and find that the line tension plays an important role in the freezing of gold nanoparticles.

  10. Shape and surface effects on the cytotoxicity of nanoparticles: Gold nanospheres versus gold nanostars.

    PubMed

    Favi, Pelagie Marlene; Gao, Ming; Johana Sepúlveda Arango, Liuda; Ospina, Sandra Patricia; Morales, Mariana; Pavon, Juan Jose; Webster, Thomas Jay

    2015-11-01

    Gold nanoparticles are materials with unique optical properties that have made them very attractive for numerous biomedical applications. With the increasing discovery of techniques to synthesize novel nanoparticles such as star-shaped gold nanoparticles for biomedical applications, the safety and performance of these new nanomaterials must be systematically assessed before use. In this study, gold nanostars (AuNSTs) with multibranched surface structures were synthesized, and their influence on the cytotoxicity of human skin fibroblasts and rat fat pad endothelial cells (RFPECs) were assessed and compared with that of gold nanospheres (AuNSPs) with unbranched surfaces. Results showed that the AuNSPs with diameters of approximately 61.46 nm showed greater toxicity with fibroblast cells and RFPECs compared with the synthesized AuNSTs with diameters of approximately 33.69 nm. The AuNSPs were lethal at concentrations of 40 μg/mL for both cell lines, whereas the AuNSTs were less toxic at higher concentrations (400 μg/mL). The calculated IC50 (50% inhibitory concentration) values of the AuNSPs exposed to fibroblast cells were greater at 1 and 4 days of culture (26.4 and 27.7 μg/mL, respectively) compared with the RFPECs (13.6 and 13.8 μg/mL, respectively), indicating that the AuNSPs have a greater toxicity to endothelial cells. It was proposed that possible factors that could be promoting the reduced toxicity effects of the AuNSTs to fibroblast cells and RFPECs, compared with the AuNSPs may be size, surface chemistry, and shape of the gold nanoparticles. The reduced cell toxicity observed with the AuNSTs suggests that AuNSTs may be a promising material for use in biomedical applications.

  11. Microscale Heat Transfer Transduced by Surface Plasmon Resonant Gold Nanoparticles

    PubMed Central

    Roper, D. Keith; Ahn, W.; Hoepfner, M.

    2008-01-01

    Visible radiation at resonant frequencies is transduced to thermal energy by surface plasmons on gold nanoparticles. Temperature in ≤10-microliter aqueous suspensions of 20-nanometer gold particles irradiated by a continuous wave Ar+ ion laser at 514 nm increased to a maximum equilibrium value. This value increased in proportion to incident laser power and in proportion to nanoparticle content at low concentration. Heat input to the system by nanoparticle transduction of resonant irradiation equaled heat flux outward by conduction and radiation at thermal equilibrium. The efficiency of transducing incident resonant light to heat by microvolume suspensions of gold nanoparticles was determined by applying an energy balance to obtain a microscale heat-transfer time constant from the transient temperature profile. Measured values of transduction efficiency were increased from 3.4% to 9.9% by modulating the incident continuous wave irradiation. PMID:19011696

  12. Adsorption of cellulose derivatives on flat gold surfaces and on spherical gold particles.

    PubMed

    Amirkhani, Masoud; Volden, Sondre; Zhu, Kaizheng; Glomm, Wilhelm R; Nyström, Bo

    2008-12-01

    The adsorption of hydroxyethylcellulose (HEC), ethyl(hydroxyethyl)cellulose (EHEC), and their hydrophobically modified counterparts HM-HEC and HM-EHEC has been studied on planar gold and citrate-covered gold surfaces by means of quartz crystal microbalance with dissipation monitoring (QCM-D), and on citrate-covered gold particles with the aid of dynamic light scattering (DLS). The QCM-D results indicate that larger amounts of polymer are adsorbed from aqueous solutions of HM-HEC and HM-EHEC on both substrates than from solutions of their unmodified analogues. The adsorption affinity for all the polymers, except EHEC, is higher on the citrate-covered surfaces than on the bare gold substrate. This indicates that more adsorption sites are activated in the presence of the citrate layer. The experimental adsorption data for all the polymers can be described fairly well by the Langmuir adsorption isotherm. However, at very low polymer concentrations significant deviations from the model are observed. The value of the hydrodynamic thickness of the adsorbed polymer layer (delta h), determined from DLS, rises with increasing polymer concentration for all the cellulose derivatives; a Langmuir type of isotherm can be used to roughly describe the adsorption behavior. Because of good solvent conditions for HEC the chains extend far out in the bulk at higher concentrations and the value of delta h is much higher than that of HM-HEC. The adsorption of EHEC and HM-EHEC onto gold particles discloses that the values of delta h are considerably higher for the hydrophobically modified cellulose derivative, and this finding is compatible with the trend in layer thickness estimated from the QCM-D measurements.

  13. Optical and electrochemical properties of ordered macroporous gold array on the ITO surface

    NASA Astrophysics Data System (ADS)

    Lu, Huidan; Liu, Yongping; Han, Guo-Cheng

    2011-06-01

    The electrochemical and optical properties of transparent, two-dimensional macroporous gold film were investigated. Colloidal crystal templates were assembled onto indium-doped tin oxide (ITO) glass surface through vertical depositing method. Following gold electrodeposition, they were removed by dissolution with tetrahydrofuran (THF). The highly ordered macroporous gold array was achieved. It was characterized by scanning electron microscope (SEM) and ultraviolet visible (UV-vis) spectrophotometry. The optical transparency of the gold film was near 25% and fairly constant between 300 and 900 nm. The macroporous gold film electrode was mounted into a thin-layer transmission cell. The electrochemical response was evaluated by thin-layer cyclic voltammograms (CV) of the Fe (CN) 63-/Fe (CN) 64- couple. Thin-layer cell exhibits good shape of waves and nearly symmetric cathodic and anodic waves. E0' value and n of TMPD + rad /TMPD (TMPD is acronyms for N,N,N',N'-tetramethyl-p-phenylenediamine, and TMPD + rad is its mono-cation radical) couple were determined. Furthermore, results demonstrated electrolytic equilibrium was faster reached in macroporous gold film than ITO electrode.

  14. Tuning the surface enhanced Raman scattering activity of gold nanocubes by silver coating

    NASA Astrophysics Data System (ADS)

    Ding, Shu-Jun; Zhu, Jian

    2015-12-01

    Colloidal gold nanocubes coated with a silver nanoshell have been synthesized via the seed mediated growth method. By changing the volume of gold seed and silver nitrate, both the edge length of gold nanocube and the thickness of silver shell could be fine-tuned. The surface-enhanced Raman scattering (SERS) activity of these core-shell structural Au-Ag bimetallic nanocubes has also been investigated by using the rhodamine 6G (R6G) as Raman active probe. It has been found the SERS activity of the silver-coated gold nanocubes greatly depends on their geometry factors. By decreasing the edge length of gold nanocubes or increasing the silver coating thickness, the SERS activity has been greatly enhanced. By comparing with other Raman bands of R6G, the enhancement of the Raman peak corresponding to the Csbnd Csbnd C ring in-plane vibration mode is more sensitive to the geometries of the nanostructure. These improved SERS properties of silver-coated gold nanocubes provide potential application for biologic and chemical sensing based on Raman spectroanalysis.

  15. Surface Plasmon-Driven Water Reduction: Gold Nanoparticle Size Matters

    SciTech Connect

    Qian, Kun; Sweeny, Brendan C.; Johnston-Peck, Aaron C.; Niu, Wenxin; Graham, Jeremy O.; DuChene, Joseph S.; Qiu, Jingjing; Wang, Yi-Chung; Engelhard, Mark H.; Su, Dong; Stach, Eric A.; Wei, Wei

    2014-07-16

    Water reduction under two visible light ranges (λ > 400 and λ > 435 nm) was investigated using gold-loaded titanium dioxide (Au-TiO2) with different sizes of Au nanoparticles (NPs). Two different mechanisms have been determined to clarify the specific role of Au NPs in visible light-induced photocatalytic reactions. Our study provides solid evidences showing that Au NPs sizes are essential for the surface plasmon-driven water reduction under λ > 435 nm. More specifically, we have demonstrated that the Au NPs sizes are vital for the SPR mediated electron transfer efficiency and play a critical role in determining the reduction potential of the transferred electrons in the TiO2 conduction band (CB) and their following activities. Our discovery provides a facile way to manipulate the reduction potential of transferred electrons by simply varying the Au NPs sizes, which will greatly facilitate the design of suitable plasmonic photocatalysts for water reduction and other valuable solar-to-fuel reactions.

  16. Surface charge of gold nanoparticles mediates mechanism of toxicity

    NASA Astrophysics Data System (ADS)

    Schaeublin, Nicole M.; Braydich-Stolle, Laura K.; Schrand, Amanda M.; Miller, John M.; Hutchison, Jim; Schlager, John J.; Hussain, Saber M.

    2011-02-01

    Recently gold nanoparticles (Au NPs) have shown promising biological and military applications due to their unique electronic and optical properties. However, little is known about their biocompatibility in the event that they come into contact with a biological system. In the present study, we have investigated whether modulating the surface charge of 1.5 nm Au NPs induced changes in cellular morphology, mitochondrial function, mitochondrial membrane potential (MMP), intracellular calcium levels, DNA damage-related gene expression, and of p53 and caspase-3 expression levels after exposure in a human keratinocyte cell line (HaCaT). The evaluation of three different Au NPs (positively charged, neutral, and negatively charged) showed that cell morphology was disrupted by all three NPs and that they demonstrated a dose-dependent toxicity; the charged Au NPs displayed toxicity as low as 10 µg ml-1 and the neutral at 25 µg ml-1. Furthermore, there was significant mitochondrial stress (decreases in MMP and intracellular Ca2+ levels) following exposure to the charged Au NPs, but not the neutral Au NPs. In addition to the differences observed in the MMP and Ca2+ levels, up or down regulation of DNA damage related gene expression suggested a differential cell death mechanism based on whether or not the Au NPs were charged or neutral. Additionally, increased nuclear localization of p53 and caspase-3 expression was observed in cells exposed to the charged Au NPs, while the neutral Au NPs caused an increase in both nuclear and cytoplasmic p53 expression. In conclusion, these results indicate that surface charge is a major determinant of how Au NPs impact cellular processes, with the charged NPs inducing cell death through apoptosis and neutral NPs leading to necrosis.Recently gold nanoparticles (Au NPs) have shown promising biological and military applications due to their unique electronic and optical properties. However, little is known about their biocompatibility in the

  17. Adsorption of vapreotide on gold colloids studied by surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Gómez, J. A.; Cabanzo, R.; Mejia Ospino, E.

    2016-02-01

    Surface Enhanced Raman Spectroscopy (SERS) has been used to investigate the somatostatin (SST) analogue Vapreotide (VAP) in gold colloids. The optimum conditions to detect SERS signals of VAP have been studied. The observed SERS bands correspond to different vibrational modes of the peptide; being the most dominant SERS signals the ones derived from the aromatic amino acids Tryptophan (Trp), Phenylalanine (Phe) and Tyrosine (Tyr). Changes in enhancement and wavenumber of the proper bands upon adsorption on gold colloid are consistent with VAP adsorption, primarily through Tryptophan residues.

  18. Investigation of nanogap localized field enhancement in gold plasmonic structures

    NASA Astrophysics Data System (ADS)

    Debu, Desalegn Tadesse; Bauman, Stephen; Saylor, Cameron; Novak, Eric; French, David; Herzog, Joseph

    2015-03-01

    Nanogaps between plasmonic structures allow confining the localized electric field with moreenhancements. Based on previously implemented two-step lithography process, we introducea nano-masking technique to fabricate nanostructrues and nanogaps for various geometrical patterns. This new method can fabricate gold nanostructures as well as nanogaps that are less than 10nm, below the limiting scale of lithography. Simulation from finite element method (FEM) shows strong gap dependence of optical properties and peak enhancement of these devices. The fabricated plasmonic nanostructure provides wide range of potential future application including highly sensitive optical antenna, surface enhanced Raman spectroscopy and biosensing.

  19. Surface-enhanced Raman spectroscopy on laser-engineered ruthenium dye-functionalized nanoporous gold

    NASA Astrophysics Data System (ADS)

    Schade, Lina; Franzka, Steffen; Biener, Monika; Biener, Jürgen; Hartmann, Nils

    2016-06-01

    Photothermal processing of nanoporous gold with a microfocused continuous-wave laser at λ = 532 nm provides a facile means in order engineer the pore and ligament size of nanoporous gold. In this report we take advantage of this approach in order to investigate the size-dependence of enhancement effects in surface-enhanced Raman spectroscopy (SERS). Surface structures with laterally varying pore sizes from 25 nm to ≥200 nm are characterized using scanning electron microscopy and then functionalized with N719, a commercial ruthenium complex, which is widely used in dye-sensitized solar cells. Raman spectroscopy reveals the characteristic spectral features of N719. Peak intensities strongly depend on the pore size. Highest intensities are observed on the native support, i.e. on nanoporous gold with pore sizes around 25 nm. These results demonstrate the particular perspectives of laser-fabricated nanoporous gold structures in fundamental SERS studies. In particular, it is emphasized that laser-engineered porous gold substrates represent a very well defined platform in order to study size-dependent effects with high reproducibility and precision and resolve conflicting results in previous studies.

  20. Cytochrome c dynamics at gold and glassy carbon surfaces monitored by in situ scanning tunnel microscopy

    NASA Astrophysics Data System (ADS)

    Andersen, Jens E. T.; Møller, Per; Pedersen, Marianne V.; Ulstrup, Jens

    1995-02-01

    We have investigated the absorption of cytochrome c on gold and glassy carbon substrates by in situ scanning tunnel microscopy under potentiostatic control of both substrate and tip. Low ionic strength and potential ranges where no Faradaic current flows were used. Cyt c aggregates into flat composite structures of about 50 nm lateral extension at gold surfaces. The aggregates evolve in time, and structures resembling individual cyt c molecules can be distinguished in the space between the 50 nm structures. Cyt c aggregates also form at glassy carbon but have a different, unbroken character where cyt c both sticks well to the surface and exhibits notable mobility. The observations suggest that characteristic surface specific, internally mobile protein aggregates are formed at both surfaces and that in situ molecular resolution of the STM pictures may have been achieved.

  1. Toward spatial control of gold nanorod surface functionalization

    NASA Astrophysics Data System (ADS)

    Eller, Jonathan R.

    Gold nanorods (GNRs) show much promise for applications in biological, optoelectronic and energy applications. The resonant generation of a localized surface plasmon resonance (LSPR) at the GNR surface results in interesting optical properties and unique interactions with molecules. Combined with their biocompatibility, ease of synthesis and facile surface functionalization, these anisotropic metal particles are excellent scaffolds for the study of the interactions between nanoscale surfaces and their chemical/biological environments. Regardless of the application, however, GNR utility will not be fully realized until the chemical nature of the surface is understood and controlled. GNRs can enhance various photophysical properties of molecules. In the case of two-photon absorption (TPA), cross-section enhancements have been shown to increase with strong distance-dependence. Here, a dual approach for the conjugation of a TPA chromophore to GNRs is presented, relying on layer-by- layer (LbL) polymer wrapping and direct thiol coating of the same parent chromophore structure. Together, these approaches allow for estimated chromophore-particle distances from <1nm to more than 15 nm. Composites were confirmed using conventional nanoparticle characterization methods. Imaging of GNR polymer shells indicated anisotropic composite structures, as confirmed by both conventional and cryo-TEM. Optical characterizations were performed using two-photon excited fluorescence and Z-scan techniques, to probe the TPA enhancement. The intrinsic nonlinear optical properties of GNRs is shown to contribute strongly to these measurements, suggesting the utility of these materials for bi-modal imaging platforms. GNR properties, like their shape, are anisotropic. The LSPR-induced near- fields are heterogeneously distributed on the nanorod surface, with the tips being much "hotter" than the sides. To understand and utilize fully the spatially- dependent interactions of GNRs with their

  2. Femtosecond nonlinear ultrasonics in gold probed with ultrashort surface plasmons.

    PubMed

    Temnov, Vasily V; Klieber, Christoph; Nelson, Keith A; Thomay, Tim; Knittel, Vanessa; Leitenstorfer, Alfred; Makarov, Denys; Albrecht, Manfred; Bratschitsch, Rudolf

    2013-01-01

    Fundamental interactions induced by lattice vibrations on ultrafast time scales have become increasingly important for modern nanoscience and technology. Experimental access to the physical properties of acoustic phonons in the terahertz-frequency range and over the entire Brillouin zone is crucial for understanding electric and thermal transport in solids and their compounds. Here we report on the generation and nonlinear propagation of giant (1 per cent) acoustic strain pulses in hybrid gold/cobalt bilayer structures probed with ultrafast surface plasmon interferometry. This new technique allows for unambiguous characterization of arbitrary ultrafast acoustic transients. The giant acoustic pulses experience substantial nonlinear reshaping after a propagation distance of only 100 nm in a crystalline gold layer. Excellent agreement with the Korteveg-de Vries model points to future quantitative nonlinear femtosecond terahertz-ultrasonics at the nano-scale in metals at room temperature.

  3. Fabrication of Localized Surface Plasmon Resonance Fiber Probes Using Ionic Self-Assembled Gold Nanoparticles

    PubMed Central

    Wan, Miao; Luo, Pengfei; Jin, Jiayi; Xing, Jiong; Wang, Zhiyong; Wong, Stephen T. C.

    2010-01-01

    An nm-thickness composite gold thin film consisting of gold nanoparticles and polyelectrolytes is fabricated through ionic self-assembled multilayers (ISAM) technique and is deposited on end-faces of optical fibers to construct localized surface plasmon resonance (LSPR) fiber probes. We demonstrate that the LSPR spectrum induced by ISAM gold films can be fine-tuned through the ISAM procedure. We investigate variations of reflection spectra of the probe with respect to the layer-by-layer adsorption of ISAMs onto end-faces of fibers, and study the spectral variation mechanism. Finally, we demonstrated using this fiber probe to detect the biotin-streptavidin bioconjugate pair. ISAM adsorbed on optical fibers potentially provides a simple, fast, robust, and low-cost, platform for LSPR biosensing applications. PMID:22163561

  4. Effect of Gold on the Corrosion Behavior of an Electroless Nickel/Immersion Gold Surface Finish

    NASA Astrophysics Data System (ADS)

    Bui, Q. V.; Nam, N. D.; Yoon, J. W.; Choi, D. H.; Kar, A.; Kim, J. G.; Jung, S. B.

    2011-09-01

    The performance of surface finishes as a function of the pH of the utilized plating solution was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5 wt.% NaCl solution. In addition, the surface finishes were examined by x-ray diffraction (XRD), and the contact angle of the liquid/solid interface was recorded. NiP films on copper substrates with gold coatings exhibited their highest coating performance at pH 5. This was attributed to the films having the highest protective efficiency and charge transfer resistance, lowest porosity value, and highest contact angle among those examined as a result of the strongly preferred Au(111) orientation and the improved surface wettability.

  5. Gold

    USGS Publications Warehouse

    Kirkemo, Harold; Newman, William L.; Ashley, Roger P.

    1998-01-01

    Through the ages, men and women have cherished gold, and many have had a compelling desire to amass great quantities of it -- so compelling a desire, in fact, that the frantic need to seek and hoard gold has been aptly named "gold fever." Gold was among the first metals to be mined because it commonly occurs in its native form -- that is, not combined with other elements -- because it is beautiful and imperishable, and because exquisite objects can be made from it.

  6. Sulfur-induced structural motifs on copper and gold surfaces

    SciTech Connect

    Walen, Holly

    2016-01-01

    The interaction of sulfur with copper and gold surfaces plays a fundamental role in important phenomena that include coarsening of surface nanostructures, and self-assembly of alkanethiols. Here, we identify and analyze unique sulfur-induced structural motifs observed on the low-index surfaces of these two metals. We seek out these structures in an effort to better understand the fundamental interactions between these metals and sulfur that lends to the stability and favorability of metal-sulfur complexes vs. chemisorbed atomic sulfur. The experimental observations presented here—made under identical conditions—together with extensive DFT analyses, allow comparisons and insights into factors that favor the existence of metal-sulfur complexes, vs. chemisorbed atomic sulfur, on metal terraces. We believe this data will be instrumental in better understanding the complex phenomena occurring between the surfaces of coinage metals and sulfur.

  7. Surface-modified gold nanorods for specific cell targeting

    NASA Astrophysics Data System (ADS)

    Wang, Chan-Ung; Arai, Yoshie; Kim, Insun; Jang, Wonhee; Lee, Seonghyun; Hafner, Jason H.; Jeoung, Eunhee; Jung, Deokho; Kwon, Youngeun

    2012-05-01

    Gold nanoparticles (GNPs) have unique properties that make them highly attractive materials for developing functional reagents for various biomedical applications including photothermal therapy, targeted drug delivery, and molecular imaging. For in vivo applications, GNPs need to be prepared with very little or negligible cytotoxicitiy. Most GNPs are, however, prepared using growth-directing surfactants such as cetyl trimethylammonium bromide (CTAB), which are known to have considerable cytotoxicity. In this paper, we describe an approach to remove CTAB to a non-toxic concentration. We optimized the conditions for surface modification with methoxypolyethylene glycol thiol (mPEG), which replaced CTAB and formed a protective layer on the surface of gold nanorods (GNRs). The cytotoxicities of pristine and surface-modified GNRs were measured in primary human umbilical vein endothelial cells and human cell lines derived from hepatic carcinoma cells, embryonic kidney cells, and thyroid papillary carcinoma cells. Cytotoxicity assays revealed that treating cells with GNRs did not significantly affect cell viability except for thyroid papillary carcinoma cells. Thyroid cancer cells were more susceptible to residual CTAB, so CTAB had to be further removed by dialysis in order to use GNRs for thyroid cell targeting. PEGylated GNRs are further modified to present monoclonal antibodies that recognize a specific surface marker, Na-I symporter, for thyroid cells. Antibody-conjugated GNRs specifically targeted human thyroid cells in vitro.

  8. Comparative hyperthermia effects of silica–gold nanoshells with different surface coverage of gold clusters on epithelial tumor cells

    PubMed Central

    Park, Sang-Eun; Lee, Jaewon; Lee, Taeksu; Bae, Saet-Byeol; Kang, Byunghoon; Huh, Yong-Min; Lee, Sang-Wha; Haam, Seungjoo

    2015-01-01

    Silica–gold nanoshell (SGNS), which is a silica core surrounded by a gold layer, was synthesized by seed-mediated coalescence of gold clusters in an electroless plating solution. SGNS variations with different surface coverage of gold clusters were prepared by adjusting the amounts of gold salts in the presence of formaldehyde-reducing agents. Fully covered SGNS (f-SGNS) with connected gold clusters exhibited stronger intensity and more redshift of plasmon bands located around 820 nm than those of partially covered SGNS (p-SGNS) with disconnected gold clusters. Upon irradiation with near-infrared light (30 W/cm2, 700–800 nm), f-SGNS caused a larger hyperthermia effect, generating a large temperature change (ΔT =42°C), as compared to the relatively small temperature change (ΔT =24°C) caused by p-SGNS. The therapeutic antibody, Erbitux™ (ERB), was further conjugated to SGNS for specific tumor cell targeting. The f-ERB-SGNS showed excellent therapeutic efficacy based on the combined effect of both the therapeutic antibody and the full hyperthermia dose under near-infrared irradiation. Thus, SGNS with well-controlled surface morphology of gold shells may be applicable for near-infrared-induced hyperthermia therapy with tunable optical properties. PMID:26425093

  9. Speciation of surface gold in pressure oxidized carbonaceous gold ores by TOF-SIMS and TOF-LIMS

    NASA Astrophysics Data System (ADS)

    Dimov, S. S.; Chryssoulis, S. L.; Sodhi, R. N.

    2003-01-01

    To the best of our knowledge, this is the first attempt ever to speciate gold preg-robbed by carbonaceous matter using a surface sensitive microbeam technique. This approach enables the direct determination of gold species sorbed on carbonaceous particulates thus providing a new tool in understanding the chemistry of gold sorption on carbon. The reasoning behind this effort was to study the detrimental effect chloride ions have on gold recovery by pressure oxidation of carbonaceous sulfide ores, a technology largely used by the mining industry. The characterization of the sorbed gold species involved three surface sensitive microbeam analytical techniques (TOF-SIMS, TOF-LIMS and XPS) providing confirmatory results for better accuracy. Optimum conditions for detection of gold compounds with minimum fragmentation by TOF-SIMS and TOF-LIMS mass spectrometers have been determined. A reference library of 16 major gold complexes with halogen, thiosulfate, cyanide and thiocyanate groups relevant to the gold recovery processes has been established. The most suitable of the microbeam techniques tested was found to be negative (-ve) ion TOF-LIMS, offering best sensitivity and a small analytical spot size.

  10. Comparative hyperthermia effects of silica-gold nanoshells with different surface coverage of gold clusters on epithelial tumor cells.

    PubMed

    Park, Sang-Eun; Lee, Jaewon; Lee, Taeksu; Bae, Saet-Byeol; Kang, Byunghoon; Huh, Yong-Min; Lee, Sang-Wha; Haam, Seungjoo

    2015-01-01

    Silica-gold nanoshell (SGNS), which is a silica core surrounded by a gold layer, was synthesized by seed-mediated coalescence of gold clusters in an electroless plating solution. SGNS variations with different surface coverage of gold clusters were prepared by adjusting the amounts of gold salts in the presence of formaldehyde-reducing agents. Fully covered SGNS (f-SGNS) with connected gold clusters exhibited stronger intensity and more redshift of plasmon bands located around 820 nm than those of partially covered SGNS (p-SGNS) with disconnected gold clusters. Upon irradiation with near-infrared light (30 W/cm(2), 700-800 nm), f-SGNS caused a larger hyperthermia effect, generating a large temperature change (ΔT =42°C), as compared to the relatively small temperature change (ΔT =24°C) caused by p-SGNS. The therapeutic antibody, Erbitux™ (ERB), was further conjugated to SGNS for specific tumor cell targeting. The f-ERB-SGNS showed excellent therapeutic efficacy based on the combined effect of both the therapeutic antibody and the full hyperthermia dose under near-infrared irradiation. Thus, SGNS with well-controlled surface morphology of gold shells may be applicable for near-infrared-induced hyperthermia therapy with tunable optical properties.

  11. Morphology modification of gold nanoparticles from nanoshell to C-shape: Improved surface enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Xing, Ting-Yang; Zhu, Jian; Li, Jian-Jun; Zhao, Jun-Wu

    2016-06-01

    Morphology modification of nanostructures is of great interest, because it can be used to fabricate nanostructures which are hard to be done using other methods. Different from traditional lithographic technique which is slow and expensive, morphology modification is easy, cheap, and reproducible. In this paper, modification of the optical and morphological properties of a hollow gold nanoshell (HGNS) is achieved by using H2O2 as an oxidizer. The reshaping of these nanostructures has been demonstrated as a consequence of an oxidation process in which HGNSs are dissolved by H2O2 under the acidic conditions provided by HCl. We investigate the oxidation process by a transmission electron microscope and propose a reshaping model involving four different shapes (HGNS, HGNS with hole, gold nanoring, and C-shaped gold nanoparticle) which are corresponding to the oxidation products of HGNSs at different pH values. Besides, the surface enhanced Raman scattering (SERS) activity of each oxidation product has been evaluated by using rhodamine 6G as the Raman active probe. It has been observed that the C-shaped gold nanoparticles which are corresponding to the oxidation products at the minimum pH value have the highest SERS activity and this result can also be interpreted by discrete-dipole approximation simulations. We demonstrate that the morphology modification of HGNSs becomes possible in a controlled manner using wet chemistry and can be used in preparation of gold nanoparticles such as HGNS with hole, gold nanoring, and C-shaped gold nanoparticle with large SERS activity. These nanostructures must have potential use in many plasmonic areas, including sensing, catalysis, and biomedicine.

  12. Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon.

    PubMed

    Cheng, Mingfei; Fang, Jinghuai; Cao, Min; Jin, Yonglong

    2010-11-01

    This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed Central

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

    2016-01-01

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

  15. Surface-Enhanced Raman Scattering of Hydroxyproline in Gold Colloids

    NASA Astrophysics Data System (ADS)

    Guerrero, Ariel R.; Aroca, Ricardo F.

    2010-08-01

    Surface-Enhanced Raman Scattering (SERS) of amino acids has proven a challenging task. The SERS of biomolecules and the formation of a reliable SERS data-base for medical application has shown to be a very challenging task for two reasons: first, the functional groups in proteins, lipid and sugars do not usually include aromatic moieties or chromophores absorbing in the visible (with intrinsic very large cross sections), and therefore, large enhancement factors are needed for ultrasensitive analysis. Second, the biomolecule-metal surface interaction leads to active surface photochemistry, photoisomerization or photodissociation, thus hindering the reproducibility of the experiment. In this work, we have employed hydroxyproline (Hyp) as our problem molecule, and tackled the problem of reproducibility by employing gold colloids instead of the usual silver to achieve SERS. We slightly modified the procedure described by Lee and Meisel to obtain the colloid, and concentrated the gold particles by centrifuging the colloid at 14000 rpm by 7 minutes. The SERS spectra show distinctive bands of Hyp, assigned by comparison to normal Raman spectra and DFT calculations. Repeated measurements using this procedure showed no significant variation in the spectra obtained.

  16. Surface plasma resonant effect of gold nanoparticles on the photoelectrodes of dye-sensitized solar cells

    PubMed Central

    2013-01-01

    In this study, we prepared different shapes of gold nanoparticles by seed-mediated growth method and applied them on the photoelectrodes of dye-sensitized solar cells (DSSCs) to study the surface plasma resonant (SPR) effect of gold nanoparticles on the photoelectrodes of dye-sensitized solar cells. The analyses of field emission scanning electron microscopy show that the average diameter of the spherical gold nanoparticles is 45 nm, the average length and width of the short gold nanorods were 55 and 22 nm, respectively, and the average length and width of the long gold nanorods were 55 and 14 nm, respectively. The aspect ratio of the short and long gold nanorods was about 2.5 and 4, respectively. The results of ultraviolet–visible absorption spectra show that the absorption wavelength is about 540 nm for spherical gold nanoparticles, and the absorption of the gold nanorods reveals two peaks. One is about 510 to 520 nm, and the other is about 670 and 710 nm for the short and long gold nanorods, respectively. The best conversion efficiency of the dye-sensitized solar cells with spherical gold nanoparticles and short and long gold nanorods added in is 6.77%, 7.08%, and 7.29%, respectively, and is higher than that of the cells without gold nanoparticles, which is 6.21%. This result indicates that the effect of gold nanoparticles on the photoelectrodes can increase the conductivity and reduce the recombination of charges in the photoelectrodes, resulting in the increase of conversion efficiency for DSSCs. In addition, the long gold nanorods have stronger SPR effect than the spherical gold nanoparticles and short gold nanorods at long wavelength. This may be the reason for the higher conversion efficiency of DSSCs with long gold nanorods than those of the cells with spherical gold nanoparticles and short gold nanorods. PMID:24172147

  17. Surface-enhanced Raman scattering spectra of tomato epidermis on gold/ silver sol active substrate

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Chen, Zhenyi; Chen, Na; Hu, Ling; Zhu, Hongfei; Liu, Shupeng; Guo, Qiang

    2011-12-01

    In this paper, tomato epidermis' surface-enhanced Raman scattering spectra were measured on gold and silver active substrates and analyzed. Preparing and using gold sol and silver sol in similar particle diameters (about 50-60nm), three comparable Raman spectra were obtained. Silver sol and gold sol can both increase Raman scattering signal of tomato epidermis. Through the Raman spectra, silver sol has greater enhancement ability than gold sol to tomato epidermis.

  18. An investigation of the impedance properties of gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Callaghan, Martina F.; Lund, Torben; Hashemzadeh, Parham; Roitt, Ivan M.; Bayford, Richard H.

    2010-04-01

    Over recent years there has been rapid growth in the research being carried out on nanoparticles. In the field of medical imaging, this interest has focussed primarily on the potential for drug delivery and using nanoparticles as a contrast agent, e.g. super-paramagnetic iron-oxide (SPIO) particles in MRI. More recently gold nanoparticles have been used in radiotherapy treatment of tumours to provide dose enhancement by increasing the efficacy of the radiation absorption. Nanoparticles coated with molecules such as glucose or cancer-specific antibodies can be directed towards specific cancer cells in vivo. Such targeting combined with the properties of nanoparticles shows great promise for localised therapy of tumours while leaving neighbouring healthy tissue unaffected. However, on the nanoparticle scale of sub-100nm the weighting of various factors and inter-atomic interactions which determine the bulk properties of a material changes. Many properties of the bulk material no longer hold. As such, each aspect of nanoparticle behaviour must be investigated afresh to explore the full extent of their potential. The property of nanoparticles we wish to explore and characterise is impedance. Bulk gold is well known to be highly conductive. If this were to remain the case on the nanoscale, it could be highly effective as a contrast agent for electrical impedance tomography, particularly when combined with tumour targeting.

  19. Molecular dynamics simulation studies of gold nano-cluster on silicon (001) surface

    NASA Astrophysics Data System (ADS)

    Sarangi, S. S.; Satyam, P. V.; Nayak, S. K.; Mahanti, S. D.

    2017-02-01

    Classical molecular dynamics simulations with modified embedded atom method model has been carried out to understand the interfacial behavior of a gold(Au) nano-cluster on a silicon(Si) surface. For illustration, a gold nano-cluster (NC) consisting of 108 atoms has been chosen on the Si (001) surface. We have investigated on the process of melting of this NC, the temperature dependent intermixing of Au and Si, and the diffusion of Au atoms into the Si substrate. It has been observed that the NC becomes semi-spherical around the room temperature and the melting process started around 450 K. In order to examine the substrate effect on the melting point temperature of the gold NC, a similar NC has been studied in vacuum. The melting point temperature of this free NC is found to be around 480 K. The observed suppression of melting temperature (by 30 K) for the supported NC can be understood in terms of substrate induced change in morphology. We observe inter-diffusion between gold and silicon atoms for temperatures greater than 650 K.

  20. Analysis of surface stains on modern gold coins

    NASA Astrophysics Data System (ADS)

    Corregidor, V.; Alves, L. C.; Cruz, J.

    2013-07-01

    It is a mandatory practice in the European Mint Houses to provide a certificate of guarantee of their products specially when issuing commemorative gold or silver coins. This practise should assure satisfaction and trust both for the mint house and for the demanding numismatic collector. For these reasons the Mint Houses follow a strict quality control in all the production steps in order to ensure a no-defect, fully supervised output. In spite of all the undertaken precautions, different surface stains with diverse origin on gold coins recently minted in Europe were observed. Those were compositionally studied by means of IBA techniques at the end-stage nuclear microprobe installed at IST/ITN. From this study it was possible to identify several possible sources for these stains. The presence of defects at the surface of these commemorative coins address the need of improving the quality control system and the results here presented point out where these improvements should occur, in order to reduce/eliminate them and give the customer a product that with time probably will be revalued.

  1. Mesoporous gold sponges: electric charge-assisted seed mediated synthesis and application as surface-enhanced Raman scattering substrates

    PubMed Central

    Yi, Zao; Luo, Jiangshan; Tan, Xiulan; Yi, Yong; Yao, Weitang; Kang, Xiaoli; Ye, Xin; Zhu, Wenkun; Duan, Tao; Yi, Yougen; Tang, Yongjian

    2015-01-01

    Mesoporous gold sponges were prepared using 4-dimethylaminopyridine (DMAP)-stabilized Au seeds. This is a general process, which involves a simple template-free method, room temperature reduction of HAuCl4·4H2O with hydroxylamine. The formation process of mesoporous gold sponges could be accounted for the electrostatic interaction (the small Au nanoparticles (~3 nm) and the positively charged DMAP-stabilized Au seeds) and Ostwald ripening process. The mesoporous gold sponges had appeared to undergo electrostatic adsorption initially, sequentially linear aggregation, welding and Ostwald ripening, then, they randomly cross link into self-supporting, three-dimensional networks with time. The mesoporous gold sponges exhibit higher surface area than the literature. In addition, application of the spongelike networks as an active material for surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol (4-ATP) molecules as a probe. PMID:26538365

  2. Attaching Thiolated Superconductor Grains on Gold Surfaces for Nanoelectronics Applications

    NASA Astrophysics Data System (ADS)

    De Los Santos Valladares, Luis; Bustamante Dominguez, Angel; Llandro, Justin; Suzuki, Seiichi; Mitrelias, Thanos; Bellido Quispe, Richard; Barnes, Crispin H. W.; Majima, Yutaka

    2010-09-01

    We report that the high critical temperature superconductor (HTCS) LaCaBaCu3O7 in the form of nanograins can be linked to Au(111) surfaces through self assembled monolayers (SAMs) of HS-C8H16-HS [octane (di)thiol]. We show that La1113 particles (100 nm mean diameter) can be functionalized by octane (di)thiol without affecting their superconducting critical temperature (TC=80 K). X-ray photoemission spectroscopy (XPS) analysis reveals that the thiol functional heads link the superconducting grain surfaces creating sulfonates and we deduce that bonding between the S atoms and Cu(1) atoms of the La1113 structure would be formed. We suggest a design for a superconducting transistor fabricated by immobilized La1113 nanograins in between two gold electrodes which could be controlled by an external magnetic field gate.

  3. Two-dimensional ultrathin gold film composed of steadily linked dense nanoparticle with surface plasmon resonance

    PubMed Central

    2012-01-01

    Background Noble metallic nanoparticles have prominent optical local-field enhancement and light trapping properties in the visible light region resulting from surface plasmon resonances. Results We investigate the optical spectral properties and the surface-enhanced Raman spectroscopy of two-dimensional distinctive continuous ultrathin gold nanofilms. Experimental results show that the one- or two-layer nanofilm obviously increases absorbance in PEDOT:PSS and P3HT:PCBM layers and the gold nanofilm acquires high Raman-enhancing capability. Conclusions The fabricated novel structure of the continuous ultrathin gold nanofilms possesses high surface plasmon resonance properties and boasts a high surface-enhanced Raman scattering (SERS) enhancement factor, which can be a robust and cost-efficient SERS substrate. Interestingly, owing to the distinctive morphology and high light transmittance, the peculiar nanofilm can be used in multilayer photovoltaic devices to trap light without affecting the physical thickness of solar photovoltaic absorber layers and yielding new options for solar cell design. PMID:23259927

  4. Spectroscopic investigation on porphyrins nano-assemblies onto gold nanorods

    NASA Astrophysics Data System (ADS)

    Trapani, Mariachiara; De Luca, Giovanna; Romeo, Andrea; Castriciano, Maria Angela; Scolaro, Luigi Monsù

    2017-02-01

    The interaction between gold nanorods (Au NRs), synthesized by a conventional seeded growth protocol, and the anionic tetrakis-(4-sulfonatophenyl)porphyrin (TPPS4) has been investigated through various spectroscopic techniques. At neutral pH, the formation of H-aggregates and the inclusion of porphyrin monomers in CTAB micelles covering the nanorods have been evidenced. Under mild acidic conditions (pH = 3) a nano-hybrid assembly of porphyrin J-aggregates and Au NRs has been revealed. For the sake of comparison, Cu(II) and Zn(II) metal porphyrin derivatives as well as a cationic porphyrin have been studied in the same experimental conditions, showing that: i) CuTPPS4 forms porphyrin H-dimers onto the Au NRs; ii) ZnTPPS4 undergoes to demetallation, followed by acidification of the central core and eventually aggregation onto Au NRs; iii) cationic porphyrin does not interact with Au NRs.

  5. Electrochemical synthesis of gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode and their application

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Li, X.; Song, Y.; Cheng, Z. P.; Zhong, H.; Xu, J. M.; Lu, J. S.; Wei, C. G.; Zhu, A. F.; Wu, F. Y.; Xu, J.

    2013-01-01

    Gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode were prepared using electrochemical synthesis method. The thin films of gold Nanoparticles/multi-walled carbon nanotubes were characterized by scanning electron microscopy, powder X-ray diffraction, and cyclic voltammetry. Electrochemical behavior of adrenaline hydrochloride at gold nanoparticles/multi-walled carbon nanotube modified glassy carbon electrode was investigated. A simple, sensitive, and inexpensive method for determination of adrenaline hydrochloride was proposed.

  6. Investigation of Hemoglobin/Gold Nanoparticle Heterolayer on Micro-Gap for Electrochemical Biosensor Application

    PubMed Central

    Lee, Taek; Kim, Tae-Hyung; Yoon, Jinho; Chung, Yong-Ho; Lee, Ji Young; Choi, Jeong-Woo

    2016-01-01

    In the present study, we fabricated a hemoglobin/gold nanoparticle (Hb/GNP) heterolayer immobilized on the Au micro-gap to confirm H2O2 detection with a signal-enhancement effect. The hemoglobin which contained the heme group catalyzed the reduction of H2O2. To facilitate the electron transfer between hemoglobin and Au micro-gap electrode, a gold nanoparticle was introduced. The Au micro-gap electrode that has gap size of 5 µm was fabricated by conventional photolithographic technique to locate working and counter electrodes oppositely in a single chip for the signal sensitivity and reliability. The hemoglobin was self-assembled onto the Au surface via chemical linker 6-mercaptohexanoic acid (6-MHA). Then, the gold nanoparticles were adsorbed onto hemoglobin/6-MHA heterolayers by the layer-by-layer (LbL) method. The fabrication of the Hb/GNP heterolayer was confirmed by atomic force microscopy (AFM) and surface-enhanced Raman spectroscopy (SERS). The redox property and H2O2 detection of Hb/GNP on the micro-gap electrode was investigated by a cyclic voltammetry (CV) experiment. Taken together, the present results show that the electrochemical signal-enhancement effect of a hemoglobin/nanoparticle heterolayer was well confirmed on the micro-scale electrode for biosensor applications. PMID:27171089

  7. Role of surface plasmon in second harmonic generation from gold nanorods

    SciTech Connect

    Hubert, C.; Billot, L.; Adam, P.-M.; Bachelot, R.; Royer, P.; Grand, J.; Gindre, D.; Dorkenoo, K. D.; Fort, A.

    2007-04-30

    The role of surface plasmon in second harmonic generation from arrays of gold nanorod particles excited by femtosecond laser pulses is investigated as a function of incident light polarization and irradiation wavelength. In addition to photoluminescence, a peak of second harmonic is observed and is found to depend on the polarization and wavelength of the fundamental frequency laser beam. In particular, the authors found similarities between extinction spectra of the nanoparticles and spectra of emmitted second harmonic. This behavior can be explained by resonant excitation of localized surface plasmon resonances.

  8. In situ GISAXS investigation of gold sputtering onto a polymer template.

    PubMed

    Metwalli, E; Couet, S; Schlage, K; Röhlsberger, R; Körstgens, V; Ruderer, M; Wang, W; Kaune, G; Roth, S V; Müller-Buschbaum, P

    2008-04-15

    Microphase-separation structures in mixed diblock-triblock copolymer thin films are used for the incorporation of gold atoms inside the polymer matrix via sputtering of gold. Polystyrene (PS) spheres are arranged in a liquidlike type with a well defined nearest neighbor distance inside a polyisoprene matrix acting as a template for directing the gold atoms. Sputtering conditions are selected with a very low sputtering rate to avoid clustering in the atmosphere so that gold reaches the polymer surface in its atomic state. Due to the mobility of the gold atoms and the selective interaction with the PS parts of the microphase separation structure, gold is accumulated inside the polymer film in the PS spheres, as probed in situ with grazing incidence small-angle X-ray scattering (GISAXS). Nominally 4.3 A of gold is deposited, which by diffusion is spread out vertically over a thickness of 280 nm. UV-vis spectroscopy reveals a small blue shift for the gold sputtered polymer film. Atomic force microscopy proves the absence of gold clusters on the film surface. For low sputtering rate, GISAXS proves good sensitivity for gold migration inside the polymer film and opens new possibilities for studying polymer-metal interaction.

  9. Comparisons between Surface-Enhanced Raman and Surface Infrared Spectroscopies for Strongly Perturbed Adsorbates: Thiocyanate at Gold Electrodes.

    DTIC Science & Technology

    1986-07-30

    tu. 3. iptt FCSa, s CATALOG NUtof SBetween Surface -Enhanced Raman anj$ YEO EOTI EIDCvfr Surface Infared Spectroscopies for StrongiV Technical Report...REPORT 8 49 0Comparisons Between Surface-Enhanced Raman and Surface Infrared Spectroscopies for Strongly Perturbed Adsorbates: Thiocyanate at Gold...for thiocyanate adsorbed at the gold-aqueous interface is examined by both surface-enhanced Raman spectroscopy (SERS) and subtractively normalized

  10. Self-organization of gold nanoparticles on silanated surfaces

    PubMed Central

    Kyaw, Htet H; Sellai, Azzouz; Dutta, Joydeep

    2015-01-01

    Summary The self-organization of monolayer gold nanoparticles (AuNPs) on 3-aminopropyltriethoxysilane (APTES)-functionalized glass substrate is reported. The orientation of APTES molecules on glass substrates plays an important role in the interaction between AuNPs and APTES molecules on the glass substrates. Different orientations of APTES affect the self-organization of AuNps on APTES-functionalized glass substrates. The as grown monolayers and films annealed in ultrahigh vacuum and air (600 °C) were studied by water contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, UV–visible spectroscopy and ultraviolet photoelectron spectroscopy. Results of this study are fundamentally important and also can be applied for designing and modelling of surface plasmon resonance based sensor applications. PMID:26734526

  11. Multiple Surface Plasmon Modes for Gold/Silver Alloy Nanorods

    SciTech Connect

    Bok, Hye-Mi; Shuford, Kevin L; Kim, Sungwan; Kim, Seong Kyu; Park, Sungho

    2009-01-01

    Alloy nanorods consisting of bimetallic gold and silver are synthesized by employing the electrochemical codeposition of Au/Ag alloy materials into the pores of anodized aluminum oxide templates. This paper presents the variation of localized surface plasmon resonance (LSPR) modes of the Au{sub x}/Ag{sub 1-x} alloy nanorods as a function of relative compositions of Au and Ag. Transverse and multiple longitudinal modes were observed when the length was longer than ca. 300 nm. For a given length, the transverse LSPR mode systematically blue-shifted as the Ag portion increased, while there was little variation in peak positions of the longitudinal LSPR modes. The optical properties of the Au{sub x}/Ag{sub 1-x} alloy nanorods were calculated using the discrete dipole approximation and showed a good agreement with the experimental measurements.

  12. Surface packing determines the redox potential shift of cytochrome c adsorbed on gold.

    PubMed

    Zanetti-Polzi, Laura; Daidone, Isabella; Bortolotti, Carlo Augusto; Corni, Stefano

    2014-09-17

    Thermodynamic and dynamic properties of iso-1-cytochrome c covalently bound to a bare gold surface are here investigated by large scale atomistic simulations. The reduction potential of the protein for low and high surface concentrations is calculated showing a good agreement with experimental estimates. The origin of the dependence of the reduction potential on the surface concentration is investigated and is demonstrated to stem from the changing polarizability of the environment surrounding the protein, a mechanism reminiscent of crowding effects. Moreover, structural analyses are performed revealing relevant changes induced by the presence of the electrode on the dynamic properties of cytochrome c. In particular, one of the two cavities previously identified on the protein surface [Bortolotti et al. J. Am. Chem. Soc., 2012, 134, 13670], and that reversibly open in cytochrome c freely diffusing in solution, is found to be deformed when the protein is adsorbed on gold. This modification exemplifies a mechanism that potentially leads to changes in the protein properties by surface-induced modification of its dynamical behavior.

  13. Gold nanoparticles surface modification using BSA and cysteine

    NASA Astrophysics Data System (ADS)

    Cardoso-Avila, P. E.; Pichardo-Molina, J. L.; Upendra Kumar, K.; Barbosa-Sabanero, G.; Barbosa-Garcia, O.

    2011-08-01

    Metal nanometer-size particles show intriguing optical properties which depend on their shape, size and local environment. For these reasons, these materials have received a lot of attention in different scientific areas, and several applications can be found, for example: fabrication of bio-sensor, electronic devices, catalysis and new drugs. However, in the case of biomedical applications, metallic nanoparticles need to satisfy several requirements: bio-compatibility, stability and functionality. To satisfy these requirements, metallic nanoparticles need to be modified in their surfaces. In this work we report the synthesis and the modification of gold nanoparticles (GNPs) surface. GNPs were fabricated following the Turkevich's method, and the bio-conjugation (surface modification) was done using cysteine and bovine serum albumin (BSA). Our results of Uv-vis spectroscopy show that BSA and cysteine permit to increase the stability of GNPs in presence of NaCl, the stability is function of BSA concentration. Also to verify the bio-conjugation we used Raman spectroscopy and gel electrophoresis.

  14. Magnetic resonance investigation of gold-doped and gold-hydrogen-doped silicon

    NASA Astrophysics Data System (ADS)

    Huy, P. T.; Ammerlaan, C. A.

    2002-10-01

    Three paramagnetic centers related to gold have been observed in gold-doped and gold-doped hydrogenated silicon by magnetic resonance. One spectrum, labeled Si-NL62, corresponding to a center with monoclinic-I symmetry, presents fourfold splitting due to the hyperfine interaction with one gold atom and further hyperfine interaction with two silicon nearest-neighbor atoms. After being diffused with hydrogen in a wet atmosphere of water vapor at 1300 °C for about 30 min, a second electron paramagnetic resonance spectrum, labeled Si-NL63, is detected, also of the monoclinic-I symmetry. The spectrum of the center is characterized by a complex hyperfine structure, in which, depending on magnetic field orientation, a sevenfold splitting with the intensities 1:2:3:4:3:2:1, a fourfold splitting 4:4:4:4, and other more arbitrary structures are observed. Extra small splitting is observed in the sample diffused with deuterium, indicating hydrogen involvement in the microscopic structure of the Si-NL63 center. Under band gap illumination the third center of a one-gold-two-hydrogen complex is observed. The center, labeled Si-NL64, has low triclinic symmetry and features the hyperfine interactions with one gold and two nearly equivalent hydrogen atoms. This results in a (1:2:1):(1:2:1):(1:2:1):(1:2:1) structure of each group of spectral lines. Spin-Hamiltonian parameters for the three spectra are determined and microscopic models are discussed.

  15. Nd:YAG laser penetration into cast titanium and gold alloy with different surface preparations.

    PubMed

    Watanabe, I; Baba, N; Chang, J; Chiu, Y

    2006-06-01

    This study investigated the effect of surface preparation on the Nd:YAG laser penetration into cast titanium and gold alloy. Cast blocks of each metal were given four different surface preparations: (i) coloured with black marker; (ii) air-abraded with 50 microm Al2O3; (iii) ground with SiC points and (iv) polished with 1 microm Al2O3 (mirror-polished). Two blocks with each of the surface preparations were abutted and laser-welded at their interface using the voltages of 210-260 V in increments of 10 V. After the welded blocks were mechanically separated, the laser penetration was measured using computer graphics. Regardless of the surface preparation, an increase in voltage increased the laser penetration for both metals. The laser penetration into titanium prepared with black marker and air-abrasion was significantly deeper than into the titanium ground with SiC points and mirror-polished. Although there were no statistical differences in penetration among the surface preparations for the gold alloy, the penetration in the mirror-polished specimens was shallower than any of the other preparation methods at higher voltages of 240-260 V. The results obtained in this study suggested that broken metal frameworks with finished surfaces should be painted with black marker or air-abraded before laser welding.

  16. Low energy slowing down of nanosize copper clusters on gold (1 1 1) surfaces

    NASA Astrophysics Data System (ADS)

    Lei, H.; Hou, Q.; Hou, M.

    2000-04-01

    The slowing down of copper clusters formed by 440 atoms on a gold (1 1 1) surface is studied in detail by means of molecular dynamics. The atomic classical molecular dynamics is based on the second moment approximation of the tight binding model and, in addition, accounts for the electron-phonon coupling in the frame of the Sommerfeld theory of metals. The slowing down energy range is 0-1 eV/atom, which is characteristic of low energy cluster beam deposition (LECBD). A pronounced epitaxy of the copper clusters is found. However, their morphology is significantly energy dependent. The structure and the radial pair correlation functions are used to study the details of the epitaxial properties as well as the pronounced relaxation in the interfacial cluster atom positions due to the lattice mismatch between copper and gold. The effect of the cluster and substrate average temperature is investigated and can be distinguished from the kinetic effect of the cluster impact.

  17. Surface enhanced Raman scattering, antibacterial and antifungal active triangular gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Smitha, S. L.; Gopchandran, K. G.

    2013-02-01

    Shape controlled syntheses of gold nanoparticles have attracted a great deal of attention as their optical, electronic, magnetic and biological properties are strongly dependent on the size and shape of the particles. Here is a report on the surface enhanced Raman scattering (SERS) activity of Cinnamomum zeylanicum leaf broth reduced gold nanoparticles consisting of triangular and spherical like particles, using 2-aminothiophenol (2-ATP) and crystal violet (CV) as probe molecules. Nanoparticles prepared with a minimum leaf broth concentration, having a greater number of triangular like particles exhibit a SERS activity of the order of 107. The synthesized nanoparticles exhibit efficient antibacterial activity against the tested gram negative bacterium Escherichia coli and gram positive bacterium Staphylococcus aureus. Investigations on the antifungal activity of the synthesized nanoparticles against Aspergillus niger and Fusarium oxysporum positive is also discussed.

  18. Gold nanoparticle based surface enhanced fluorescence for detection of organophosphorus agents

    NASA Astrophysics Data System (ADS)

    Dasary, Samuel S. R.; Rai, Uma S.; Yu, Hongtao; Anjaneyulu, Yerramilli; Dubey, Madan; Ray, Paresh Chandra

    2008-07-01

    Organophosphorus agents (OPA) represent a serious concern to public safety as nerve agents and pesticides. Here we report the development of gold nanoparticle based surface enhanced fluorescence (NSEF) spectroscopy for rapid and sensitive screening of organophosphorus agents. Fluorescent from Eu 3+ ions that are bound within the electromagnetic field of gold nanoparticles exhibit a strong enhancement. In the presence of OPA, Eu 3+ ions are released from the gold nanoparticle surface and thus a very distinct fluorescence signal change was observed. We discussed the mechanism of fluorescence enhancement and the role of OPA for fluorescence intensity change in the presence of gold nanoparticles.

  19. Simulation studies of electroless metal deposition using gold nano-clusters on polymeric surfaces

    NASA Astrophysics Data System (ADS)

    Lively, Mike; Bhattacharya, Aniket; Grabill, Chris; Kuebler, Stephen M.; Dutta, Aniruddha; Heinrich, Helge

    2010-03-01

    We report lattice Monte Carlo (MC) simulation studies of deposition of metallic silver on randomly distributed gold nano clusters on a polymeric surface. The gold nano-clusters act as seeds for further deposition of silver atoms. We assume ballistic growth for the growth of metallic silver on gold clusters but treat the lateral growth (which eventually form bridges among original clusters) with different rules and study the evolving morphologies of the deposited silver atoms as a function of the surface density and the size distribution of gold nano-clusters and compare simulation results with those obtained from TEM studies of the prepared samples.

  20. Mussel-inspired block copolymer lithography for low surface energy materials of teflon, graphene, and gold.

    PubMed

    Kim, Bong Hoon; Lee, Duck Hyun; Kim, Ju Young; Shin, Dong Ok; Jeong, Hu Young; Hong, Seonki; Yun, Je Moon; Koo, Chong Min; Lee, Haeshin; Kim, Sang Ouk

    2011-12-15

    Mussel-inspired interfacial engineering is synergistically integrated with block copolymer (BCP) lithography for the surface nanopatterning of low surface energy substrate materials, including, Teflon, graphene, and gold. The image shows the Teflon nanowires and their excellent superhydrophobicity.

  1. Surface plasmon-driven water reduction: gold nanoparticle size matters.

    PubMed

    Qian, Kun; Sweeny, Brendan C; Johnston-Peck, Aaron C; Niu, Wenxin; Graham, Jeremy O; DuChene, Joseph S; Qiu, Jingjing; Wang, Yi-Chung; Engelhard, Mark H; Su, Dong; Stach, Eric A; Wei, Wei David

    2014-07-16

    Water reduction under two different visible-light ranges (λ > 400 nm and λ > 435 nm) was investigated in gold-loaded titanium dioxide (Au-TiO2) heterostructures with different sizes of Au nanoparticles (NPs). Our study clearly demonstrates the essential role played by Au NP size in plasmon-driven H2O reduction and reveals two distinct mechanisms to clarify visible-light photocatalytic activity under different excitation conditions. The size of the Au NP governs the efficiency of plasmon-mediated electron transfer and plays a critical role in determining the reduction potentials of the electrons transferred to the TiO2 conduction band. Our discovery provides a facile method of manipulating photocatalytic activity simply by varying the Au NP size and is expected to greatly facilitate the design of suitable plasmonic photocatalysts for solar-to-fuel energy conversion.

  2. Mixed DNA/Oligo(ethylene glycol) Functionalized Gold Surface Improve DNA Hybridization in Complex Media

    SciTech Connect

    Lee,C.; Gamble, L.; Grainger, D.; Castner, D.

    2006-01-01

    Reliable, direct 'sample-to-answer' capture of nucleic acid targets from complex media would greatly improve existing capabilities of DNA microarrays and biosensors. This goal has proven elusive for many current nucleic acid detection technologies attempting to produce assay results directly from complex real-world samples, including food, tissue, and environmental materials. In this study, we have investigated mixed self-assembled thiolated single-strand DNA (ssDNA) monolayers containing a short thiolated oligo(ethylene glycol) (OEG) surface diluent on gold surfaces to improve the specific capture of DNA targets from complex media. Both surface composition and orientation of these mixed DNA monolayers were characterized with x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS). XPS results from sequentially adsorbed ssDNA/OEG monolayers on gold indicate that thiolated OEG diluent molecules first incorporate into the thiolated ssDNA monolayer and, upon longer OEG exposures, competitively displace adsorbed ssDNA molecules from the gold surface. NEXAFS polarization dependence results (followed by monitoring the N 1s{yields}{pi}* transition) indicate that adsorbed thiolated ssDNA nucleotide base-ring structures in the mixed ssDNA monolayers are oriented more parallel to the gold surface compared to DNA bases in pure ssDNA monolayers. This supports ssDNA oligomer reorientation towards a more upright position upon OEG mixed adlayer incorporation. DNA target hybridization on mixed ssDNA probe/OEG monolayers was monitored by surface plasmon resonance (SPR). Improvements in specific target capture for these ssDNA probe surfaces due to incorporation of the OEG diluent were demonstrated using two model biosensing assays, DNA target capture from complete bovine serum and from salmon genomic DNA mixtures. SPR results demonstrate that OEG incorporation into the ssDNA adlayer improves surface resistance to both nonspecific DNA and protein

  3. [Preparation, characterization and surface-enhanced Raman properties of agarose gel/gold nanoparticles hybrid].

    PubMed

    Ma, Xiao-yuan; Liu, Ying; Wang, Zhou-ping

    2014-08-01

    Agarose gel/gold nanoparticles hybrid was prepared by adding gold nanoparticles to preformed agarose gel. Naniocomposite structures and properties were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and UV-Vis-NIR absorption spectroscopy. Experimental data indicated a uniform distribution of gold nanoparticles adsorbed on agarose gel network And the excellent optical absorption properties were shown. Based on the swelling-contraction characteristics of agarose gel and the adjustable localized surface plasmon resonance (LSPR) of the gold nanoparticles, the nano-composites were used as surface enhanced Raman scattering (SERS) substrate to detect the Raman signal molecules Nile blue A. Results revealed that the porous structure of the agarose gel provided a good carrier for the enrichment of the gold nanoparticles. The gold nanoparticles dynamic hot-spot effect arising from the agarose gel contraction loss of water in the air greatly enhanced the Raman signal.

  4. Pharmacological Investigation of Fluoro-Gold Entry into Spinal Neurons

    PubMed Central

    Falgairolle, Melanie; O’Donovan, Michael J.

    2015-01-01

    The fluorescent tracer Fluoro-Gold has been widely used to label neurons retrogradely. Here we show that Fluoro-Gold can also enter neurons through AMPA receptor endocytosis. We found that a 30 minute application of Fluoro-Gold to the isolated spinal cord labeled neurons under control conditions and in the presence of glutamatergic agonists including NMDA and AMPA. The labeling was abolished or greatly reduced by glutamatergic antagonists and the endocytic inhibitors Dynasore and dynamin inhibitory peptide. Whole cell recordings from spinal neurons exposed to extracellular AMPA revealed large inward currents that spontaneously decayed in the presence of the agonist but were maintained when a dynamin inhibitory peptide was included in the electrode. These findings suggest that Fluoro-Gold enters spinal neurons through AMPA-mediated receptor internalization. Drugs used to induce locomotor-like activity in the spinal cord also increased and decreased Fluoro-Gold labeling in a drug and lamina specific manner, indicating that AMPAR endocytosis is altered in the presence of the locomotor cocktail. Our findings suggest that endocytosis of Fluoro-Gold could potentially complicate the interpretation of experiments in which the tracer is used to label neurons retrogradely. Moreover, they also demonstrate that many drugs, including the locomotor cocktail, can modulate the number and/or the composition of AMPA receptors on spinal neurons and thereby affect network excitability. PMID:26102354

  5. Pharmacological Investigation of Fluoro-Gold Entry into Spinal Neurons.

    PubMed

    Falgairolle, Melanie; O'Donovan, Michael J

    2015-01-01

    The fluorescent tracer Fluoro-Gold has been widely used to label neurons retrogradely. Here we show that Fluoro-Gold can also enter neurons through AMPA receptor endocytosis. We found that a 30 minute application of Fluoro-Gold to the isolated spinal cord labeled neurons under control conditions and in the presence of glutamatergic agonists including NMDA and AMPA. The labeling was abolished or greatly reduced by glutamatergic antagonists and the endocytic inhibitors Dynasore and dynamin inhibitory peptide. Whole cell recordings from spinal neurons exposed to extracellular AMPA revealed large inward currents that spontaneously decayed in the presence of the agonist but were maintained when a dynamin inhibitory peptide was included in the electrode. These findings suggest that Fluoro-Gold enters spinal neurons through AMPA-mediated receptor internalization. Drugs used to induce locomotor-like activity in the spinal cord also increased and decreased Fluoro-Gold labeling in a drug and lamina specific manner, indicating that AMPAR endocytosis is altered in the presence of the locomotor cocktail. Our findings suggest that endocytosis of Fluoro-Gold could potentially complicate the interpretation of experiments in which the tracer is used to label neurons retrogradely. Moreover, they also demonstrate that many drugs, including the locomotor cocktail, can modulate the number and/or the composition of AMPA receptors on spinal neurons and thereby affect network excitability.

  6. Rough SERS substrate based on gold coated porous silicon layer prepared on the silicon backside surface

    NASA Astrophysics Data System (ADS)

    Dridi, H.; Haji, L.; Moadhen, A.

    2017-04-01

    We report in this paper a novel method to elaborate rough Surface Enhanced Raman Scattering (SERS) substrate. A single layer of porous silicon was formed on the silicon backside surface. Morphological characteristics of the porous silicon layer before and after gold deposition were influenced by the rough character (gold size). The reflectance measurements showed a dependence of the gold nano-grains size on the surface nature, through the Localized Surface Plasmon (LSP) band properties. SERS signal of Rhodamine 6G used as a model analyte, adsorbed on the rough porous silicon layer revealed a marked enhancement of its vibrational modes intensities.

  7. Sequence and Temperature Influence on Kinetics of DNA Strand Displacement at Gold Electrode Surfaces.

    PubMed

    Biala, Katarzyna; Sedova, Ada; Flechsig, Gerd-Uwe

    2015-09-16

    Understanding complex contributions of surface environment to tethered nucleic acid sensing experiments has proven challenging, yet it is important because it is essential for interpretation and calibration of indispensable methods, such as microarrays. We investigate the effects of DNA sequence and solution temperature gradients on the kinetics of strand displacement at heated gold wire electrodes, and at gold disc electrodes in a heated solution. Addition of a terminal double mismatch (toehold) provides a reduction in strand displacement energy barriers sufficient to probe the secondary mechanisms involved in the hybridization process. In four different DNA capture probe sequences (relevant for the identification of genetically modified maize MON810), all but one revealed a high activation energy up to 200 kJ/mol during hybridization, that we attribute to displacement of protective strands by capture probes. Protective strands contain 4 to 5 mismatches to ease their displacement by the surface-confined probes at the gold electrodes. A low activation energy (30 kJ/mol) was observed for the sequence whose protective strand contained a toehold and one central mismatch, its kinetic curves displayed significantly different shapes, and we observed a reduced maximum signal intensity as compared to other sequences. These findings point to potential sequence-related contributions to oligonucleotide diffusion influencing kinetics. Additionally, for all sequences studied with heated wire electrodes, we observed a 23 K lower optimal hybridization temperature in comparison with disc electrodes in heated solution, and greatly reduced voltammetric signals after taking into account electrode surface area. We propose that thermodiffusion due to temperature gradients may influence both hybridization and strand displacement kinetics at heated microelectrodes, an explanation supported by computational fluid dynamics. DNA assays with surface-confined capture probes and temperature

  8. Thiol adsorption at gold surfaces: self-assembly, chiral recognition, and enantioselective adsorption at chiral surfaces.

    NASA Astrophysics Data System (ADS)

    Hammer, Bjork

    2003-03-01

    Density functional theory calculations are presented for the adsorption of thiol containing molecules on to Au(111), Au(110), and Au(17 11 9). The thiol group becomes dehydrogenated during the adsorption process and the resulting thiolate group shows a strong preference for the Au-Au bridging adsorption site.[1] For methylthiolate adsorption, a restructuring of the Au(111) surface in to a honeycomb pattern with every 3rd Au atom missing is found to lead an overall strengthening of the thiolate-gold bonding.[2] Since the surface restructuring must happen through-out the system, it represents a net attractive interaction between the adsorbates and it is speculated to have implications for the self-assembly of alkanethiols found at close packed gold surfaces. Adsorption studies of the naturally occuring amino acid, cysteine, at Au(110) also reveal enhanced thiolate-gold bonding at restructured Au sites.[3] The cysteine molecules are found to interact pairwise forming dimers that are hydrogen bonded through the cysteine carboxyl groups. The gold surface restructuring required to hold this complex involves the creation of a four Au atom wide vacancy in the outermost close packed row of the Au(110) surface. The binding of the the cysteine dimer to this vacancy site causes chiral recognition -- only cysteine dimers formed between like cysteine enantiomers are able to bind to the surface. For cysteine adsorption over the chiral (kinked) Au(17 11 9) surface no enantiospecific adsorption is found since the molecule only binds through the thiolate and amino groups.[4] Modifying the adsorbate by substituting the noninteracting carboxyl group with a dimethylphosphino group provides a third strong adsorbate-surface bond thereby enabling the discrimination during adsorption of two molecular enantiomers by one particular chiral Au surface. [1] J. Gottschalck and B. Hammer, J. Chem. Phys. 116, 784 (2002). [2] L.M. Molina and B. Hammer, Chem. Phys. Lett. 360, 264 (2002). [3] A

  9. Surface functionalization by gold nanoparticles and its prospects for application in conductometric metal oxide gas sensors

    NASA Astrophysics Data System (ADS)

    Korotcenkov, G.; Brinzari, V.; Cho, B. K.

    2017-03-01

    Approaches to surface functionalizing by gold nanoparticles of metal oxides aimed for gas sensors applications are discussed in this paper. It is demonstrated that surface modification by gold nanoparticles is accompanied by improvement of sensor performance. However, analysis of obtained results has shown that the achievement of strong improvement of gas sensor parameters is not a trivial task. For its reduction, it is necessary to ensure several specific conditions related to the size and density of gold clusters on the surface of metal oxide crystallites, the state of gold in the cluster, and to the properties of the metal oxide support used. It is also demonstrated that additional studies are required before conductometric gas sensors modified by gold nanoclusters will appear in gas-sensor market.

  10. Characterization of silver ions adsorbed on gold nanorods: surface analysis by using surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Niidome, Yasuro; Nakamura, Yuki; Honda, Kanako; Akiyama, Yasuyuki; Nishioka, Koji; Kawasaki, Hideya; Nakashima, Naotoshi

    2009-04-07

    Surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-MS) indicated AgBr2-, which adsorbed on gold nanorod surfaces, was a key material to control the anisotropic growth of gold nanorods.

  11. Geologic, geophysical, and in situ stress investigations in the vicinity of the Dining Car Chimney, Dining Car/Hybla gold tunnels, Nevada Test Site, with sections on geologica investigations, geophysical investigations, and in situ stress investigations

    USGS Publications Warehouse

    Townsend, D.R.; Baldwin, M.J.; Carroll, R.D.; Ellis, W.L.; Magner, J.E.

    1982-01-01

    The Hybla Gold experiment was conducted in the U12e.20 drifts of the E-tunnel complex beneath the surface of Rainier Mesa at the Nevada Test Site. Though the proximity of the Hybla Gold working point to the chimney of the Dining Car event was important to the experiment, the observable geologic effects from Dining Car on the Hybla Gold site were minor. Overburden above the working point is approximately 385 m (1,263 ft). The pre-Tertiary surface, probably quartzite, lies approximately 254 m (833 ft) below the working point. The drifts are mined in zeolitized ash-fall tuffs of tunnel bed 4, subunits K and J, all of Miocene age. The working point is in subunit 4J. Geologic structure in the region around the working point is not complex. The U12e.20 main drift follows the axis of a shallow depositional syncline. A northeast-dipping fault with displacement of approximately 3 m (10 ft) passes within 15.2 m (50 ft) of the Hybla Gold working point. Three faults of smaller displacement pass within 183-290 m (600-950 ft) of the working point, and are antithetic to the 3-m (10-ft) fault. Three exploratory holes were drilled to investigate the chimney of the nearby Dining Car event. Four horizontal holes were drilled during the construction of the U12e.20 drifts to investigate the geology of the Hybla Gold working point.

  12. Role of nanostructured gold surfaces on monocyte activation and Staphylococcus epidermidis biofilm formation

    PubMed Central

    Svensson, Sara; Forsberg, Magnus; Hulander, Mats; Vazirisani, Forugh; Palmquist, Anders; Lausmaa, Jukka; Thomsen, Peter; Trobos, Margarita

    2014-01-01

    The role of material surface properties in the direct interaction with bacteria and the indirect route via host defense cells is not fully understood. Recently, it was suggested that nanostructured implant surfaces possess antimicrobial properties. In the current study, the adhesion and biofilm formation of Staphylococcus epidermidis and human monocyte adhesion and activation were studied separately and in coculture in different in vitro models using smooth gold and well-defined nanostructured gold surfaces. Two polystyrene surfaces were used as controls in the monocyte experiments. Fluorescent viability staining demonstrated a reduction in the viability of S. epidermidis close to the nanostructured gold surface, whereas the smooth gold correlated with more live biofilm. The results were supported by scanning electron microscopy observations, showing higher biofilm tower formations and more mature biofilms on smooth gold compared with nanostructured gold. Unstimulated monocytes on the different substrates demonstrated low activation, reduced gene expression of pro- and anti-inflammatory cytokines, and low cytokine secretion. In contrast, stimulation with opsonized zymosan or opsonized live S. epidermidis for 1 hour significantly increased the production of reactive oxygen species, the gene expression of tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β), IL-6, and IL-10, as well as the secretion of TNF-α, demonstrating the ability of the cells to elicit a response and actively phagocytose prey. In addition, cells cultured on the smooth gold and the nanostructured gold displayed a different adhesion pattern and a more rapid oxidative burst than those cultured on polystyrene upon stimulation. We conclude that S. epidermidis decreased its viability initially when adhering to nanostructured surfaces compared with smooth gold surfaces, especially in the bacterial cell layers closest to the surface. In contrast, material surface properties neither strongly

  13. Gold Nanoparticles with Externally Controlled, Reversible Shifts of Local Surface Plasmon Resonance Bands

    PubMed Central

    Yavuz, Mustafa S.; Jensen, Gary C.; Penaloza, David P.; Seery, Thomas A. P.; Pendergraph, Samuel A.; Rusling, James F.; Sotzing, Gregory A.

    2010-01-01

    We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

  14. DNA-Origami-Driven Lithography for Patterning on Gold Surfaces with Sub-10 nm Resolution.

    PubMed

    Gállego, Isaac; Manning, Brendan; Prades, Joan Daniel; Mir, Mònica; Samitier, Josep; Eritja, Ramon

    2017-01-06

    Sub-10 nm lithography of DNA patterns is achieved using the DNA-origami stamping method. This new strategy utilizes DNA origami to bind a preprogrammed DNA ink pattern composed of thiol-modified oligonucleotides on gold surfaces. Upon denaturation of the DNA origami, the DNA ink pattern is exposed. The pattern can then be developed by hybridization with complementary strands carrying gold nanoparticles.

  15. Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

    NASA Astrophysics Data System (ADS)

    Berlanga, Isadora; Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo; Gómez, Victoria Alejandra; Aliaga-Alcalde, Núria; Fuenzalida, Victor; Flores, Marcos; Soler, Monica

    2017-01-01

    We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

  16. Vibrational properties of an adamantane monolayer on a gold surface

    NASA Astrophysics Data System (ADS)

    Sakai, Yuki; Nguyen, Giang D.; Capaz, Rodrigo B.; Coh, Sinisa; Pechenezhskiy, Ivan V.; Hong, Xiaoping; Crommie, Michael F.; Wang, Feng; Saito, Susumu; Louie, Steven G.; Cohen, Marvin L.

    2014-03-01

    We study the vibrational properties of an adamantane monolayer on a Au(111) surface. The IR spectrum of a self-assembled monolayer of adamantane on Au(111) is measured by a newly developed infrared scanning tunneling microscopy (IRSTM) technique. We analyze the IR spectrum of this system by a density functional theory and find that the IR spectrum is severely modified by both adamantane-gold and adamantane-adamantane interactions. One of three gas-phase C-H bond stretching modes is significantly red-shifted due to the molecule-substrate interactions. The intermolecular interactions cause a suppression of the IR intensity of another gas-phase IR peak. The techniques used in this work can be applied for an independent estimate of molecule-substrate and intermolecular interactions in related diamondoid/metal-substrate systems. This work was supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.

  17. [Dithiobis-succinimidyl propionate on gold island films: surface-enhanced infrared absorption spectroscopy study].

    PubMed

    Guo, Hao; Ding, Li; Zhang, Tian-Jie; Mao, Yan-Li

    2013-05-01

    Dithiobis-succinimidyl propionate (DTSP), an important homobifunctional crosslinker, has been widely used for the covalent immobilization of proteins onto solid supports by amine coupling. In the present study, adsorption of DTSP on vacuum-deposited gold island films was analyzed by means of surface-enhanced infrared absorption spectroscopy (SEIRAS). For the sake of a reliable assignment of the vibrational spectra, IR intensity of the adsorption model of TSP on one gold surface was calculated using density functional theory (DFT) at the Beck' s three-parameter Lee-Yang-Parr (B3LYP) level with the LANL2DZ basis set. SEIRAS and multiple-angle-of-incidence polarization infrared reflection-absorption spectroscopy indicated that TSP is arranged orderly in a tilted fashion with a dihedral angle of 65 degrees between the plane of succinimidyl ring and the gold surface. The binding kinetics revealed that that the time constant of self-assembly of the TSP layer is 220 sec. Furthermore, the coupling process of amino-nitrilotriacetic acid (ANTA) with surface-bound TSP monolayer was monitored in situ by SEIRAS. Three negative bands observed at 1 807, 1 776, and 1 728 cm(-1) respectively provided direct evidence for the reaction of the succinimidyl ester. The appearance of one intense band at 1 566 cm(-1) gave a clear support for the presence of the cross-link between ANTA and TSP. We hope that the results in current investigation will contribute to the better understanding of properties of DTSP and related reactions at the molecular level.

  18. Gold and aluminum based surface plasmon resonance biosensors: sensitivity enhancement

    NASA Astrophysics Data System (ADS)

    Biednov, Mykola; Lebyedyeva, Tetyana; Shpylovyy, Pavlo

    2015-05-01

    In this work we considered Gold and Aluminum thin films coated with additional dielectric layers as sensing platforms. Operation of these sensors is based on measuring shift in the position of the reflectivity dip in angular reflectivity spectrum of the sample. Shift can be caused by changes in the refraction index of either liquid that interacts with sensors surface (refractometric measurements) or thin adjacent biolayer on top of the sensor due to immobilization of the target molecules (biosensing). Calculations based on Fresnel equations and transfer matrix formalism allowed us to make comprehensive analysis of the angular sensitivity, shape of the reflectivity dip and dynamic range of the sensors with different dielectric coatings. Calculations were performed for both cases of bio and refractometric sensing. Results showed different dependence of the sensitivity of Au an Al based sensors upon refraction index of the dielectric coating. For Au-based surface Plasmon resonance sensor up to two times increased sensitivity can be achieved using dielectric coating with high refraction index 2.3 of proper thickness. For sensors based on aluminum we were able to achieve 50% increased angular sensitivity. At the same time width of the reflectivity dip increased proportionally to the optical thickness of the dielectric coating. For estimating sensors quality we analyzed ratio of the angular sensitivity to the width of the reflectivity dip. This ratio decreased with increase in optical thickness of the dielectric, however angular sensitivity of the sensor increased significantly. Deposition of the additional dielectric layer with high refraction index such as Niobium Oxide can also improve chemical and mechanical stability of the sensor.

  19. Quantitative surface acoustic wave detection based on colloidal gold nanoparticles and their bioconjugates.

    PubMed

    Chiu, Chi-Shun; Gwo, Shangjr

    2008-05-01

    The immobilization scheme of monodispersed gold nanoparticles (10-nm diameter) on piezoelectric substrate surfaces using organosilane molecules as cross-linkers has been developed for lithium niobate (LiNbO3) and silicon oxide (SiO2)/gold-covered lithium tantalate (LiTaO3) of Rayleigh and guided shear horizontal- (guided SH) surface acoustic wave (SAW) sensors. In this study, comparative measurements of gold nanoparticle adsorption kinetics using high-resolution field-emission scanning electron microscopy and SAW sensors allow the frequency responses of SAW sensors to be quantitatively correlated with surface densities of adsorbed nanoparticles. Using this approach, gold nanoparticles are used as the "nanosized mass standards" to scale the mass loading in a wide dynamical range. Rayleigh-SAW and guided SH-SAW sensors are employed here to monitor the surface mass changes on the device surfaces in gas and liquid phases, respectively. The mass sensitivity ( approximately 20 Hz.cm2/ng) of Rayleigh-SAW device (fundamental oscillation frequency of 113.3 MHz in air) is more than 2 orders of magnitude higher than that of conventional 9-MHz quartz crystal microbalance sensors. Furthermore, in situ (aqueous solutions), real-time measurements of adsorption kinetics for both citrate-stabilized gold nanoparticles and DNA-gold nanoparticle conjugates are also demonstrated by guided SH-SAW (fundamental oscillation frequency of 121.3 MHz). By comparing frequency shifts between the adsorption cases of gold nanoparticles and DNA-gold nanoparticle conjugates, the average number of bound oligonucleotides per gold nanoparticle can also be determined. The high mass sensitivity ( approximately 6 Hz.cm2/ng) of guided SH-SAW sensors and successful detection of DNA-gold nanoparticle conjugates paves the way for real-time biosensing in liquids using nanoparticle-enhanced SAW devices.

  20. Thermodynamic and kinetic analysis of the interaction between hepatitis B surface antibody and antigen on a gold electrode modified with cysteamine and colloidal gold via electrochemistry.

    PubMed

    He, Yan Bin; Luo, Hong Qun; Li, Nian Bing

    2007-06-15

    Hepatitis B surface antibody (HBsAb) was immobilized to the surface of a gold electrode modified with cysteamine and colloidal gold as matrices to detect hepatitis B surface antigen (HBsAg). Differential pulse voltammetry (DPV) method was used for the investigation of the specific interaction between the immobilized HBsAb and HBsAg in solution, which was followed as a change of peak current in DPV with time. With the modified gold electrode, the differences in affinity of HBsAb with HBsAg at the temperatures of 37 and 40 degrees C were easily distinguished and the kinetic rate constants (k(ass) and k(diss)) and kinetic affinity constant K were determined from the curves of current versus time. In addition, the thermodynamic constants, DeltaG, DeltaH and DeltaS, of the interaction at 37 degrees C were calculated, which were -56.65, -64.54 and -25.45 kJ mol(-1), respectively.

  1. Ultrasmooth gold surfaces prepared by chemical mechanical polishing for applications in nanoscience.

    PubMed

    Miller, Michael S; Ferrato, Michael-Anthony; Niec, Adrian; Biesinger, Mark C; Carmichael, Tricia Breen

    2014-12-02

    For over 20 years, template stripping has been the best method for preparing ultrasmooth metal surfaces for studies of nanostructures. However, the organic adhesives used in the template stripping method are incompatible with many solvents, limiting the conditions that may subsequently be used to prepare samples; in addition, the film areas that can be reliably prepared are typically limited to ∼1 cm(2). In this article, we present chemical-mechanical polishing (CMP) as an adhesive-free, scalable method of preparing ultrasmooth gold surfaces. In this process, a gold film is first deposited by e-beam evaporation onto a 76-mm-diameter silicon wafer. The CMP process removes ∼4 nm of gold from the tops of the grains comprising the gold film to produce an ultrasmooth gold surface supported on the silicon wafer. We measured root-mean-square (RMS) roughness values using atomic force microscopy of 12 randomly sampled 1 μm × 1 μm areas on the surface of the wafer and repeated the process on 5 different CMP wafers. The average RMS roughness was 3.8 ± 0.5 Å, which is comparable to measured values for template-stripped gold (3.7 ± 0.5 Å). We also compared the use of CMP and template-stripped gold as bottom electrical contacts in molecular electronic junctions formed from n-alkanethiolate self-assembled monolayers as a sensitive test bed to detect differences in the topography of the gold surfaces. We demonstrate that these substrates produce statistically indistinguishable values for the tunneling decay coefficient β, which is highly sensitive to the gold surface topography.

  2. Raman spectroscopy and quantum-mechanical analysis of tautomeric forms in cytosine and 5-methylcytosine on gold surfaces

    NASA Astrophysics Data System (ADS)

    Nguyen, Dinh Bao; Nguyen, Thanh Danh; Kim, Sangsoo; Joo, Sang-Woo

    2017-03-01

    Spectral differences between cytosine (Cyt) and 5-methylcytosine (5MC) were investigated by means of Raman spectroscopy with a combination of density functional theory (DFT) calculations. Surface-enhanced Raman scattering (SERS) revealed discriminating peaks of 5MC from those of Cyt upon adsorption on gold nanoparticles (AuNPs). Among the notable features, the multiple bands between 850 and 700 cm- 1 for the ring-breathing modes of 5MC and Cyt could be correlated well with the simulated spectra based on the DFT calculations of the adsorbates on the gold cluster atoms. The relative energetic stabilities of the enol/keto and the amino/imino tautomeric forms of Cyt and 5MC have been estimated using DFT calculations, before and after binding six atom gold clusters. Among the six tautomeric forms, the 7H keto amino and the 4H imino trans forms are expected to be predominant in binding gold atoms, whereas the enol trans/cis conformers would coexist in the free gas phase. Our approach may provide useful theoretical guidelines for identifying 5MC from Cyt by analyzing Raman spectra on gold surfaces on the basis of quantum-mechanical calculations.

  3. Investigating the use of in situ liquid cell scanning transmission electron microscopy to explore DNA-mediated gold nanoparticle growth

    NASA Astrophysics Data System (ADS)

    Nguy, Amanda

    Engineering nanoparticles with desired shape-dependent properties is the key to many applications in nanotechnology. Although many synthetic procedures exist to produce anisotropic gold nanoparticles, the dynamics of growth are typically unknown or hypothetical. In the case of seed-mediated growth in the presence of DNA into anisotropic nanoparticles, it is not known exactly how DNA directs growth into specific morphologies. A series of preliminary experiments were carried out to contribute to the investigation of the possible mechanism of DNA-mediated growth of gold nanoprisms into gold nanostars using liquid cell scanning transmission electron microscopy (STEM). Imaging in the liquid phase was achieved through the use of a liquid cell platform and liquid cell holder that allow the sample to be contained within a “chip sandwich” between two electron transparent windows. Ex situ growth experiments were performed using Au-T30 NPrisms (30-base thymine oligonucleotide-coated gold nanoprisms) that are expected to grow into gold nanostars. Growth to form these nanostars were imaged using TEM (transmission electron microscopy) and liquid cell STEM (scanning transmission electron microscopy). An attempt to perform in situ growth experiments with the same Au-T30 nanoprisms revealed challenges in obtaining desired morphology results due to the environmental differences within the liquid cell compared to the ex situ environment. Different parameters in the experimental method were explored including fluid line set up, simultaneous and alternating reagent addition, and the effect of different liquid cell volumes to ensure adequate flow of reagents into the liquid cell. Lastly, the binding affinities were compared for T30 and A30 DNA incubated with gold nanoparticles using zeta potential measurements, absorption spectroscopy, and isothermal titration calorimetry (ITC). It was previously reported thymine bases have a lower binding affinity to gold surfaces than

  4. Electroless Gold-Modified Diatoms as Surface-Enhanced Raman Scattering Supports.

    PubMed

    Pannico, Marianna; Rea, Ilaria; Chandrasekaran, Soundarrajan; Musto, Pellegrino; Voelcker, Nicolas H; De Stefano, Luca

    2016-12-01

    Porous biosilica from diatom frustules is well known for its peculiar optical and mechanical properties. In this work, gold-coated diatom frustules are used as low-cost, ready available, functional support for surface-enhanced Raman scattering. Due to the morphology of the nanostructured surface and the smoothness of gold deposition via an electroless process, an enhancement factor for the p-mercaptoaniline Raman signal of the order of 10(5) is obtained.

  5. Electroless Gold-Modified Diatoms as Surface-Enhanced Raman Scattering Supports

    NASA Astrophysics Data System (ADS)

    Pannico, Marianna; Rea, Ilaria; Chandrasekaran, Soundarrajan; Musto, Pellegrino; Voelcker, Nicolas H.; De Stefano, Luca

    2016-06-01

    Porous biosilica from diatom frustules is well known for its peculiar optical and mechanical properties. In this work, gold-coated diatom frustules are used as low-cost, ready available, functional support for surface-enhanced Raman scattering. Due to the morphology of the nanostructured surface and the smoothness of gold deposition via an electroless process, an enhancement factor for the p-mercaptoaniline Raman signal of the order of 105 is obtained.

  6. Gold surface supported spherical liposome-gold nano-particle nano-composite for label free DNA sensing.

    PubMed

    Bhuvana, M; Narayanan, J Shankara; Dharuman, V; Teng, W; Hahn, J H; Jayakumar, K

    2013-03-15

    Immobilization of 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) liposome-gold nano-particle (DOPE-AuNP) nano-composite covalently on 3-mercaptopropionic acid (MPA) on gold surface is demonstrated for the first time for electrochemical label free DNA sensing. Spherical nature of the DOPE on the MPA monolayer is confirmed by the appearance of sigmoidal voltammetric profile, characteristic behavior of linear diffusion, for the MPA-DOPE in presence of [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+) redox probes. The DOPE liposome vesicle fusion is prevented by electroless deposition of AuNP on the hydrophilic amine head groups of the DOPE. Immobilization of single stranded DNA (ssDNA) is made via simple gold-thiol linkage for DNA hybridization sensing in the presence of [Fe(CN)(6)](3-/4-). The sensor discriminates the hybridized (complementary target hybridized), un-hybridized (non-complementary target hybridized) and single base mismatch target hybridized surfaces sensitively and selectively without signal amplification. The lowest target DNA concentration detected is 0.1×10(-12)M. Cyclic voltammetry (CV), electrochemical impedance (EIS), differential pulse voltammetry (DPV) and quartz crystal microbalance (QCM) techniques are used for DNA sensing on DOPE-AuNP nano-composite. Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS) and Ultraviolet-Visible (UV) spectroscopic techniques are used to understand the interactions between the DOPE, AuNP and ssDNA. The results indicate the presence of an intact and well defined spherical DOPE-AuNP nano-composite on the gold surface. The method could be applied for fabrication of the surface based liposome-AuNP-DNA composite for cell transfection studies at reduced reagents and costs.

  7. Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

    SciTech Connect

    Harnisch, Jennifer Anne

    2001-01-01

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

  8. An Electrochemical and Raman Spectroelectrochemical Investigation of Underpotentially Deposited Silver on a Gold Substrate.

    DTIC Science & Technology

    1986-07-30

    Raman Spectroelectrochemical Investigation of Underpotentially Deposited Silver on a Gold Substrate By Stanley Pons. J. Li, J. Liang DTIC S ELECTE APR 14...ACCCSSIONd 14U. 3. i4CCipIa.ti rs CATALOG. PiumnRi - 4. ITL (sa~utfie) . TYPE Of REPORT a PCI3ioo covEuiv Investigation of Underpotentially Deposited ...spectroelectrochemical data indicate that underpotentially * deposited silver adatoms on gold substrates are photolyzed to form silver meta clusters. *DD

  9. Gold Rush!

    ERIC Educational Resources Information Center

    Brahier, Daniel J.

    1997-01-01

    Describes a mathematical investigation of gold--how it is weighed, stored, used, and valued. For grades 3-4, children estimate the value of treasure chests filled with gold coins and explore the size and weight of gold bars. Children in grades 5-6 explore how gold is mined and used, and how the value of gold changes over time. (PVD)

  10. Reconnaissance investigation of the placer gold deposits in the Zarkashan Area of Interest, Ghazni Province, Afghanistan

    USGS Publications Warehouse

    Malpeli, Katherine C.; Chirico, Peter G.; McLoughlin, Isabel H.

    2013-01-01

    This study is a reconnaissance investigation of the placer gold deposits in the Zarkashan Area of Interest (AOI) in Ghazni Province, Afghanistan. Detailed investigations of the Zarkashan gold deposits were conducted by Soviet and Afghan geologists in the 1960s and 1970s, prior to the development of satellite-based remote-sensing platforms and new methods of geomorphic mapping. The purpose of this study was to integrate new mapping techniques with previously collected concentration and borehole sampling data and geomorphologic interpretations to reassess the placer gold deposits in the Zarkashan AOI. A methodology combining the collection and analysis of historical sampling data, digital database development, hydrologic analysis, and geomorphic modeling was used. The analysis led to the reinterpretation of four gold-bearing seams along the Zarkashan River, and the calculation of an estimated gold reserve of approximately 3,000 kilograms (kg). This estimate is approximately 1,500 kg greater than the Soviet estimate. The result differs in large part due to the reinterpretation of the seams based on a much lower cutoff grade of 100 mg/m3. Because cutoff grade is dependent in part on the price of gold, the sevenfold increase in the price of gold since the undertaking of the Soviet investigation warranted our re-evaluation of their 500 mg/m3 cutoff grade.

  11. Adsorption and Exchange Kinetics of Hydrophilic and Hydrophobic Phosphorus Ligands on Gold Surface

    NASA Astrophysics Data System (ADS)

    Zhuge, X. Q.; Bian, Z. C.; Luo, Z. H.; Mu, Y. Y.; Luo, K.

    2017-02-01

    The adsorption kinetics process of hydrophobic ligand (triphenylphosphine, PPh3) and hydrophilic ligand (tris(hydroxymethyl)phosphine oxide, THPO) on the surface of gold electrode were estimated by using electrical double layer capacitance (EDLC). Results showed that the adsorption process of both ligands included fast and slow adsorption processes, and the fast adsorption process could fit the first order kinetic equation of Langmuir adsorption isotherm. During the slow adsorption process, the surface coverage (θ) of PPh3 was higher than that of THPO due to the larger adsorption kinetic constant of PPh3 than that of THPO, which implied that PPh3 could replace THPO on the gold electrode. The exchange process of both ligands on the surface of gold electrode proved that PPh3 take the place of THPO by testing the variation of EDLC which promote the preparation of Janus gold, and the theoretic simulation explained the reason of ligands exchange from the respect of energy..

  12. Straightforward and robust synthesis of monodisperse surface-functionalized gold nanoclusters

    PubMed Central

    Varela-Aramburu, Silvia; Wirth, Richard; Lai, Chian-Hui; Orts-Gil, Guillermo

    2016-01-01

    Summary Gold nanoclusters are small (1–3 nm) nanoparticles with a high surface area that are useful for biomedical studies and drug delivery. The synthesis of small, surface-functionalized gold nanoclusters is greatly dependent on the reaction conditions. Here, we describe a straightforward, efficient and robust room temperature one-pot synthesis of 2 nm gold nanoclusters using thioglucose as a reducing and stabilizing agent, which was discovered by serendipity. The resultant monodisperse gold nanoclusters are more stable than those generated using some other common methods. The carboxylic acid contained in the stabilizing agent on the cluster surface serves as anchor for nanocluster functionalization. Alternatively, the addition of thiols serves to functionalize the nanoclusters. The resulting non-cytotoxic nanoclusters are taken up by cells and constitute a tuneable platform for biomedical applications including drug delivery. PMID:27826501

  13. Annealing Effects on the Surface Plasmon of MgO Implanted with Gold

    NASA Technical Reports Server (NTRS)

    Ueda, A.; Mu, R.; Tung, Y. -S.; Henderson, D. O.; White, C. W.; Zuhr, R. A.; Zhu, Jane G.; Wang, P. W.

    1997-01-01

    Gold ion implantation was carried out with the energy of 1.1 MeV into (100) oriented MgO single crystal. Implanted doses are 1, 3, 6, 10 x 10(exp 16) ions/sq cm. The gold irradiation results in the formation of gold ion implanted layer with a thickness of 0.2 microns and defect formation. In order to form gold colloids from the as-implanted samples, we annealed the gold implanted MgO samples in three kinds of atmospheres: (1)Ar only, (2)H2 and Ar, and (3)O2 and Ar. The annealing over 1200 C enhanced the gold colloid formation which shows surface plasmon resonance band of gold. The surface plasmon bands of samples annealed in three kinds of atmospheres were found to be at 535 nm (Ar only), 524 nm(H2+Ar), and 560 nm (02+Ar), The band positions of surface plasmon can be reversibly changed by an additional annealing.

  14. Ultrafast Electron Dynamics in Gold in the Presence of Laser Excited Surface Plasma Waves

    SciTech Connect

    Raynaud, M.

    2010-02-02

    Surface plasmon excitation with ultrashort intense laser pulses enhances efficiently laser absorption in metals and creates local high fields and non-equilibrium hot electrons population that have attractivity for numerous applications such as the development of intense sources of high-energy particles or photons and in the fast ignitor scheme in the framework of inertial fusion. In this context, the knowledge of the dynamics of relaxation of the collective electrons behavior is of importance. Using gold grating, we have investigated electrons relaxation in the presence of laser excited surface plasmon waves using a multiple-wavelengh femtosecond pump-probe technique. The results yield evidence of longer relaxation time in the presence of the collective excitation than that of individual electronic states.

  15. Electroanalysis using macro-, micro-, and nanochemical architectures on electrode surfaces. Bulk surface modification of glassy carbon microspheres with gold nanoparticles and their electrical wiring using carbon nanotubes.

    PubMed

    Dai, Xuan; Wildgoose, Gregory G; Salter, Chris; Crossley, Alison; Compton, Richard G

    2006-09-01

    Gold nanoparticles (approximately 30-60 nm in diameter) were deposited onto the surface of glassy carbon microspheres (10-20 microm) through electroless plating to produce bulk (i.e., gram) quantities of nanoparticle surface-modified microspheres. The gold nanoparticle-modified powder was then characterized by means of scanning electron microscopy and cyclic voltammetry. The voltammetric response of a macroelectrode consisting of a film of gold nanoparticle-modified glassy carbon microspheres, bound together and "wired-up" using multiwalled carbon nanotubes (MWCNTs), was investigated. We demonstrate that by intelligently exploiting both nano- and microchemical architectures and wiring up the electroactive centers using MWCNTs in this way, we can obtain macroelectrode voltammetric behavior while only using approximately 1% by mass of the expensive gold material that would be required to construct the equivalent gold film macrodisk electrode. The potential utility of electrodes constructed using chemical architectures such as this was demonstrated by applying them to the analytical determination of arsenic(III) concentration. An optimized limit of detection of 2.5 ppb was obtained.

  16. Gold nanoparticles assisted characterization of amine functionalized polystyrene multiwell plate and glass slide surfaces

    NASA Astrophysics Data System (ADS)

    Dharanivasan, Gunasekaran; Rajamuthuramalingam, Thangavelu; Michael Immanuel Jesse, Denison; Rajendiran, Nagappan; Kathiravan, Krishnan

    2015-01-01

    We demonstrated citrate-capped gold nanoparticles assisted characterization of amine functionalized polystyrene plate and glass slide surfaces through AuNPs staining method. The effect of AuNPs concentration on the characterization of amine modified surfaces was also studied with different concentration of AuNPs (ratios 1.0-0.0). 3-Aminopropylyl triethoxy silane has been used as amine group source for the surface modification. The interactions of AuNPs on modified and unmodified surfaces were investigated using atomic force microscopy and the dispersibility, and the aggregation of AuNPs was analyzed using UV-visible spectrophotometer. Water contact angle measurement and X-ray photoelectron spectroscopy (XPS) were used to further confirmation of amine modified surfaces. The aggregation of AuNPs in modified multiwell plate leads to the color change from red to purple and they are found to be adsorped on the modified surfaces. Aggregation and adsorption of AuNPs on the modified surfaces through the electrostatic interactions and the hydrogen bonds were revealed by XPS analysis. Remarkable results were found even in the very low concentration of AuNPs (ratio 0.2). This AuNPs staining method is simple, cost-effective, less time consuming, and required very low concentration of AuNPs. These results can be read out through the naked eye without the help of sophisticated equipments.

  17. Surface Engineering of Triboelectric Nanogenerator with an Electrodeposited Gold Nanoflower Structure

    PubMed Central

    Park, Sang-Jae; Seol, Myeong-Lok; Jeon, Seung-Bae; Kim, Daewon; Lee, Dongil; Choi, Yang-Kyu

    2015-01-01

    A triboelectric nanogenerator composed of gold nanoflowers is demonstrated. The proposed triboelectric nanogenerator creates electricity by contact-separation-based electrification between an anodic metal and a cathodic polymer. For the improvement of output power via the enlargement of the effective surface area in the anodic metal, gold nanoflowers that produce a hierarchical morphology at a micro-to-nano scale by electrodeposition are utilized. The hierarchical morphology is controlled by the applied voltage and deposition time. Even though the triboelectric coefficient of gold is inferior to those of other metals, gold is very attractive to make a flower-like structure by electrodeposition. Moreover, gold is stable against oxidation by oxygen in air. From a reliability and practicality point of view, the aforementioned stability against oxidation is preferred. PMID:26365054

  18. Surface enhanced Raman scattering of amino acids assisted by gold nanoparticles and Gd(3+) ions.

    PubMed

    López-Neira, Juan Pablo; Galicia-Hernández, José Mario; Reyes-Coronado, Alejandro; Pérez, Elías; Castillo-Rivera, Francisco

    2015-05-07

    The surface enhanced raman scattering (SERS) signal from the l-tyrosine (tyr) molecule adsorbed on gold nanoparticles (Au-tyr) is compared with the SERS signal assisted by the presence of gadolinium ions (Gd(3+)) coordinated with the Au-tyr system. An enhancement factor of the SERS signal in the presence of Gd(3+) ions was ∼5 times higher than that produced by l-tyrosine adsorbed on gold nanoparticles. The enhancement of the SERS signal can be attributed to a corresponding increase in the local electric field due to the presence of Gd(3+) ions in the vicinity of a gold dimer configuration. This scenario was confirmed by solving numerically Maxwell equations, showing an increase of 1 order of magnitude in the local electric scattered field when the Gd(3+) ion is located in between a gold dimer compared with naked gold nanoparticles.

  19. Where's the silver? Imaging trace silver coverage on the surface of gold nanorods.

    PubMed

    Jackson, Stephen R; McBride, James R; Rosenthal, Sandra J; Wright, David W

    2014-04-09

    The development of the seeded growth synthesis for gold nanorods provided the first simple, convenient wet chemistry route to these nanomaterials. Over the past decade, the original silver-assisted seeded growth procedure has been the subject of further modifications that have continuously expanded access to anisotropic gold nanoparticles; however, the role of silver in formation of gold nanorods remains poorly understood. We report the first experimental evidence on the position of silver present on gold nanorods using advanced energy dispersive X-ray spectroscopy. Our results indicate the deposition of silver ions on the surface shows no preference for a specific face or axis. Furthermore, we show that the "dog bone" structures developed from gold nanorod solutions show preferential deposition of silver atoms on the ends and in the crevices.

  20. Gold Nanostars For Surface-Enhanced Raman Scattering: Synthesis, Characterization and Optimization

    PubMed Central

    Khoury, Christopher G.; Vo-Dinh, Tuan

    2008-01-01

    The controlled synthesis of high-yield gold nanostars of varying sizes, their characterization and use in surface-enhanced Raman scattering (SERS) measurements are reported for the first time. Gold nanostars ranging from 45 to 116-nm in size were synthesized in high-yield, physically modeled and optically characterized using transmission and scanning electron microscopy and UV-Visible absorption spectroscopy. The nanostar characterization involved both studying morphology evolution over time and size as a function of nucleation. The nanostars properties as substrates for SERS were investigated and compared with respect to size. As the overall star size increases, so does the core size, the number of branches and branch aspect ratio; the number of branch tips per star surface area decreases with increasing size. The stars become more inhomogeneous in shape, although their yield is high and overall size remains homogeneous. Variations in star size are also accompanied by shifts of the long plasmon band in the NIR region, which hints towards tuning capabilities that may be exploited in specific SERS applications. The measured SERS enhancement factors suggest an interesting correlation between nanostar size and SERS efficiencies, and were relatively consistent across different star samples, with the enhancement factor estimated as 5×103 averaged over the 52-nm nanostars for 633-nm excitation. PMID:23977403

  1. Interaction of bombesin and its fragments with gold nanoparticles analyzed using surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Tąta, Agnieszka; Szkudlarek, Aleksandra; Kim, Younkyoo; Proniewicz, Edyta

    2017-02-01

    This work demonstrates the application of commercially available stable surface composed of gold nanograins with diameters ranging from 70 to 226 nm deposited onto silicon wafer for surface-enhanced Raman scattering investigations of biologically active compounds, such as bombesin (BN) and its fragments. BN is an important neurotransmitter involved in a complex signaling pathways and biological responses; for instance, hypertensive action, contractive on uterus, colon or ileum, locomotor activity, stimulation of gastric and insulin secretion as well as growth promotion of various tumor cell lines, including: lung, prostate, stomach, colon, and breast. It has also been shown that 8-14 BN C-terminal fragment partially retains the biological activity of BN. The SERS results for BN and its fragment demonstrated that (1) three amino acids from these peptides sequence; i.e., L-histidine, L-methionine, and L-tryptophan, are involved in the interaction with gold coated silicon wafer and (2) the strength of these interactions depends upon the aforementioned amino acids position in the peptide sequence.

  2. Investigation of gold as a material for thermal radiation shielding

    NASA Astrophysics Data System (ADS)

    Munshi, Amit Harenkumar

    CdS/CdTe thin film solar cells technology is one of the fastest growing carbon neutral energy sources in the world today. Manufacturing of CdS/CdTe solar modules is carried out at temperature in the range of 620350°C under a vacuum of 40 millitorr using a Heated Pocket Deposition (HPD) system in the materials engineering laboratory. Since this system operates in vacuum, majority of the heat loss is due to thermal radiation. The concept here is to conserve the heat by reflecting the infrared radiation back into the deposition system thus increasing the thermal efficiency. Various metals may be used but calculations show that using a Gold thin film mirror can effectively reflect almost 97% of the incident radiation, thus conserving energy required for the manufacturing process. However, a phenomenon called thermal grooving or island formation inhibits its use. Thermal grooving occurs when the stress concentration at the grain boundaries causes grain separation. This phenomenon is observed in thin gold films that are exposed to a temperature in excess of 350°C for over 3 to 5 hours. In this study, these films are exposed to temperature upto 620350°C for cycles as long as 200 hours. The goal of this research is to explore the solutions for elimination of the phenomenon of thermal grooving and thus extract maximum life out of these thin gold films for conservation of heat. After carefully exploring literature on past research and conducting experiments it was found that within the range of the films that were tested, a 2000 A350° film with a 150 A350° of Indium underlay showed the best performance after thermal annealing and testing.

  3. Investigation of thiol derivatized gold nanoparticle sensors for gas analysis

    NASA Astrophysics Data System (ADS)

    Stephens, Jared S.

    Analysis of volatile organic compounds (VOCs) in air and exhaled breath by sensor array is a very useful testing technique. It can provide non-invasive, fast, inexpensive testing for many diseases. Breath analysis has been very successful in identifying cancer and other diseases by using a chemiresistor sensor or array with gold nanoparticles to detect biomarkers. Acetone is a biomarker for diabetes and having a portable testing device could help to monitor diabetic and therapeutic progress. An advantage to this testing method is it is conducted at room temperature instead of 200 degrees Celsius. 3. The objective of this research is to determine the effect of thiol derivatized gold nanoparticles based on sensor(s) detection of VOCs. The VOCs to be tested are acetone, ethanol, and a mixture of acetone and ethanol. Each chip is tested under all three VOCs and three concentration levels (0.1, 1, and 5.0 ppm). VOC samples are used to test the sensors' ability to detect and differentiate VOCs. Sensors (also referred to as a chip) are prepared using several types of thiol derivatized gold nanoparticles. The factors are: thiol compound and molar volume loading of the thiol in synthesis. The average resistance results are used to determine the VOC selectivity of the sensors tested. The results show a trend of increasing resistance as VOC concentration is increased relative to dry air; which is used as baseline for VOCs. Several sensors show a high selectivity to one or more VOCs. Overall the 57 micromoles of 4-methoxy-toluenethiol sensor shows the strongest selectivity for VOCs tested. 3. Gerfen, Kurt. 2012. Detection of Acetone in Air Using Silver Ion Exchanged ZSM-5 and Zinc Oxide Sensing Films. Master of Science thesis, University of Louisville.

  4. Investigation of nanoparticle formation in a plasma produced by femtosecond laser ablation of gold

    SciTech Connect

    Spiga, P.; Hermann, J.; Itina, T.; Grojo, D.; Neamtu, D.; Pailharey, D.; Marine, W.

    2005-10-31

    The formation of nanoparticles in a plasma produced by the interaction of ultrashort laser pulses with gold has been investigated. Three different experimental techniques were employed. (i) The plume expansion was characterized using fast imaging with the aid of an intensified charge-coupled device. (ii) The plasma composition was analyzed using time- and space-resolved optical emission spectroscopy. (iii) The ablated material was deposited on mica substrates and analyzed by means of atomic force microscopy. As a result, the size-distribution and the overall number of nanoparticles were determined as a function of the laser energy density incident on the target surface. The detection of particles with sizes in the nanometer range supports theoretical modeling according to which phase explosion is the dominant mechanism of metal ablation by ultrashort laser pulses.

  5. Effects of changes in the interparticle separation induced by alkanethiols on the surface plasmon band and other properties of nanocrystalline gold films.

    PubMed

    Agrawal, Ved Varun; Varghese, Neenu; Kulkarni, G U; Rao, C N R

    2008-03-18

    Effects of changing the interparticle separation on the surface plasmon bands of ultrathin films of gold nanoparticles have been investigated by examining the interaction of alkanethiols of varying chain length on nanocrystalline gold films generated at the organic-aqueous interface. Adsorption of alkanethiols causes blue-shifts of the surface plasmon adsorption band, the magnitude of the shift being proportional to the chain length. The disordered nanocrystals thus created (lambdamax, 530 m) are in equilibrium with the ordered nanocrystals in the film (lambdamax, 700 m) as indicated by an isosbestic point around 600 nm. Long chain thiols disintegrate or disorder the gold films more effectively, as demonstrated by the increased population of the thiol-capped gold nanocrystals in solution. The rate of interaction of the thiols with the film decreases with the decreasing chain length. The effect of an alkanethiol on the spectrum of the gold film is specific, in that the effects with long and short chains are reversible. The changes in the plasmon band of gold due to interparticle separation can be satisfactorily modeled on the basis of the Maxwell-Garnett formalism. Spectroscopic studies, augmented by calorimetric measurements, suggest that the interaction of alkanethiols involves two steps, the first step being the exothermic gold film-thiol interaction and the second step includes the endothermic disordering process followed by further thiol capping of isolated gold particles.

  6. Far- and near-field properties of gold nanoshells studied by photoacoustic and surface-enhanced Raman spectroscopies.

    PubMed

    Weber, V; Feis, A; Gellini, C; Pilot, R; Salvi, P R; Signorini, R

    2015-09-07

    Gold nanoshells, with a silica core and different core and shell dimensions, have been extensively investigated. Optical far-field properties, namely extinction and absorption, have been separately determined by means of spectrophotometry and photoacoustic spectroscopy, respectively, in the 440-900 nm range. The enhancement factor for surface-enhanced Raman scattering, which is related to near-field effects, has been measured from 568 to 920 nm. The absorption contribution to extinction decreases as the overall diameter increases. Moreover, absorption and scattering display different spectral distributions, the latter being red shifted. The Surface Enhanced Raman Scattering enhancement profile, measured using thiobenzoic acid as a Raman probe, is further shifted to the red. The latter result suggests that the enhancement is dominated by the presence of hot spots, which are possibly related to the surface roughness of gold nanoshell particles.

  7. Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applicationsa

    PubMed Central

    Li, M.; Kim, D.-P.; Jeong, G.-Y.; Seo, D.-K.; Park, C.-P.

    2012-01-01

    Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip. PMID:24324531

  8. Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applications.

    PubMed

    Li, M; Kim, D-P; Jeong, G-Y; Seo, D-K; Park, C-P

    2012-01-01

    Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip.

  9. 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.

  10. Photoacoustic investigation of gold nanoshells for bioimaging applications

    NASA Astrophysics Data System (ADS)

    Sathiyamoorthy, K.; Strohm, Eric M.; Kolios, Michael C.

    2016-03-01

    In this study, we report photoacoustic (PA) measurements of gold-covered polystyrene nanoparticles (Au nanoshells). Two types of Au nanoshells were examined: 1) polystyrene core with sparsely covered Au nanoparticles, and 2) polystyrene core which were fully covered by Au nanoparticles. The fully covered Au nanoshell exhibited a broad extinction cross section (500 nm - 850 nm), which is in the first infrared optical window where light transmission is optimal for optical based studies in tissues. The optical properties were compared to numerical simulations using Mie scattering theory. Using a photoacoustic microscope, the PA signal measured from fully covered Au nanoshells was 1.27 +/- 0.18 mV per fluence (mJ/cm2), which was 10x greater than the PA signal from sparsely covered Au nanoshells (0.12 +/- 0.14 mV). These novel Au nanoshell nanoparticles can be used for multispectral optical and PA imaging.

  11. Theoretical study of atomic oxygen on gold surface by Hückel theory and DFT calculations.

    PubMed

    Sun, Keju; Kohyama, Masanori; Tanaka, Shingo; Takeda, Seiji

    2012-09-27

    It is fundamental to understand the behavior of atomic oxygen on gold surfaces so as to elucidate the mechanism of nano gold catalysts for low-temperature CO oxidation reactions since the atomic oxygen on gold system is an important intermediate involved in both the processes of O(2) dissociation and CO oxidation. We performed theoretical analysis of atomic oxygen adsorption on gold by using Hückel theory. It is found that formation of linear O-Au-O structure on Au surfaces greatly stabilizes the atomic oxygen adsorption due to stronger bond energy and bond order, which is confirmed subsequently by density functional theory (DFT) calculations. The linear O-Au-O structure may explain the surprising first order kinetics behavior of O(2) desorption from gold surfaces. This view of the linear O-Au-O structure as the natural adsorption status is quite different from the conventional view, which may lead to new understanding toward the reaction mechanism of low-temperature CO oxidation reaction on nano gold catalysts.

  12. Effect of Gold Nanorod Surface Chemistry on Cellular Response

    DTIC Science & Technology

    2011-03-15

    distribution unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT Recently gold nanoparticles (Au NPs) have shown promising biological and military applications...tion after exposure to nanoparticles , but Trypan Blue exclusion assay and protein quantification did not show increased cell viability. It was...the literature showed that nanoparticles caused DNA damage to cells indirectly, without ever being directly exposed to or taken up by the cells.45 It is

  13. Mechanisms of Reduced Astrocyte Surface Coverage in Cortical Neuron-Glia Co-cultures on Nanoporous Gold Surfaces.

    PubMed

    Chapman, Christopher A R; Chen, Hao; Stamou, Marianna; Lein, Pamela J; Seker, Erkin

    2016-09-01

    Nanoporous gold (np-Au) is a promising multifunctional material for neural electrodes. We have previously shown that np-Au nanotopography reduces astrocyte surface coverage (linked to undesirable gliosis) while maintaining high neuronal coverage in a cortical primary neuron-glia co-culture model as long as two weeks in vitro. Here, we investigate the potential influence of secreted soluble factors from cells grown on np-Au on the cell type-specific surface coverage of cells grown on conventional tissue culture plastic and test the hypothesis that secretion of factors is responsible for inhibiting astrocyte coverage on np-Au. In order to assess whether factors secreted from cells grown on np-Au surfaces reduced surface coverage by astrocytes, we seeded fresh primary rat neuron-glia co-cultures on conventional polystyrene culture dishes, but maintained the cells in conditioned media from co-cultures grown on np-Au surfaces. After one week in vitro, a preferential reduction in astrocyte surface coverage was not observed, suggesting that soluble factors are not playing a role. In contrast, four hours after cell seeding there were a significant number of non-adhered, yet still viable, cells for the cultures on np-Au surfaces. We hypothesize that the non-adherent cells are mainly astrocytes, because: (i) there was no difference in neuronal cell coverage between np-Au and pl-Au for long culture durations and (ii) neurons are post-mitotic and not expected to increase in number upon attaching to the surface. Overall, the results suggest that the np-Au topography leads to preferential neuronal attachment shortly after cell seeding and limits astrocyte-specific np-Au surface coverage at longer culture durations.

  14. CO2 laser-cleaning of dimethylsilicone contamination on the surface of gold films

    NASA Astrophysics Data System (ADS)

    Ye, Yayun; Yuan, Xiaodong; Xiang, Xia; Chen, Meng; Miao, Xinxiang; Lv, Haibing; Wang, Haijung; Wang, Chengcheng; Zheng, Wanguo

    2009-08-01

    As a non-contact cleaning method, laser cleaning can effectively remove particulate contaminations of sizes as small as 0.1 μm without damage to the optics. In this work, 10.6 μm CO2 laser was utilized to clean the dimethylsilicone oil contaminated on the surface of the gold-coated K9 glass. The dimethylsilicone oil contaminants with different degree were obtained by 10-30 minutes of vapor condensation. Single point irradiation mode was used to study the removal of the dimethylsilicone oil. The cleaning different degree of contaminations was investigated at the variable laser parameters, including laser power, laser frequency, and irradiation time. Optical microscope was used to analyze the cleaning effect. The results show that CO2 laser can effectively remove the dimethylsilicone oil. On the premise that the gold-coated K9 glasses are not damaged, the cleaning area increases with the increase of radiation time and laser power. The cleaning area doesn't change much with the variation of laser frequency when the other parameters are the same. In addition, at the same laser parameters, the cleaning area increases as contamination degree increases.

  15. Gold nanoparticles on the surface of soda-lime glass: morphological, linear and nonlinear optical characterization.

    PubMed

    Romani, E C; Vitoreti, Douglas; Gouvêa, Paula M P; Caldas, P G; Prioli, R; Paciornik, S; Fokine, Michael; Braga, Arthur M B; Gomes, Anderson S L; Carvalho, Isabel C S

    2012-02-27

    Materials presenting high optical nonlinearity, such as materials containing metal nanoparticles (NPs), can be used in various applications in photonics. This motivated the research presented in this paper, where morphological, linear and nonlinear optical characteristics of gold NPs on the surface of bulk soda-lime glass substrates were investigated as a function of nanoparticle height. The NPs were obtained by annealing gold (Au) thin films previously deposited on the substrates. Pixel intensity histogram fitting on Atomic Force Microscopy (AFM) images was performed to obtain the thickness of the deposited film. Image analysis was employed to obtain the statistical distribution of the average height of the NPs. In addition, absorbance spectra of the samples before and after annealing were measured. Finally, the nonlinear refractive index (n2) and the nonlinear absorption index (α2) at 800 nm were obtained before and after annealing by using the thermally managed eclipse Z-scan (TM-EZ) technique with a Ti:Sapphire laser (150 fs pulses). Results show that both n2 and α2 at this wavelength change signs after the annealing and that the samples presented a high nonlinear refractive index.

  16. Gold Induced SILICON(111) Surface Reconstructions Studied by Ultrahigh Vacuum Transmission Electron Microscopy

    NASA Astrophysics Data System (ADS)

    Plass, Richard Anton

    Due to its growing scientific and technical importance in semiconductor metallization, the Au on Si(111) system has recently drawn the attention of many researchers. Therefore, the atomic structures of two gold induced Si(111) surface reconstructions were determined using ultrahigh vacuum transmission electron microscopy. The Si(111)-(5 x 2) Au atomic structure was determined using a combination of off-zone HREM imaging, "heavy-atom holography", and chi^2 electron diffraction refinement. It contains two rows of gold atoms between expanded surface arrangements of silicon atoms. Si(111) -(5 x 2) Au passivates the surface to oxygen attack and room temperature gold deposition onto it indicates surface diffusion is important in its disordering. Transmission electron diffraction data of the Si(111)-(surd 3 x surd3)R30 ^circAu surface support the missing top layer twisted trimer model of this surface in which gold and silicon atoms in the top two layers form rotated like-atom trimers. This gold-silicon structure is quite similar to part of the Si(111)-(5 x 2) Au structure. The degree of trimer rotation and the interatomic spacings of the Si(111)-(surd3 x surd3)R30 ^circAu structure vary significantly with the sharpness of the structure's diffraction spots. These variations and large fitted Debye Waller term values indicate substantial static disorder is present. Evidence of subsurface displacements and charge transfer was also found. The presence of gold trimers is confirmed by the local symmetry seen in high resolution micrographs, which also show surface domain morphology differences between diffuse and sharp diffraction spot regions. Based on these images, models for the Si(111)-(surd3 x surd3)R30 ^circAu domain walls are proposed. Room temperature gold deposition onto the Si(111) -(surd3timessurd3)R30 ^circAu surface shows that higher order surface diffracted beams decay more quickly with coverage than lower order beams. Direct phasing analysis of this result

  17. Numerical investigation of the enhancement factor of Raman scattering using plasmonic properties of gold nanorhomb arrays

    NASA Astrophysics Data System (ADS)

    Mehrvar, L.; Dizaji, Z. V.; Tavassoli, S. H.

    2017-03-01

    Plasmonic nanostructures with sharp tips like nanorhomb array provide strong electric field enhancement and consequently meaningful Raman signal enhancement. In this study, the near-field electromagnetic enhancement of the gold nanorhomb array formed by a new proposed approach has been investigated using the finite element method (FEM). Feasibility and ease of fabrication, which are very important in practical applications, are intended in this approach. This nanorhomb array is achieved by arranging holes tangentially together in a square lattice. In other words, nanorhombs are formed by transition from nanohole to nanoparticle array. Optimization of this structure for a surface-enhanced Raman spectroscopy (SERS) substrate is performed by sweeping through the geometric parameters. The most privileged nanorhomb array substrate with highest hot spot density and EM field enhancement is obtained by calculating the enhancement factor (EF) and normalized EF (EFN) for Raman lines of pyridine. Our simulations indicate that the localized surface plasmon resonance (LSPR) mode of such nanorhomb array leads to high electromagnetic enhancement factor (EMEF) and average surface integral of field enhancement factor (\\overlineEF), which are hundreds of times greater than the nanohole arrays. It is found that this LSPR mode is thickness-dependent besides being periodicity-dependent. Finally, accurate EF is calculated by considering local incident field enhancement in terms of the excitation process and local density of states (LDOS) enhancements on emission process and then the best structure with highest EF is obtained.

  18. Gold nanorods for surface Plasmon resonance detection of mercury (II) in flow injection analysis.

    PubMed

    Trieu, Khang; Heider, Emily C; Brooks, Scott C; Barbosa, Fernando; Campiglia, Andres D

    2014-10-01

    This article investigates the flow injection analysis of mercury (II) ions in tap water samples via surface Plasmon resonance detection. Quantitative analysis of mercury (II) is based on the chemical interaction of metallic mercury with gold nanorods immobilized on a glass substrate. A new flow cell design is presented with the ability to accommodate the detecting substrate in the sample compartment of commercial spectrometers. Two alternatives are here considered for mercury (II) detection, namely stop-flow and continuous flow injection analysis modes. The best limit of detection (2.4 ng mL(-1)) was obtained with the continuous flow injection analysis approach. The accurate determination of mercury (II) ions in samples of unknown composition is demonstrated with a fortified tap water sample.

  19. Localized surface plasmon resonances in gold nano-patches on a gallium nitride substrate.

    PubMed

    D'Antonio, Palma; Inchingolo, Alessio Vincenzo; Perna, Giuseppe; Capozzi, Vito; Stomeo, Tiziana; De Vittorio, Massimo; Magno, Giovanni; Grande, Marco; Petruzzelli, Vincenzo; D'Orazio, Antonella

    2012-11-16

    In this paper we describe the design, fabrication and characterization of gold nano-patches, deposited on gallium nitride substrate, acting as optical nanoantennas able to efficiently localize the electric field at the metal-dielectric interface. We analyse the performance of the proposed device, evaluating the transmission and the electric field localization by means of a three-dimensional finite difference time domain (FDTD) method. We detail the fabrication protocol and show the morphological characterization. We also investigate the near-field optical transmission by means of scanning near-field optical microscope measurements, which reveal the excitation of a localized surface plasmon resonance at a wavelength of 633 nm, as expected by the FDTD calculations. Such results highlight how the final device can pave the way for the realization of a single optical platform where the active material and the metal nanostructures are integrated together on the same chip.

  20. Utilizing the photothermal effect for releasing molecules from the surfaces of gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Samsam Bakhtiari, Amir Bahman

    Nanomaterials, with unique physical and chemical properties, have the potential to help in the development of drug delivery systems. Some of these properties can be attributed to the nanoscale dimension of these materials. By masking, targeting, and release of a therapeutic agent, these nanomaterials can provide a delivery system that would reduce side effects. Gold nanoparticles have been studied as a candidate for the drug delivery system. These materials can be decorated with molecules that have a thermally responsive reaction (i.e., Diels-Alder). In addition, gold nanoparticles when irradiated with a right wavelength of light produce heat. Consequently, the generated heat from nanoparticles causes a retro-Diels-Alder reaction, which release a segment of molecule (i.e., payload) from gold surfaces. This controlled release mechanism is a novel method to take advantage of the properties inherent in gold nanoparticles and have the potential to be used in drug delivery system.

  1. Slanted gold mushroom array: a switchable bi/tridirectional surface plasmon polariton splitter.

    PubMed

    Shen, Yang; Fang, Guisheng; Cerjan, Alexander; Chi, Zhenguo; Fan, Shanhui; Jin, Chongjun

    2016-08-25

    Surface plasmon polaritons (SPPs) show great promise in providing an ultracompact platform for integrated photonic circuits. However, challenges remain in easily and efficiently coupling light into and subsequently routing SPPs. Here, we theoretically propose and experimentally demonstrate a switchable bi/tridirectional beam splitter which can simultaneously perform both tasks. The photonic device consists of a periodic array of slanted gold 'mushrooms' composed of angled dielectric pillars with gold caps extruding from a periodic array of perforations in a gold film. The unidirectional coupling results from the interference of the in-plane guided modes scattered by a pair of dislocated gold gratings, while the output channel is determined by the polarization of the incident beam. This device, in combination with dynamic polarization modulation techniques, has the potential to serve as a router or switch in plasmonic integrated circuits.

  2. Gold nanonetwork film on the ITO surface exhibiting one-dimensional optical properties

    PubMed Central

    2012-01-01

    A network of gold nanostructures exhibiting one-dimensional gold nanostructure properties may become a prospective novel structure for optical, electrical and catalytic applications benefited by its unusual characteristics resulting from the collective properties of individual nanostructures in the network. In this paper, we demonstrate a facile method for the formation of high-density gold nanonetwork film on the substrate surface composed of quasi-1D nanoparticles (typically fusiform) with length ca. 10 nm - via reduction of gold ions in the presence of nanoseeds attached surface, binary surfactants of cetyltrimethylammonium bromide and hexamethyleneteramine and Ag+ ions. The length of the nanonetworks can be up to ca. 100 nm, which corresponds to the aspect ratio of ca. 10. The quasi-1D gold nanostructures as well as the nanonetworks were found to be sensitive to the binary surfactants system and the Ag+ ions as they can only be formed if all the chemicals are available in the reaction. The nanonetworks exhibit unique 1D optical properties with the presence of transverse and longitudinal surface plasmon resonance absorption. Owing to their peculiar structures that are composed of small quasi-1D nanoparticles, the nanonetworks may produce unusual optical and catalytic properties, which are potentially used in surface-enhanced Raman scattering, catalysis and optical and non-linear optical applications. PMID:22587640

  3. Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species (Au11L53+, L = 1,3-bis(diphenylphosphino)propane) which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (TOF-SIMS) it is demonstrated that the Au11L53+ cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-

  4. Atom and Amine Adsorption on Flat and Stepped Gold Surfaces & Structure, Stability and Spin Ordering in Manganese Sulfide Clusters

    NASA Astrophysics Data System (ADS)

    Lewoczko, April D.

    In part I, we investigate gold catalysis in the chemistry of organonitrogen compounds. We examine the adsorption of oxygen, nitrogen and sulfur atoms on the gold (111), (100) and (211) surfaces using density functional theory (DFT). Sulfur atoms bind most strongly, followed by oxygen and nitrogen atoms with stronger adsorption for greater coordination to the surface. We see a trend of stronger adsorption to undercoordinated gold, but find it is non-universal with the adsorption strength trend: (111) > (211) > (100). We consider the diffusion of oxygen, nitrogen and sulfur adatoms and find facile long-range diffusion of oxygen atoms on the (100) surface. Lastly, we compare the adsorption of methylamine on gold to that of a selection of alkylamines, methanol and methanethiol. In each case, the ontop site is preferred with stronger adsorption at low coordinated gold. At oxygen atom coverages of 0.125 -- 0.25 ML on Au (111), we find cooperative adsorption of methylamine and oxygen atoms. Energetic costs for adsorbate tilt from the surface normal and rotation about the gold-nitrogen bond are calculated. While methylamine rotation is barrierless on the (111) and (211) surfaces, it has a low energetic barrier for the 0.125 ML and 0.25 ML O atom pre-covered Au (111) surfaces. In part II, we interpret the experimental mass spectrum of small gas phase manganese sulfide clusters using DFT and elucidate the role of ionicity and spin ordering in sizes with special stability, i.e. magic clusters. We first consider nine low lying minima (MnS)6 structures and reveal antiferromagnetic (AFM) spin ordering with a ˜0.1 eV/pair AFM energy benefit and a ˜0.1 A shrinkage of average Mn-Mn distances over clusters with ferromagnetic (FM) spin ordering. We calculate energetic barriers for interconversion between the two lowest lying (MnS)6 isomers and predict an elevated cluster melting temperature due to increased configurational entropy in a pre-melted state. Second, we demonstrate the

  5. Preparation, Surface Properties, and Therapeutic Applications of Gold Nanoparticles in Biomedicine.

    PubMed

    Panahi, Yunes; Mohammadhosseini, Majid; Nejati-Koshki, Kazem; Abadi, Azam Jafari Najaf; Moafi, Hadi Fallah; Akbarzadeh, Abolfazl; Farshbaf, Masoud

    2017-02-01

    Gold nanoparticles (AuNPs) due to their unique properties and manifold surface functionalities have been applied in bio-nanotechnology. The application of GNPs in recent medical and biological research is very extensive. Especially it involves applications such as detection and photothermalysis of microorganisms and cancer stem cells, biosensors; optical bio-imaging and observing of cells and these nanostructures also serve as practical platforms for therapeutic agents. In this review we studied all therapeutic applications of gold nanoparticles in biomedicine, synthesis methods, and surface properties.

  6. Anchoring gold nanoparticles onto a mica surface by oxygen plasma ashing for sequential nanocomponent assembly

    NASA Astrophysics Data System (ADS)

    Takagi, Akihiko; Ojima, Kaoru; Mikamo, Eriko; Matsumoto, Takuya; Kawai, Tomoji

    2007-01-01

    Water-soluble gold nanoparticles were immobilized in both polar (water) and nonpolar (chloroform) liquids on hydrophilic mica surface by oxygen plasma ashing. It is then demonstrated that a DNA with a thiol at an extremity is attached to the immobilized nanoparticles due to the gold-thiol coupling and stretched in the flow direction of the following water rinse. This technique allows a sequential integration of nanoparticles and molecules for various solutions, since the nanoparticles remain on a solid surface rather than dissolve into the solution.

  7. Multichannel biosensing platform of surface-immobilized gold nanospheres for linear and nonlinear optical imaging.

    PubMed

    Tsuboi, Kazuma; Fukuba, Shinya; Naraoka, Ryo; Fujita, Katsuhiko; Kajikawa, Kotaro

    2007-07-10

    What we believe to be a new label-free multichannel biosensing platform is proposed. It is composed of surface-immobilized gold nanospheres (SIGNs) above a gold surface with a nanogap supported by a merocyanine self-assembled monolayer. The circular SIGN spots with a diameter of 120 microm were arrayed for multichannel biosensing on a glass slide. Two kinds of sensing methods were examined: One is a reflectivity measurement of a blue ray and the other is a second-harmonic generation measurement. It was found that the SIGN system can be used as a promising platform for multichannel biosensing in both sensing methods.

  8. Efficient Coupling and Transport of a Surface Plasmon at 780 nm in a Gold Nanostructure

    SciTech Connect

    Gong, Yu; Joly, Alan G.; El-Khoury, Patrick Z.; Hess, Wayne P.

    2015-08-28

    We studied plasmonic nanostructures in single-crystal gold with scanning electron and femtosecond photoemission electron microscopies. We designed an integrated laser coupling and nanowire waveguide structure by focused ion beam lithography in single-crystal gold flakes. The photoemission results show that the laser field is efficiently coupled into a propagating surface plasmon by a simple hole structure and propagates efficiently in an adjacent nano-bar waveguide. A strong local field is created by the propagating surface plasmon at the nano-bar tip. A similar structure, with a decreased waveguide width and thickness, displayed significantly more intense photoemission indicating enhanced local electric field at the sharper tip.

  9. Electroless-plated gold films for sensitive surface plasmon resonance detection of white spot syndrome virus.

    PubMed

    Lei, Yun; Chen, Hongyu; Dai, Heping; Zeng, Zhaorui; Lin, Yi; Zhou, Feimeng; Pang, Daiwen

    2008-02-28

    The paper describes the rapid and label-free detection of the white spot syndrome virus (WSSV) using a surface plasmon resonance (SPR) device based on gold films prepared by electroless plating. The plating condition for obtaining films suitable for SPR measurements was optimized. Gold nanoparticles adsorbed on glass slides were characterized by transmission electron microscopy (TEM). Detection of the WSSV was performed through the binding between WSSV in solution and the anti-WSSV single chain variable fragment (scFv antibody) preimmobilized onto the sensor surface. Morphologies of the as-prepared gold films, gold films modified with self-assembled alkanethiol monolayers, and films covered with antibody were examined using an atomic force microscope (AFM). To demonstrate the viability of the method for real sample analysis, WSSV of different concentrations present in a shrimp hemolymph matrix was determined upon optimizing the surface density of the antibody molecules. The SPR device based on the electroless-plated gold films is capable of detecting concentration of WSSV as low as 2.5 ng/mL in 2% shrimp hemolymph, which is one to two orders of magnitude lower than the level measurable by enzyme-linked immunosorbant assays.

  10. Effect of gold immersion time on the electrochemical migration property of electroless nickel/immersion gold surface finishing.

    PubMed

    Bui, Q V; Yoon, Jeong-Won; Jung, Seung-Boo

    2012-04-01

    In this study, the electrochemical performance of an electroless nickel/immersion gold (ENIG) surface finish was evaluated as a function of the Au immersion time by the water immersion migration test. As the Au plating time increased, the electroless nickel phosphorous (EN-P) changed from amorphous to crystalline and then increased in crystallinity. X-ray diffraction (XRD) was used to evaluate the crystallinity of the plating layer. The electrical resistance of the electrodes was tracked as the sample was immersed in water with a 5 V bias. The microstructures of the electrodes after the electrochemical migration test were observed by using secondary electron microscopy (SEM) and energy dispersive spectroscopy (EDS). As the Au immersion time increased, the EN-P's crystallinity and Au thickness increased. This enhanced the electrochemical migration protection of the surface finish layer.

  11. Microstructural and surface characterization of thin gold films on n-Ge (1 1 1)

    NASA Astrophysics Data System (ADS)

    Nel, J. M.; Chawanda, A.; Auret, F. D.; Jordaan, W.; Odendaal, R. Q.; Hayes, M.; Coelho, S.

    2009-12-01

    Thin gold films were fabricated by vacuum resistive deposition on the n-Ge (1 1 1) wafers. The films were annealed between 300 and 600 °C. These resulting thin films were then characterised using scanning electron microscopy (field emission and back-scattering modes), Rutherford back scattering spectroscopy and time of flight secondary ion mass spectroscopy (TOF-SIMS). For temperatures below the eutectic temperature the distribution of both the gold and the germanium on the surface are uniform. Above the eutectic temperature, the formation of gold rich islands on the surface of the Germanium were observed. These changes in the microstructure were found to correspond to changes in the electrical characteristics of the diodes.

  12. Targeting and molecular imaging of HepG2 cells using surface-functionalized gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Rathinaraj, Pierson; Lee, Kyubae; Choi, Yuri; Park, Soo-Young; Kwon, Oh Hyeong; Kang, Inn-Kyu

    2015-07-01

    Mercaptosuccinic acid (M)-conjugated gold nanoparticles (GM) were prepared and characterized by transmission electron microscope and dynamic light scattering. M was used to improve the monodispersity and non-specific intracellular uptake of nanoparticles. Lactobionic acid (L) was subsequently conjugated to the GM to target preferentially HepG2 cells (liver cancer cells) that express asialoglycoprotein receptors (ASGPR) on their membrane surfaces and facilitate the transit of nanoparticles across the cell membrane. The mean size of lactobionic acid-conjugated gold nanoparticle (GL) was approximately 10 ± 0.2 nm. Finally, the Atto 680 dye (A6) was coupled to the nanoparticles to visualize their internalization into HepG2 cells. The interaction of surface-modified gold nanoparticles with HepG2 cells was studied after culturing cells in media containing the GM or L-conjugated GM (GL).

  13. Gold nanodome-patterned microchips for intracellular surface-enhanced Raman spectroscopy.

    PubMed

    Wuytens, Pieter C; Subramanian, Ananth Z; De Vos, Winnok H; Skirtach, Andre G; Baets, Roel

    2015-12-21

    While top-down substrates for surface-enhanced Raman spectroscopy (SERS) offer outstanding control and reproducibility of the gold nanopatterns and their related localized surface plasmon resonance, intracellular SERS experiments heavily rely on gold nanoparticles. These nanoparticles often result in varying and uncontrollable enhancement factors. Here we demonstrate the use of top-down gold-nanostructured microchips for intracellular sensing. We develop a tunable and reproducible fabrication scheme for these microchips. Furthermore we observe the intracellular uptake of these structures, and find no immediate influence on cell viability. Finally, we perform a proof-of-concept intracellular SERS experiment by the label-free detection of extraneous molecules. By bringing top-down SERS substrates to the intracellular world, we set an important step towards time-dependent and quantitative intracellular SERS.

  14. Surface plasmon enhanced heating of gold nanoparticles: A plasmonic optical switch

    NASA Astrophysics Data System (ADS)

    Evans, Philip G.

    Recent work by Lereu et al. (Appl. Phys. Lett. Vol. 86, 154101, 2005) demonstrates a method of all-optical transfer of modulation signals using surface plasmon excitation on thin gold films. Localized heating of the film, resulting from surface plasmon decay, alter the optical properties of the device. A similar optical modulation method is now presented using gold nanoparticles. Computational models are used to generate realistic values of the thermo-optical response of gold and the thermal dynamics of a hot nanoparticle-substrate device. Differential pump-probe reflectivity measurements were perferomed and demonstrate modulation frequencies of upto 10kHz, an improvement of two orders of magnitude over the thin-film device. Sample fabrication techniques using physical vapor deposition and interference lithography, and heat transport on the nanoscale are also discussed.

  15. Optimization of second harmonic generation of gold nanospheres and nanorods in aqueous solution: the dominant role of surface area.

    PubMed

    Ngo, Hoang Minh; Nguyen, Phuong Phong; Ledoux-Rak, Isabelle

    2016-01-28

    Size and shape of gold nanoparticles (AuNPs) have a strong influence on their second order nonlinear optical properties. In this work, we propose a systematic investigation of surface and shape effects in the case of small gold nanoparticles. Colloidal solutions on AuNPs with different sizes and shapes have been synthesized, i.e. nanospheres (diameters 3.0; 11.6; 15.8; 17.4; 20.0 and 43 nm) and nanorods (aspect ratios 1.47; 1.63 and 2.30). The first hyperpolarizability β values of these AuNPs have been measured by harmonic light scattering (HLS) at 1064 nm. For nanospheres and nanorods, we found that their β values are governed by a purely local, dipolar contribution, as confirmed by their surface area dependence. As an important consequence of these surface effects, we have revisited the previously reported aspect ratio dependence of β values for gold nanorods, and evidenced the predominant influence of nanoparticle area over aspect ratio considerations.

  16. In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles.

    PubMed

    Hernández, J; Solla-Gullón, J; Herrero, E; Feliu, J M; Aldaz, A

    2009-04-01

    Gold nanoparticles of different shapes/surface structures were synthesized and electrochemically characterized. An in-situ surface characterization of the Au nanoparticles, which was able to obtain qualitative information about the type and relative sizes of the different facets present in the surface of the Au nanoparticles, was carried out by using Pb Under Potential Deposition (UPD) in alkaline solutions as a surface sensitive tool. The results obtained show that the final atomic arrangement on the surface can be different from that expected from the bulk structure of the well-defined shape Au nanoparticles. In this way, the development of precise in-situ methods to measure the distribution of the different sites on the nanoparticle surface, as lead UPD on gold surfaces, is highlighted. Oxygen Reduction Reaction (ORR) was performed on the different Au nanoparticles. In agreement with the particular sensitivity of the oxygen reduction to the presence of Au(100) surface domains, cubic Au nanoparticles show much better electrocatalytic activity for ORR than small spherical particles and long nanorods, in agreement with the presence of a great fraction of (100) terrace sites on the surface of cubic gold nanoparticles.

  17. Findings on the interaction of the antimicrobial peptide cecropin-melittin with a gold surface from molecular dynamics studies.

    PubMed

    Ferreira, André F; Rai, Akhilesh; Ferreira, Lino; Simões, Pedro N

    2017-04-01

    The immobilization of gold nanoparticles (AuNPs) with antimicrobial peptides (AMPs) is a new and promising way to enhance both the activity and targeting capabilities of AMPs. However, a full understanding of the adsorption process underlying these materials is still lacking. Cecropin-melittin is a peptide with a broad antimicrobial activity while displaying low hemolytic properties, whose conjugation with AuNPs has not been studied before. In this context, we report the investigation of the adsorption process of the cecropin-melittin peptide, with (CM-SH) and without (CM) cysteine at its C-terminus, onto a gold surface based on all-atom MD simulations. Our results show that the way the peptides approach the surface dictates the final conformation and the time required to achieve it in both CM-SH and CM cases. Most important, it is demonstrated that the presence of cysteine promotes a faster conformational stabilization during the lockdown regime of the CM-SH peptide, noticeably affecting this by acting as a preferential anchoring point. This investigation represents a first step in rationalizing, with atomistic detail, some experimentally observed features of CM-SH and CM immobilized gold nanoparticles.

  18. Gold nanomolecules: Developing synthetic protocols, characterization and investigating the ligand effects on structure and properties

    NASA Astrophysics Data System (ADS)

    Nimmala, Praneeth Reddy

    The term "Nano" in chemistry refers to particles/molecules in the size range 1 to 100 nm. Gold nanoparticles were used in ancient times in making decorative glass as they produce vibrant, size dependent, colors upon interaction with light. Gold is a preferred choice of metal for the synthesis of nanoparticles mainly due to its inertness to atmospheric conditions and most chemicals. Gold thiolate nanomolecules, which is the primary focus of this dissertation research, are chemical molecules with a fixed number of gold atoms and organo-thiolate ligands. They are of the form Aux(SR)y and possess molecule-like properties as a result of distinctive quantum confinement effects occurring at the nanoscale size. The optical and electronic properties of these molecules change as a function of "x" and "y" in the formulation Aux(SR) y. The stability of these nanomolecules can be attributed due in part to their symmetrical geometry as evidenced by the X-ray crystallography. Recent research in the field has focused on exploiting the size-dependent properties of gold nanomolecules in applications like nano-electronics, biological sensing and catalysis. But much of the hindrance to these advances come from the lack of established protocols to synthesize monodisperse nanomolecules in high yields. Brust-schiffrin protocol for the synthesis of nanomolecules yields stable products in a two-phase system which can be dried and re-dispersed without affecting the stability. But the protocol has a major drawback of producing a polydisperse mixture of different sizes of nanomolecules. A major portion of my dissertation focuses on addressing this issue of polydispersity of products. In this regard, I have investigated the one-phase synthesis protocol for synthesis of gold-thiolate nanomolecules wherein the gold salt and the capping ligands are essentially dissolved in a single solvent system. This protocol is peculiar in that it yields various sizes which are otherwise not observed.

  19. In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

    2017-04-01

    Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ. In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage.

  20. Adhesion and Atomic Structures of Gold on Ceria Nanostructures: The Role of Surface Structure and Oxidation State of Ceria Supports.

    PubMed

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Ding, Kunlun; Yang, Xiaoyun; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-08-12

    We report an aberration-corrected electron microscopy analysis of the adhesion and atomic structures of gold nanoparticle catalysts supported on ceria nanocubes and nanorods. Under oxidative conditions, the as-prepared gold nanoparticles on the ceria nanocubes have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod supports. Under the reducing conditions of water-gas shift reaction, the extended gold atom layers and rafts vanish. In addition, the gold particles on the nanocubes change in morphology and increase in size while those on the nanorods are almost unchanged. The size, morphology, and atomic interface structures of gold strongly depend on the surface structures of ceria supports ((100) surface versus (111) surface) and the reaction environment (reductive versus oxidative). These findings provide insights into the deactivation mechanisms and the shape-dependent catalysis of oxide supported metal catalysts.

  1. Understanding the effect of size and shape of gold nanomaterials on nanometal surface energy transfer.

    PubMed

    Rakshit, Soumyadipta; Moulik, Satya Priya; Bhattacharya, Subhash Chandra

    2017-04-01

    Gold Nanomaterials (GNMs) interact with fluorophores via electromagnetic coupling under excitation. In this particular work we carried out (to the best of our knowledge for the first time) a comprehensive study of systematic quenching of a blue emitter 2-Anthracene Sulfonate (2-AS) in the presence of gold nanoparticles of different size and shape. We synthesized gold nanomaterials of four different dimensions [nanoparticle (0D), nanorod (1D), nanotriangle (2D) and nanobipyramids (3D)] and realized the underlying effect on the emitting dipole in terms of steady and time resolved fluorescence. Nanometal Surface Energy Transfer (NSET) has already been proved to be the best long range spectroscopic ruler so far. Many attempts have been made to understand the interaction between a fluorescent molecule and gold nanomaterials. But not a single model can interpret alone the interaction phenomena. We have opted three different models to compare the experimental and theoretical data. Due to the presence of size dependent absorptivity and dielectric function, modified CPS-Kuhn model was proved to be the worthiest to comprehend variance of behavior of an emitting dipole in close proximity to nanometal surface by coupling with the image dipole of gold nanomaterials.

  2. DFT study of the adsorption of D-(L-)cysteine on flat and chiral stepped gold surfaces.

    PubMed

    Fajín, José L C; Gomes, José R B; Cordeiro, M Natália D S

    2013-07-16

    The adsorption of cysteine onto the intrinsically chiral gold surface, Au(321)(R,S), was investigated by means of a periodic supercell density functional theory approach. The results are compared to those obtained at the same level of theory with a nonchiral surface having the same terrace orientation, the Au(111) surface. Neutral and zwitterionic cysteine forms of the L and D enantiomers are considered, as are surface coverage effects. It was found that at high coverage the zwitterionic forms of L- and D-cysteine are more stable on the Au(321)(R,S) faces of the stepped surface and also on the flat Au(111) surface, leading to highly organized cysteine monolayers. However, at low coverage the adsorption of cysteine dimers, with the pairs interacting through their carbonyl groups, is more favorable than or at least equally favorable to the adsorption of single cysteine molecules on both surfaces. A comparison between the cysteine adsorption on the two different surface structures shows that the adsorption on the stepped surface is clearly more favorable than on the flat surface, revealing the importance of the low-coordinated gold atoms in the adsorption of these species. Furthermore, non-negligible differences between the adsorption energy of the enantiomers of cysteine were found both at high and low coverage, thus showing the enantiospecificity of this intrinsically chiral surface regarding cysteine adsorption. This adsorption occurs with the cysteine binding the surface through only one contact point (by its sulfur atom), in contrast to previous work where the enantiospecific adsorption of cysteine has been related to two nonequivalent binding sites of the cysteine enantiomers with the surface.

  3. Investigation of the influence of protein corona composition on gold nanoparticle bioactivity using machine learning approaches.

    PubMed

    Papa, E; Doucet, J P; Sangion, A; Doucet-Panaye, A

    2016-07-01

    The understanding of the mechanisms and interactions that occur when nanomaterials enter biological systems is important to improve their future use. The adsorption of proteins from biological fluids in a physiological environment to form a corona on the surface of nanoparticles represents a key step that influences nanoparticle behaviour. In this study, the quantitative description of the composition of the protein corona was used to study the effect on cell association induced by 84 surface-modified gold nanoparticles of different sizes. Quantitative relationships between the protein corona and the activity of the gold nanoparticles were modelled by using several machine learning-based linear and non-linear approaches. Models based on a selection of only six serum proteins had robust and predictive results. The Projection Pursuit Regression method had the best performances (r(2) = 0.91; Q(2)loo = 0.81; r(2)ext = 0.79). The present study confirmed the utility of protein corona composition to predict the bioactivity of gold nanoparticles and identified the main proteins that act as promoters or inhibitors of cell association. In addition, the comparison of several techniques showed which strategies offer the best results in prediction and could be used to support new toxicological studies on gold-based nanomaterials.

  4. Enhanced detection sensitivity of higher-order vibrational modes of gold nanodisks on top of a GaN nanorod array through localized surface plasmons

    NASA Astrophysics Data System (ADS)

    Yang, Szu-Chi; Wei, Pei-Kuen; Hsiao, Hui-Hsin; Mante, Pierre-Adrien; Huang, Yu-Ru; Chen, I.-Ju; Chang, Hung-Chun; Sun, Chi-Kuang

    2014-11-01

    We report a method that enables the excitation of localized surface plasmons (LSPs) in a gold nanodisk array by placing each nanodisk on top of a GaN nanorod. When the rod length was much longer than the plasmon penetration depth inside the nanorod, the plasmonic field was found to be localized, and coupling between neighboring gold nanodisks was eliminated. The interaction between LSPs and acoustic vibrations in gold nanodisks was then investigated. Owing to the strong localization of the plasmonic field, weak, higher-order vibrational modes of gold nanodisk could be optically observed. Furthermore, such an LSP-based acoustic sensor could be operated at any angle of incident light. Our study not only provides an approach to excite LSPs in high-density metallic arrays, but also opens one of the possible solutions for the development of highly sensitive sub-terahertz hypersonic sensors with high angle tolerance of incident light.

  5. Influence of pH upon surface-enhanced enzyme-catalyzed luminol chemiluminescence at vicinity of nanoscale-corrugated gold and silver films.

    PubMed

    Ou, Meigui; Lu, Guowei; Shen, Hong; Descamps, Armel; Marquette, Christophe André; Blum, Loïc Jacques; Roux, Stéphane; Tillement, Olivier; Cheng, Bolin; Perriat, Pascal

    2008-01-01

    Au and Ag biochips were fabricated to investigate the influence of pH upon the chemiluminescence (CL) of luminol at vicinity of surface-adsorbed peroxidase. A nanoscaled-corrugation of the metal induces an enhancement of the luminol CL which is maximal in the pH range favoring peroxidase catalysis and greater for gold than for silver. This is the proof that, in the CL process, the reactions involving peroxidase are surface-enhanced near corrugated surfaces.

  6. Effect of Pore Size and Film Thickness on Gold-Coated Nanoporous Anodic Aluminum Oxide Substrates for Surface-Enhanced Raman Scattering Sensor

    PubMed Central

    Kassu, Aschalew; Farley, Carlton; Sharma, Anup; Kim, Wonkyu; Guo, Junpeng

    2015-01-01

    A sensitive surface enhanced Raman scattering chemical sensor is demonstrated by using inexpensive gold-coated nanoporous anodic aluminum oxide substrates. To optimize the performance of the substrates for sensing by the Surface-enhanced Raman scattering (SERS) technique, the size of the nanopores is varied from 18 nm to 150 nm and the gold film thickness is varied from 30 nm to 120 nm. The sensitivity of gold-coated nanoporous surface enhanced Raman scattering sensor is characterized by detecting low concentrations of Rhodamine 6G laser dye molecules. The morphology of the SERS substrates is characterized by atomic force microscopy. Optical properties of the nanoporous SERS substrates including transmittance, reflectance, and absorbance are also investigated. Relative signal enhancement is plotted for a range of substrate parameters and a detection limit of 10−6 M is established. PMID:26633402

  7. DNA-directed gold nanodimers with tailored ensemble surface-enhanced Raman scattering properties.

    PubMed

    Lan, Xiang; Chen, Zhong; Lu, Xuxing; Dai, Gaole; Ni, Weihai; Wang, Qiangbin

    2013-11-13

    Gold nanodimers (GNDs) are assembled with high uniformity as ideal surface-enhanced Raman scattering (SERS) substrates through DNA-directed self-assembly of gold nanoparticles. The interparticle distance within GNDs is precisely tailored on the order of a few nanometers with changing the molecule length of DNA bridge. The ensemble SERS activity of monodispersed GNDs is then rationally engineered by modifying the structural parameters of GNDs including the particle size and interparticle distance. Theoretical studies on the level of single GND evidence the particle size- and interparticle-distance-dependent SERS effects, consistent with the ensemble averaged measurements.

  8. Nonlinear effects in propagation of long-range surface plasmon polaritons in gold strip waveguides

    NASA Astrophysics Data System (ADS)

    Lysenko, Oleg; Bache, Morten; Malureanu, Radu; Lavrinenko, Andrei

    2016-04-01

    This paper is devoted to experimental and theoretical studies of nonlinear propagation of a long-range surface plasmon polariton (LRSPP) in gold strip waveguides. The plasmonic waveguides are fabricated in house, and contain a gold layer, tantalum pentoxide adhesion layers, and silicon dioxide cladding. The optical characterization was performed using a high power picosecond laser at 1064 nm. The experiments reveal two nonlinear optical effects: nonlinear power transmission and spectral broadening of the LRSPP mode in the waveguides. Both nonlinear optical effects depend on the gold layer thickness. The theoretical model of these effects is based on the third-order susceptibility of the constituent materials. The linear and nonlinear parameters of the LRSPP mode are obtained, and the nonlinear Schrödinger equation is solved. The dispersion length is much larger than the waveguides length, and the chromatic dispersion does not affect the propagation of the plasmonic mode. We find that the third-order susceptibility of the gold layer has a dominant contribution to the effective third-order susceptibility of the LRSPP mode. The real part of the effective third-order susceptibility leads to the observed spectral broadening through the self-phase modulation effect, and its imaginary part determines the nonlinear absorption parameter and leads to the observed nonlinear power transmission. The experimental values of the third-order susceptibility of the gold layers are obtained. They indicate an effective enhancement of the third-order susceptibility for the gold layers, comparing to the bulk gold values. This enhancement is explained in terms of the change of the electrons motion.

  9. XPS and NRA investigations during the fabrication of gold nanostructured functionalized screen-printed sensors for the detection of metallic pollutants

    NASA Astrophysics Data System (ADS)

    Jasmin, Jean-Philippe; Miserque, Frédéric; Dumas, Eddy; Vickridge, Ian; Ganem, Jean-Jacques; Cannizzo, Caroline; Chaussé, Annie

    2017-03-01

    An all covalent nanostructured lead sensor was built by the successive grafting of gold nanoparticles and carboxylic ligands at the surface of self-adhesive carbon screen-printed electrodes (SPEs). Surface analysis techniques were used in each step in order to investigate the structuration of this sensor. The self-adhesive surfaces were made from the electrochemical grafting of p-phenylenediamine at the surface of the SPEs via diazonium salts chemistry. The quantity of grafted aniline functions, estimated by Nuclear Reaction Analysis (NRA) performed with p-phenylenediamine labelled with 15N isotope, is in agreement with an almost complete coverage of the electrode surface. The subsequent diazotization of the aniline functions at the surface of the SPEs was performed; X-ray Photoelectron Spectroscopy (XPS) allowed us to consider a quantitative conversion of the aniline functions into diazonium moieties. The spontaneous grafting of gold nanoparticles on the as-obtained reactive surfaces ensures the nanostructuration of the material, and XPS studies showed that the covalent bonding of the gold nanoparticles at the surface of the SPEs induces a change both in the Au-4f (gold nanoparticles) and Cl-2p (carbon ink) core level signals. These unusual observations are explained by an interaction between the carbon ink constituting the substrate and the gold nanoparticles. Heavy and toxic metals are considered of major environmental concern because of their non-biodegradability. In a final step, the grafting of the carboxylic ligands at the surface of the SPEs and an accumulation step in the presence of lead(II) cations allowed us to evidence the interest of nanostructured materials as metallic pollutants sensors.

  10. Single-particle Raman measurements of gold nanoparticles used in surface-enhanced Raman scattering (SERS)-based sandwich immunoassays

    NASA Astrophysics Data System (ADS)

    Park, Hye-Young; Lipert, Robert J.; Porter, Marc D.

    2004-12-01

    The effect of particle size on the intensity of surface-enhanced Raman scattering (SERS) using labeled gold nanoparticles has been investigated. Two sets of experiments were preformed, both of which employed 632.8-nm laser excitation. The first entailed a sandwich immunoassay in which an antibody coupled to a smooth gold substrate selectively captured free-prostate specific antigen (f-PSA) from buffered aqueous solutions. The presence of captured f-PSA was then detected by the response of Raman-labeled immunogold nanoparticles with nominal diameters of 30, 40, 50, 60, or 80 nm. The resulting SERS responses were correlated to particle densities, which were determined by atomic force microscopy, by calculating the average response per particle after accounting for differences in particle surface area. This analysis showed that the magnitude of the SERS response increased with increasing particle size. The second set of experiments examined the response of individual nanoparticles. These experiments differed in that the labeled nanoparticles were coupled to the smooth gold substrate by an amine-terminated thiolate, yielding a much smaller average separation between the particles and substrate. The results revealed that particles with a diameter of ~70 nm exhibited the largest enhancement. The origin of the difference in the two sets of findings, which is attributed to the distance dependence of the plasmon coupling between the nanoparticles and underlying substrate, is briefly discussed.

  11. Dynamic Monitoring of Mechano-Sensing of Cells by Gold Nanoslit Surface Plasmon Resonance Sensor

    PubMed Central

    Wu, Shu-Han; Lee, Kuang-Li; Weng, Ruei-Hung; Zheng, Zhao-Xian; Chiou, Arthur; Wei, Pei-Kuen

    2014-01-01

    We demonstrated a real-time monitoring of live cells upon laminar shear stress stimulation via surface plasmon resonance (SPR) in gold nanoslit array. A large-area gold nanostructure consisted of 500-nm-period nanoslits was fabricated on a plastic film using the thermal-annealed template-stripping method. The SPR in the gold nanoslit array provides high surface sensitivity to monitor cell adhesion changes near the sensor surface. The human non-small cell lung cancer (CL1-0), human lung fibroblast (MRC-5), and human dermal fibroblast (Hs68) were cultured on the gold nanoslits and their dynamic responses to laminar shear stress were measured under different stress magnitudes from 0 to 30 dyne/cm2. Cell adhesion was increased in CL1-0 under shear flow stimulation. No adhesion recovery was observed after stopping the flow. On the other hand, MRC-5 and Hs68 decreased adhesion and recovered from the shear stress. The degree of recovery was around 70% for MRC-5. This device provides dynamic study and early detection of cell adhesion changes under shear flow conditions. PMID:24586846

  12. In situ controlled sputtering deposition of gold nanoparticles on MnO2 nanorods as surface-enhanced Raman scattering substrates for molecular detection.

    PubMed

    Jiang, Tao; Zhang, Li; Jin, Han; Wang, Xiaolong; Zhou, Jun

    2015-04-28

    Single-crystal tetragonal α-MnO2 nanorods with different amounts of gold nanoparticles (NPs) attached were successfully prepared by a facile sputtering deposition technique. Initially, the morphology and crystal structure of the bare α-MnO2 nanorods synthesized via a hydrothermal approach were investigated. Then, the amount of gold NPs at different sputtering times was analyzed. It was confirmed that the amount of the decorated gold NPs increased with the lengthening of the sputtering time until they completely covered the α-MnO2 nanorods. Theoretical calculation results indicated the advantages of the composite structure by showing the enhanced electromagnetic fields around both the bare α-MnO2 nanorods and the gold NP decorated ones. The surface-enhanced Raman scattering (SERS) efficiency of these nanocomposites was evaluated using methylene blue and 4-mercaptobenzoic acid as Raman probe molecules. It was found that the SERS intensity of the substrates strongly depended on the degree of aggregation of the gold NPs. Uniform SERS signals across the entire surface of these samples were obtained. Moreover, a typical chemical toxin, methyl parathion, was effectively detected over a broad concentration range from 1 × 10(-3) to 100 ppm using the gold NP decorated α-MnO2 nanorods, suggesting this hybrid structure is highly valuable for further applications on the rapid detection of organic environmental pollutants.

  13. Synthesis of gold nanoflowers using deep eutectic solvent with high surface enhanced Raman scattering properties

    NASA Astrophysics Data System (ADS)

    Aghakhani Mahyari, Farzaneh; Tohidi, Maryam; Safavi, Afsaneh

    2016-09-01

    A facile, seed-less and one-pot method was developed for synthesis of gold nanoflowers with multiple tips through reduction of HAuCl4 with deep eutectic solvent at room temperature. This solvent is eco-friendly, low-cost, non-toxic and biodegradable and can act as both reducing and shape-controlling agent. In this protocol, highly branched and stable gold nanoflowers were obtained without using any capping agent. The obtained products were characterized by different techniques including, field emission scanning electron microscopy, transmission electron microscopy, x-ray diffraction and UV-vis spectroscopy. The as-prepared gold nanoflowers exhibit efficient surface-enhanced Raman scattering (SERS) properties which can be used as excellent substrates for SERS.

  14. Candida rugosa lipase immobilization on hydrophilic charged gold nanoparticles as promising biocatalysts: Activity and stability investigations.

    PubMed

    Venditti, Iole; Palocci, Cleofe; Chronopoulou, Laura; Fratoddi, Ilaria; Fontana, Laura; Diociaiuti, Marco; Russo, Maria Vittoria

    2015-07-01

    In this work, a simple and versatile methodology to obtain two different bioconjugated systems has been developed by the immobilization of Candida rugosa lipase (CRL) on hydrophilic gold nanoparticles functionalized with 2-diethylaminoethanethiol hydrochloride (DEA) or with sodium 3-mercapto-1-propanesulfonate (3MPS), namely Au-DEA@CRL and Au-3MPS@CRL. Both spectroscopic and morphological properties of metal nanoparticles have been deeply investigated. The enzyme loading and lipolytic activity of AuNPs@CRL bioconjugates have been studied with respect to different surface functionalization and compared with the free enzyme. Some physical and chemical parameters had a strong effect on enzyme activity and stability, that were improved in the case of the Au-DEA@CRL bioconjugate, which showed a remarkable biocatalytic performance (95% of residual lipolytic activity compared with free CRL) and stability in experimental conditions concerning pH (range 5-8) and temperature (range 20-60°C), as often required for the industrial scale up of catalytic systems.

  15. Random Surface Texturing of Silicon Dioxide Using Gold Agglomerates

    DTIC Science & Technology

    2016-07-01

    photons incident on the surface of the solar cell actually end up in the active region able to convert photon energy into electrical energy . Several...mechanisms contribute to energy losses in solar cells, including heat loss, recombination loss, and reflective loss. Of those, reflection of incident...in an AR coating on solar cells. 15. SUBJECT TERMS anti-reflective, AR coatings, textured surface structures, silicon dioxide, SiO2 16. SECURITY

  16. Self-Catalyzed Carbon Dioxide Adsorption by Metal-Organic Chains on Gold Surfaces

    SciTech Connect

    Feng, Min; Sun, Hao; Zhao, Jin; Petek, Hrvoje

    2014-08-26

    Efficient capture of CO2 by chemical means requires a microscopic understanding of the interactions of the molecule-substrate bonding and adsorption-induced collective phenomena. By molecule-resolved imaging with scanning tunneling microscopy (STM), we investigate self-catalyzed CO2 adsorption on one-dimensional (1D) substrates composed of self-assembled metal-organic chains (MOCs) supported on gold surfaces. CO2 adsorption turns on attractive interchain interactions, which induce pronounced surface structural changes; the initially uniformly dispersed chains gather into close packed bundles, which are held together by highly ordered, single molecule wide CO2 ranks. CO2 molecules create more favorable adsorption sites for further CO2 adsorption by mediating the interchain attraction, thereby self-catalyzing their capture. The release of CO2 molecules by thermal desorption returns the MOCs to their original structure, indicating that the CO2 capture and release are reversible processes. The real space microscopic characterization of the self-catalyzed CO2 adsorption on 1D substrates could be exploited as platform for design of molecular materials for CO2 capture and reduction.

  17. Deep eutectic solvents for the self-assembly of gold nanoparticles: a SAXS, UV-Vis, and TEM investigation.

    PubMed

    Raghuwanshi, Vikram Singh; Ochmann, Miguel; Hoell, Armin; Polzer, Frank; Rademann, Klaus

    2014-06-03

    In this work, we report the formation and growth mechanisms of gold nanoparticles (AuNPs) in eco-friendly deep eutectic solvents (DES; choline chloride and urea). AuNPs are synthesized on the DES surface via a low-energy sputter deposition method. Detailed small angle X-ray scattering (SAXS), UV-Vis, and cryogenic transmission electron microscopy (cryo-TEM) investigations show the formation of AuNPs of 5 nm diameter. Data analysis reveals that for a prolonged gold-sputtering time there is no change in the size of the particles. Only the concentration of AuNPs increases linearly in time. More surprisingly, the self-assembly of AuNPs into a first and second shell ordered system is observed directly by in situ SAXS for prolonged gold-sputtering times. The self-assembly mechanism is explained by the templating nature of DES combined with the equilibrium between specific physical interaction forces between the AuNPs. A disulfide-based stabilizer, bis((2-mercaptoethyl)trimethylammonium) disulfide dichloride, was applied to suppress the self-assembly. Moreover, the stabilizer even reverses the self-assembled or agglomerated AuNPs back to stable 5 nm individual particles as directly evidenced by UV-Vis. The template behavior of DES is compared to that of nontemplating solvent castor oil. Our results will also pave the way to understand and control the self-assembly of metallic and bimetallic nanoparticles.

  18. Investigation of active biomolecules involved in the nucleation and growth of gold nanoparticles by Artocarpus heterophyllus Lam leaf extract

    NASA Astrophysics Data System (ADS)

    Jiang, Xinde; Sun, Daohua; Zhang, Genlei; He, Ning; Liu, Hongyu; Huang, Jiale; Odoom-Wubah, Tareque; Li, Qingbiao

    2013-06-01

    The effects of different biomolecules in Artocarpus heterophyllus Lam leaf extract on the morphology of obtained gold nanoparticles were investigated in this study. The results indicated that reducing sugars, flavones, and polyphenols consisting of about 79.8 % dry weight of the leaf extract were mainly involved in providing the dual function of reduction and the size/shape control during the biosynthesis. The gold nanoparticles present included 64 ± 10 nm nanospheres, 131 ± 18 nm nanoflowers, and 347 ± 136 nm (edge length) nanoplates and they were synthesized using the main content of reducing sugars, flavones, and polyphenols, respectively, after they were desorbed by the AB-8 macroporous adsorption resin column. Particularly, flower-like and triangular/hexagonal gold nanoparticles with a yield more than 80 % were obtained. Possible shape-directed agents for the nucleation and growth were characterized by FTIR, it can be seen that ketones were bound on the surface of the spherical and flower-like GNPs, while both the ketones and carbonyls bound on the Au {111} plane this may have favored the formation of the twin defects, which are very essential for nanoplates' formation.

  19. Rotational invariance and double frustration in the structures of gold clusters growing around the F(s)-defected MgO (100) surface.

    PubMed

    Barcaro, Giovanni; Fortunelli, Alessandro

    2006-10-26

    The interaction of small gold clusters (Au(n), n = 1-4, 20) and a gold monolayer with the MgO (100) surface surrounding a neutral oxygen vacancy (F(s) center) is investigated using density-functional (DF) calculations. It is found that the presence of the defect modifies the interaction of gold not only with the vacancy itself, but also with the oxygen and magnesium atoms around it by increasing both the adhesion energy and the equilibrium bond distances. This is at variance with the interaction of metal atoms with the regular MgO (100) surface or the F(s) defect itself, in which an increase of the adhesion energy is associated with a shortening of the metal-surface distance. The resulting double frustration and cylindrical invariance of the metal-surface interaction cause small gold clusters growing around an F(s) nucleation center to be highly fluxional in terms both of rotational freedom and of multiple competing structural motifs. Fragmentation energies of the gold clusters are also discussed, finding that the lowest-energy pathway corresponds to the detachment of a dimer.

  20. Regenerating Titanium Ventricular Assist Device Surfaces after Gold/ Palladium Coating for Scanning Electron Microscopy

    PubMed Central

    Achneck, Hardean E.; Serpe, Michael J; Jamiolkowski, Ryan; Eibest, Leslie M.; Craig, Stephen L.; Lawson, Jeffrey H.

    2014-01-01

    Titanium is one of the most commonly used materials for implantable devices in human s. Scanning electron microscopy (SEM) serves as an important tool for imaging titanium surfaces and analyzing cells and other organic matter adhering to titanium implants. However, high-vacuum SEM imaging of a non-conductive sample requires a conductive coating on the surface. A gold/ palladium coating is commonly used and to date no method has been described to ‘clean’ such gold/ palladium covered surfaces for repeated experiments without etching the titanium itself. This constitutes a major problem with titanium based implantable devices which are very expensive and thus in short supply. Our objective was to devise a protocol to regenerate titanium surfaces after SEM analysis. In a series of experiments, titanium samples from implantable cardiac assist devices were coated with fibronectin, seeded with cells and then coated with gold/palladium for SEM analysis. X-ray photoelectron spectroscopy spectra were obtained before and after five different cleaning protocols. Treatment with aqua regia (a 1:3 solution of concentrated nitric and hydrochloric acid), with or without ozonolysis, followed by sonication in soap solution and sonication in deionized water, allowed regenerating titanium surfaces to their original state. Atomic force microscopy confirmed that the established protocol did not alter the titanium microstructure. The protocol described herein is applicable to almost all titanium surfaces used in biomedical sciences and because of its short exposure time to aqua regia, will likely work for many titanium alloys as well. PMID:19642216

  1. Catalytic and surface properties of nanocrystalline gold water gas shift catalysts

    NASA Astrophysics Data System (ADS)

    Kim, Chang Hwan

    A series of CeO2 supported gold catalysts were prepared and found to possess a high activities for the water gas shift reaction (WGS), a critical step in the production of H2 for use in petroleum refining, chemicals synthesis, and proton exchange membrane fuel cells. The deposition-precipitation method was employed in synthesizing these highly active, nanocrystalline gold catalysts. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and dynamic sorption analyses were performed to characterize the gold catalysts. While some of these catalysts were initially four times more active than a commercial Cu-based catalyst, they were susceptible to deactivation. Characterization using techniques including temperature programmed oxidation, XPS, and FT-IR indicated that the deactivation was caused primarily by blockage of the active sites by carbonates and/or formates. Formation of these carbonaceous species appeared to be facilitated by oxygen deficient sites on the ceria surface and may have been associated with hydroxyl groups formed on the nanocrystalline gold particles under the H2 rich conditions. The deactivation could be managed by conditioning the CeO2 surface or adding constituents to minimize oxygen deficiency. The catalytic activity was fully recovered by calcining the deactivated materials in flowing air at elevated temperatures. The gold catalyst was washcoated onto microporous Fe-Al alloy foams for use in a micro-channel WGS reactor. The performance of these coated foams was inferior to that of the powder catalyst; however, a two stage micro-channel WGS reactor employing the gold catalyst was sufficient for a 100 W fuel processor system.

  2. Spectroscopic and microscopic investigations of phthalocyanine aggregates on Gold(111)

    NASA Astrophysics Data System (ADS)

    Nishida, Krista Rachel Akiko

    Self-assembled organic pi systems are of interest because of their potential applications in light harvesting and electron transfer. Phthalocyanines (Pc) demonstrate desirable photonic and electronic properties, thus making them excellent candidates for functional nanostructures. The specific focus of this research has been the nanoscale aggregation of a metal-free organic dye, tetrasulfonic acid phthalocyanine (TSPc) and includes the use of UV-visible Spectroscopy, Resonance Light Scattering Spectroscopy (RLS), X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and ambient and ultra-high-vacuum Scanning Tunneling Microscopy (STM) and Scanning Tunneling Spectroscopy (STS). The UV-visible absorption studies show that TSPc aggregates upon dissolution in water and obeys Beer's Law within the concentration range of 10 -7M to 10-4M, indicating that TSPc concentration has no further effect on aggregation in aqueous solution. In addition, both ionic strength in NaCl and pH changes in the presence of NaOH, HCl or acetic acid (HAc) do affect aggregation. The RSL studies confirm these effects of pH only in the presence of HAc. The XPS studies show that the ratio of non-protonated to protonated nitrogens does not change with decreasing solution pH. STM images of TSPc deposited from pH<1 solutions reveal ordered branched web-like assemblies hundreds of nanometers in length, generally 2 nm tall and having variable widths. STM imaging shows TSPc aggregates decrease in order as pH increases. STM images of TSPc deposited from solutions with pH>10 show monolayer coverage of TSPc in salt form. High-resolution UHV-STM images of TSPc aggregates deposited from pH 0 solution on Au(111) reveal detailed coherent columnar architecture with the phthalocyanine macrocycles orientated parallel to the substrate surface. OMTS was used to identify the HOMO and LUMO of the TSPc aggregates and the results are contrasted with the same molecular states in unsubstituted metallated

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

    PubMed Central

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

    2016-01-01

    Gold nanoclusters (Au NCs) have exhibited great advantages in medical diagnostics and therapies due to their efficient renal clearance and high tumor uptake. The in vivo effects of the surface chemistry of Au NCs are important for the development of both nanobiological interfaces and potential clinical contrast reagents, but these properties are yet to be fully investigated. In this study, we prepared glutathione-protected Au NCs of a similar hydrodynamic size but with three different surface charges: positive, negative, and neutral. Their in vivo biodistribution, excretion, and toxicity were investigated over a 90-day period, and tumor uptake and potential application to radiation therapy were also evaluated. The results showed that the surface charge greatly influenced pharmacokinetics, particularly renal excretion and accumulation in kidney, liver, spleen, and testis. Negatively charged Au NCs displayed lower excretion and increased tumor uptake, indicating a potential for NC-based therapeutics, whereas positively charged clusters caused transient side effects on the peripheral blood system. PMID:27555769

  4. Investigation on micro-patterned gold-plated polymer substrate for a micro hydraulic actuator

    NASA Astrophysics Data System (ADS)

    Sundaresan, Vishnu Baba; Akle, Barbar; Leo, Donald J.

    2006-03-01

    Plants have the ability to develop large mechanical force from chemical energy available with bio-fuels. The energy released by the cleavage of a terminal phosphate ion during the hydrolysis of a bio-fuel assists the transport of ions and fluids in cellular homeostasis. Materials that develop pressure and hence strain similar to the response of plants to an external stimuli are classified as nastic materials. This new class of actuators use protein transporters as functional units to move species and result in deformation [Leo et al 2005 (Proceedings of IMECE - 06)]. The ion transporters are hydrocarbons which are formed across the cellular membranes. The membranes that house the ion transporters are aggregates of phospholipids rigidized by cytoskeleton. Reconstituting these nano-machines on a harder matrix is quintessential to build a functional device. Artificial phospholipid membranes or Biliayer lipid membranes (BLM) have poor structural integrity and do not adhere to most surfaces. Patterned arrays of pores made on Poly-propylene glycol-diacrylate (PPG-DA) substrate, a photo curable polymer was made available to us for initial design iterations for an actuator. Hydrophobicity of PPG-DA posed initial problems to support a BLM. We modified the surface of micropatterned PPG-DA membrane by gold plating it. The surface of the porous PPG-DA membranes was plated with gold (Au). A 10nm seeding layer of Au was sputtered on the surface of the membrane. Further gold was reduced onto the sputtered gold surface [Supriya et al(Langmuir 2004, 20, 8870-8876)] by suspending the samples in a solution of hydroxylamine and Hydrogen tetrachloroaurate(III) trihydrate [HAuCl4.3H2O]. This reduction process increased the thickness of the gold, enhanced its adhesion to the PPG-DA substrate and improved the shapes of the pores. This surface modification of PPG-DA helped us form stable BLM with 1-Palmitoyl-2-Oleoyl-sn-Glycero-3- [Phospho-L-Serine] (Sodium Salt) (POPS), 1-Palmitoyl-2

  5. Surface Plasmon Mediated Chemical Solution Deposition of Gold Nanoparticles on a Nanostructured Silver Surface

    SciTech Connect

    Qiu, Jingjing; Wu, Yung-Chen; Wang, Yi-Chung; Engelhard, Mark H.; McElwee-White, Lisa; Wei, Wei

    2013-01-01

    Utilizing intrinsic surface properties to direct and control nanostructure growth on a large-scale surface is fundamentally interesting and holds great technological promise. Reported here is a novel "bottom-up" approach to fabricating sub-15 nm Au nanoparticles on a nanostructured Ag surface via a liquid-phase chemical deposition by using localized surface plasmon resonance (SPR) excitation. A molecular thermometry strategy was employed to investigate the SPR-mediated photothermal heating of the Ag film on nanosphere (AgFON) substrate and measured the surface temperature to be above 230 °C, which led to an efficient decomposition of CH3AuPPh3 to form Au nanoparticles on the Ag surface. Particle sizes were tunable between 3 to 10 nm by adjusting the deposition time. Moreover, investigation of the deposition kinetics revealed that the Au nanoparticle deposition was surface-limited by the Ag substrate. This SPR-mediated chemical solution deposition (SPMCSD) strategy should be extendable to the deposition of many other materials for various applications.

  6. Investigation of Mercury Reduction in Gold Stripping Process at Elevated Temperature

    NASA Astrophysics Data System (ADS)

    Pramudya, Irawan

    Mercury is present in many gold ores. By processing these ores, there is a potential of emitting mercury to the environment. Carbon regeneration kiln stacks have been observed as one of the primary source of mercury emission into the atmosphere. Before it is recycled back into the carbon in leach (CIL) or carbon in columns (CIC), carbon used in the gold extraction process needs to be reactivated thermally. Emission of mercury can be minimized by keeping the mercury left in the carbon low before it goes to the carbon regeneration kiln stacks. The objective of this study is establishing the optimum elution conditions of mercury cyanide from loaded carbon (which includes the eluent, concentration, temperature and elution time) with respect to gold stripping. Several methods such as acid washing (UNR-100, HCl or ethanol/UNR-100) were investigated prior to the stripping process. Furthermore, conventional pressurized Zadra and modified Zadra were also studied with regards to mercury concentration in the solution and vapor state as well as maximizing the gold stripping from industrial loaded carbon. 7% UNR-100 acid washing of loaded carbon at 80°C was able to wash out approximately 90% of mercury while maintaining the gold adsorption on the carbon (selective washing). The addition of alcohol in the UNR-100 acid washing solution was able to enhance mercury washing from 90% to 97%. Furthermore, mercury stripping using conventional pressurized (cyanide-alkaline) Zadra was best performed at 80°C (minimal amount of mercury reduced and volatilized) whereas using the same process only 40% of gold was stripped, which makes this process not viable. When alcohol was added to the stripping solution, at 80°C, 95% of gold was detected in the solution while keeping the reduction and volatilization of mercury low. The outcome of this study provides a better understanding of mercury behavior during the acid washing and stripping processes so that the risk of mercury exposure and

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  8. Gold nanostructures for detection of pesticides, nitrates and drugs using Surface Enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nedyalkov, N.; Nikov, Ru.; Nikov, Ro.; Nikolov, A.; Atanasov, P.; Nakajima, Y.; Terakawa, M.; Sawczak, M.; Grochowska, K.; Sliwinski, G.

    2016-01-01

    In this work laser-assisted methods for metal nanostructures formation and their application as active substrates in Surface Enhanced Raman Spectroscopy are presented. The nanostructures are fabricated by laser processing of gold thin films deposited on low cost substrates as glass, ceramic, polymer and paper. The films are deposited by classical PLD technology. The produced films are then processed by nanosecond pulses delivered by nanosecond Nd:YAG laser system. At certain conditions the laser treatment leads to formation of discrete nanostructure on the substrate surface. Femtosecond Pulsed Laser Deposition in air is also applied for direct deposition of gold nanostructure. In another set of experiments gold nanoparticle colloids are fabricated by laser ablation of gold target in chloroform. The fabricated structures are then tested as active systems in SERS, as detection of pesticides (DDT), nitrates (NH4NO3), and drugs (Methylene blue) is demonstrated. The obtained results show that these nanostructures can be efficiently used in the detection and monitoring of materials with a high social impact.

  9. Self-assembly of gold nanoparticles on deep eutectic solvent (DES) surfaces.

    PubMed

    Raghuwanshi, V S; Ochmann, M; Polzer, F; Hoell, A; Rademann, K

    2014-08-14

    Self-assembly of gold nanoparticles was obtained by sputter deposition on DES. SAXS and TEM investigations reveal the formation of spherical nanoparticles with a mean diameter of 5 ± 0.5 nm. For extended sputtering times, the number density of AuNPs increases linearly and a very pronounced 1st and 2nd shell ordering is observed.

  10. The effect of surface symmetry on the adsorption energetics of SCH 3 on gold surfaces studied using Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Masens, C.; Ford, M. J.; Cortie, M. B.

    2005-04-01

    Adsorption of methanethiol onto the three, high symmetry gold surfaces has been studied at the density functional level using a linear combination of atomic orbitals approach. In all three cases the bond energy between the thiolate radical and surface is typical of a covalent bond, and is of the order of 40 kcal mol -1. For the (1 1 1) surface the fcc hollow site is slightly more stable than the bridge site. For the (1 0 0) surfaces the four-fold hollow is clearly the most stable, and for the reconstructed (1 1 0) surface the bridge/edge sites either side of the first layer atoms are preferred. The calculated differences in binding energy between the three surfaces indicate that the thiolate will preferentially bind to the Au(1 1 0) or (1 0 0) before (1 1 1) surface, by about 10 kcal mol -1. The (1 1 0) surface is slightly more favourable than the (1 0 0), although the energy difference is only 3 kcal mol -1. The results suggest the possibility of selectively functionalising the different facets offered by a gold nanoparticle.

  11. Surface diffusion of gold nanoclusters on Ru(0001): effects of cluster size, surface defects and adsorbed oxygen atoms.

    PubMed

    Stein, Ori; Ankri, Jonathan; Asscher, Micha

    2013-08-28

    Understanding thermal behavior of metallic clusters on their solid supports is important for avoiding sintering and aggregation of the active supported metallic particles in heterogeneous catalysis. As a model system we have studied the diffusion of gold nano-clusters on modified Ru(0001) single crystal surfaces, employing surface density grating formation via a laser induced ablation technique. Surface modifications included damage induced by varying periods of Ne(+) ion sputtering at a collision energy of 2.8 keV and the effect of pre-adsorbed oxygen on the clean, defect free ruthenium surface. High density of surface damage, obtained at long sputter times, has led to enhanced diffusivity with lower onset temperature for diffusion. It is attributed to reduced cluster-surface commensurability which gives rise to smaller effective activation energy for diffusion. The diffusion of gold nano-clusters, 2 nm in size, was found to be insensitive to the oxygen surface concentration. The adsorbed oxygen acted as an "atomic layer lubricant", reducing friction between the cluster and the underlying surface. This has led to lower diffusivity onset temperatures (150 K) of the nano-clusters, with a stronger effect on smaller clusters.

  12. Molecularly resolved images of peptide-functionalized gold surfaces by scanning tunneling microscopy.

    PubMed

    Raigoza, Annette F; Webb, Lauren J

    2012-11-28

    Peptide-terminated monolayers were formed through a Huisgen cycloaddition reaction between an α-helical peptide containing two propargylglycine unnatural functional groups 20 Å apart and an alkanethiol self-assembled monolayer (SAM) on a gold surface containing 25% surface density of reactive azide terminal groups. The azide- and peptide-terminated surfaces were imaged by scanning tunneling microscopy (STM) using a low tunneling current of 10 pA. On the peptide-terminated surface, oblong features ~30 Å long and ~20 Å wide were observed and attributed to individual surface-bound α-helical peptides oriented parallel to the gold surface. These features covered an area of the surface corresponding to a density of 0.11 ± 0.01 peptides nm(-2), compared with a theoretical density of ~0.14 peptides nm(-2) for a fully reacted surface. Finally, no evidence of peptide aggregation was observed on either short (<10 nm) or long (~100 nm) length scales.

  13. Biotin avidin amplified magnetic immunoassay for hepatitis B surface antigen detection using GoldMag nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, An; Geng, Tingting; Fu, Qiang; Chen, Chao; Cui, Yali

    2007-04-01

    Using GoldMag (Fe3O4/Au) nanoparticles as a carrier, a biotin-avidin amplified ELISA was developed to detect hepatitis B surface antigen (HBsAg). A specific antibody was labeled with biotin and then used to detect the antigen with an antibody coated on GoldMag nanoparticles by a sandwich ELISA assay. The results showed that 5 mol of biotin were surface bound per mole of antibody. The biotin-avidin amplified ELISA assay has a higher sensitivity than that of the direct ELISA assay. There is 5-fold difference between HBsAg positive and negative serum even at dilution of 1:10000, and the relative standard deviation of the parallel positive serum at dilution of 1:4000 is 5.98% (n=11).

  14. Surface enhanced Raman scattering detection of single R6G molecules on nanoporous gold films

    NASA Astrophysics Data System (ADS)

    Liu, Hongwen; Zhang, L.; Yamaguchi, Y.; Iwasaki, H.; Inouye, Y.; Xue, Q. K.; Chen, M. W.

    2011-03-01

    Detecting single molecules with high sensitivity and molecular specificity is of great practical interest in many fields such as chemistry, biology, medicine, and pharmacology. For this purpose, cheap and highly active substrates are of crucial importance. Recently, nanoporous metals (NPMs), with a three-dimensional continuous network structure and pore channels usually much smaller than the wavelength of visible light, revealed outstanding optical properties in surface enhanced Raman scattering (SERS). In this work, we further modify the nanoporous gold films by growing a high density of gold nano-tips on the surface. Extremely focused electromagnetic fields can be produced at the apex of the nano-tips, resulting in so-called hot spots. With this NPM-based and affordable substrate, single molecule-detection is achievable with ultrahigh enhancement in SERS.

  15. Surface plasmon polaritons in a composite system of porous silicon and gold

    SciTech Connect

    Vainshtein, J. S.; Goryachev, D. N.; Ken, O. S. Sreseli, O. M.

    2015-04-15

    A composite system of silicon quantum dots and gold particles with properties periodically changing along the surface (i.e., a system exhibiting the properties of a diffraction grating) is obtained by a one-step metal-assisted chemical etching. The spectral and angular dependences of the photoresponse for the composite system on single-crystal silicon are studied. The photoresponse peaks were observed, which behavior (the dependence on the parameters of the diffraction grating, wavelength and incidence angles of light) is attributed to the excitation of plasmon-polariton modes at the surface of the composite system with the diffraction grating. At the same time, the obtained values of the wave vectors for these modes are smaller than those calculated for plasmon polaritons excited at the interface between air and metal (gold) diffraction grating.

  16. pH effect on protein G orientation on gold surfaces and characterization of adsorption thermodynamics.

    PubMed

    Johnson, Blake N; Mutharasan, Raj

    2012-05-01

    The pH effect on adsorbed antibody-binding protein (protein G) orientation on gold (Au) and its adsorption thermodynamic characteristics were investigated using quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS). The adsorbed protein G orientation was measured by binding response of two antibody-antigen systems: the model bovine serum albumin (BSA) and the foodborne pathogen E. coli O157:H7. Surface coverage was not significantly affected by pH, but its orientation was. The most properly oriented protein G for antibody binding was achieved at near-neutral pH. Adsorption was verified by XPS measurements using nitrogen (N) 1s, oxygen (O) 1s, and Au 4p peak heights. Adsorption energetics were determined by van't Hoff and Langmuir kinetic analyses of adsorption data obtained at 296, 303, and 308 K. Large characteristic entropy change of protein adsorption was observed (ΔS° = 0.52 ± 0.01 kcal/mol·K). The adsorption process was not classical physisorption but exhibited chemisorption characteristics based on significant enthalpy change (ΔH° = -25 ± 6 kcal/mol).

  17. Precise modulation of gold nanorods aspect ratio based on localized surface plasmon resonance

    NASA Astrophysics Data System (ADS)

    Wen, Xiaoyan; Shuai, Huang; Min, Li

    2016-10-01

    Gold nanorods (GNRs) aspect ratio is significant to GNRs-based biomedical sensors. In this paper precise modulation of GNRs aspect ratio was realized by H2O2 oxidation based on localized surface plasmon resonance (LSPR) of GNRs. The oxidation process was studied in detail. A linear relationship was revealed between H2O2 oxidation time and the longitudinal LSPR wavelength of GNR, the latter depending on GNRs aspect ratio. Using the relationship GNRs aspect ratios could be modulated by H2O2 oxidation time. Oxidation time deduced aspect ratio was verified by transmission electron microscope (TEM) characterization and the average error is 2.92%. Influences of temperature and pH value on the modulation process were investigated. Increase in temperature (from 30 °C to 60 °C) or solution acidity (pH value from 2.6 to 1.2) facilitated the oxidation process. The proposed method is characterized by its simplicity and efficiency, and would find extensive application prospects in GNRs-based biomedical sensing fields.

  18. Evidence for surface plasmons in a liquid crystal containing gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Tiwari, Kunal; Singh, Ankit K.; Sharma, Suresh C.

    2012-12-01

    We present evidence for surface plasmons (SPs) in a nematic liquid crystal (LC) containing dispersion of gold nanoparticles (Au NPs). The evidence originates from observations of attenuated total reflection (ATR) of p-polarized laser incident upon a high-index prism/LC-Au NPs/glass structure. We argue that SPs are generated through evanescent waves interacting with Au NPs embedded in the LC and NPs' dispersing medium.

  19. Gold replica of olive branch left on moons surface by Apollo 11

    NASA Technical Reports Server (NTRS)

    1969-01-01

    A gold replica of an olive branch, the traditional symbol of peace, which was left on the Moon's surface by the Apollo 11 crew members. Astronaut Neil A. Armstrong, commander, was in charge of placing the replica (less than half a foot in length) on the Moon. The gesture represents a fresh wish for peace for all mankind. astronauts will be released from quarantine on August 11, 1969. Donald K. Slayton (right), MSC Director of Flight Crew Operations; and Lloyd Reeder, training coordinator.

  20. Sensitive surface plasmon resonance enabled by templated periodic arrays of gold nanodonuts

    NASA Astrophysics Data System (ADS)

    Dou, Xuan; Lin, Yuh-Chieh; Choi, Baeck; Wu, Kedi; Jiang, Peng

    2016-05-01

    Here we report a simple and scalable colloidal lithography technology for fabricating periodic arrays of gold nanodonuts for sensitive surface plasmon resonance (SPR) analysis. This new bottom-up approach leverages a unique polymer wetting layer between a self-assembled, non-close-packed monolayer silica colloidal crystal and a silicon substrate to template ordered gold nanodonuts with tunable geometries over wafer-sized areas. The processes involved in this templating nanofabrication approach, including spin coating, oxygen plasma etching, and metal sputtering, are all compatible with standard microfabrication technologies. Specular reflection measurements reveal that the efficient electromagnetic coupling of the incident light with the tunable SPR modes of the templated gold nanodonut arrays enables good spectral tunability. Bulk refractive index sensing experiments show that a high SPR sensitivity of ∼758 nm per refractive index unit, which outperforms many plasmonic nanostructures fabricated by both top-down and bottom-up approaches, can be achieved using the templated gold nanodonut arrays. Numerical finite-difference time-domain simulations have also been performed to complement the optical characterization and the theoretical results match well with the experimental measurements.

  1. Synthesis of gold nanorods with a longitudinal surface plasmon resonance peak of around 1250 nm

    NASA Astrophysics Data System (ADS)

    Nguyen, Thi Nhat Hang; Le Trinh Nguyen, Thi; Thanh Tuyen Luong, Thi; Thang Nguyen, Canh Minh; Nguyen, Thi Phuong Phong

    2016-03-01

    We prepared gold nanorods and joined them to chemicals such as tetrachloauric (III) acid trihydrate, silver nitrate, hydroquinone, hexadecyltrimethylammonium bromide, sodium hydroxide and sodium borohydride using the seed-mediated method. The combination of hydroquinone, with or without salicylic acid, influences the size of the gold nanorods, and this is demonstrated by the results of TEM images, UV-vis spectra and the value of the longitudinal surface plasmon resonance peak with respect to the UV-vis spectra. By changing the Ag+ ion and hydroquinone concentration and the combination of hydroquinone and salicylic acid, the size of the gold nanorods can be controlled and this is manifested by longitudinal surface plasmon resonance peaks forming between 875 and 1278 nm. In particular, sample E2 achieved a longitudinal surface plasmon peak at 1273 nm and an aspect ratio of more than 10 by modifying the hydroquinone to 2.5 mM and salicylic acid to 0.5 mM concentration in the growth solution.

  2. Influence of ceramic surface texture on the wear of gold alloy and heat-pressed ceramics.

    PubMed

    Saiki, Osamu; Koizumi, Hiroyasu; Nogawa, Hiroshi; Hiraba, Haruto; Akazawa, Nobutaka; Matsumura, Hideo

    2014-01-01

    The purpose of this study was to evaluate the influence of ceramic surface texture on the wear of rounded rod specimens. Plate specimens were fabricated from zirconia (ZrO2), feldspathic porcelain, and lithium disilicate glass ceramics (LDG ceramics). Plate surfaces were either ground or polished. Rounded rod specimens with a 2.0-mm-diameter were fabricated from type 4 gold alloy and heat-pressed ceramics (HP ceramics). Wear testing was performed by means of a wear testing apparatus under 5,000 reciprocal strokes of the rod specimen with 5.9 N vertical loading. The results were statistically analyzed with a non-parametric procedure. The gold alloy showed the maximal height loss (90.0 µm) when the rod specimen was abraded with ground porcelain, whereas the HP ceramics exhibited maximal height loss (49.8 µm) when the rod specimen was abraded with ground zirconia. There was a strong correlation between height loss of the rod and surface roughness of the underlying plates, for both the gold alloy and HP ceramics.

  3. Phosphane-stabilized gold clusters: investigation of the stability of [Au(13)(PMe (2)Ph) (10)Cl (2)] (3+).

    PubMed

    Li, Jia; Wang, Shu-Guang

    2010-03-01

    The phosphane-stabilized gold cluster [Au(13)(PMe(2)Ph)(10)Cl(2)](3+) was studied using density functional theory. The extraordinary stability of the cluster has been attributed to the stability of the gold core and the protection conferred by ligands. Here, five stability factors of the gold core were explained and verified by investigating the Au (13) (5+) core in detail. Interactions between the gold core and several PR(3) ligands (R = Me, H, I, Br, Cl, F) were investigated according to the different electron donor abilities of each ligand; bonding energy between the ligand and the gold core was found to increase with the electronegativity of the R substituent. Furthermore, two other aspects of the ligands were clarified: how the ligand stabilizes the Au (13) (5+) core, and which kind of ligand provides the best stabilization for the cluster.

  4. Facile in situ characterization of gold nanoparticles on electrode surfaces by electrochemical techniques: average size, number density and morphology determination.

    PubMed

    Wang, Ying; Laborda, Eduardo; Salter, Chris; Crossley, Alison; Compton, Richard G

    2012-10-21

    A fast and cheap in situ approach is presented for the characterization of gold nanoparticles from electrochemical experiments. The average size and number of nanoparticles deposited on a glassy carbon electrode are determined from the values of the total surface area and amount of gold obtained by lead underpotential deposition and by stripping of gold in hydrochloric acid solution, respectively. The morphology of the nanoparticle surface can also be analyzed from the "fingerprint" in lead deposition/stripping experiments. The method is tested through the study of gold nanoparticles deposited on a glassy carbon substrate by seed-mediated growth method which enables an easy control of the nanoparticle size. The procedure is also applied to the characterization of supplied gold nanoparticles. The results are in satisfactory agreement with those obtained via scanning electron microscopy.

  5. Band bending at copper and gold interfaces with ferroelectric Pb(Zr,Ti)O3 investigated by photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Apostol, Nicoleta G.; Ştoflea, Laura E.; Tănase, Liviu C.; Bucur, Ioana Cristina; Chirilă, Cristina; Negrea, Raluca F.; Teodorescu, Cristian M.

    2015-11-01

    Interfaces formed by gold and copper on single crystal layers of (0 0 1) PbZr0.2Ti0.8O3 (PZT) produced by pulsed laser deposition and exhibiting outwards polarization are analyzed by X-ray photoelectron spectroscopy. The stoichiometry of the layers reproduces reasonably that of the PZT target. The band bending occurring at the interface between PZT and the metals is investigated by analyzing the core level shifts as function on the metal deposition. It is found that for Au/PZT(0 0 1) the gold layer is not continuous and the observed band bendings can be attributed to a Schottky mechanism, whereas for Cu/PZT(0 0 1) the copper layer is continuous; in this latter case, the observed band bendings towards higher energies (lower binding energies) can be attributed to a concomitant bending due to the Schottky effect together with the disappearance of the initial bending due to the outwards polarization of the samples. Metal Pb is observed to segregate only in the case of Cu/PZT(0 0 1), therefore the surface self-reduction might also be connected to the presence of a metal with lower work function, which for larger coverage forms a continuous metal layer, able to provide electrons to the surface. High resolution transmission electron spectroscopy yielded the disappearance of the tetragonal distortion in the case of Cu/PZT(0 0 1), in line with the assumption of disappearance of the polarization-induced band bending.

  6. Sign-inverted surface stress-charge response in nanoporous gold

    NASA Astrophysics Data System (ADS)

    Jin, Hai-Jun; Parida, Smrutiranjan; Kramer, Dominik; Weissmüller, Jörg

    2008-12-01

    The surface stress-charge coefficient, ς, quantifies the response of the surface stress - a fundamental property of solid surfaces - to the addition or removal of superficial electric charge. So far, all experiments have found ς negative at clean metal surfaces. Here we report in situ dilatometry experiments on nanoporous gold samples prepared by dealloying. The results reveal a large reversible elastic contraction during the anodic part of cyclic potential scans. The behavior, which indicates an abnormal positive sign of ς, can be linked to a monolayer of strongly adsorbed oxygen formed during dealloying, and to the extraordinarily small (1-2 nm) structure scale of the material while the oxide is in place. After cathodic reduction, ς reverts to the conventional, negative sign of the clean metal surface. We discuss the sign of ς in relation to the electronic screening at metallic and oxide-covered surfaces.

  7. Morphology, stresses, and surface reactivity of nanoporous gold synthesized from nanostructured precursor alloys

    NASA Astrophysics Data System (ADS)

    Rouya, Eric

    Nanoporous metallic materials (NMMs) are generally synthesized using dealloying, whereby the more reactive component is dissolved from a homogeneous alloy in a suitable electrolyte, and the more noble metal atoms simultaneously diffuse into 3-D clusters, forming a bi-continuous network of interconnected ligaments. Nanoporous gold (NPG) in particular is a well-known NMM; it is inert, bio-compatible, and capable of developing large surface areas with 1--100nm pores. While several studies have demonstrated its potential usefulness in fuel cell and sensing devices, its structural, mechanical, and electrocatalytic properties still require further investigation, particularly if NPG is synthesized from precursor alloy films exhibiting metastable nanostructures. In this dissertation, the electrodeposition (ECD) process, microstrucural characteristics, and metatstability of Au-Ni precursor alloys are investigated. The stresses evolved during Au-Ni alloy nucleation and growth are investigated in situ and correlated with microstructural and electrochemical data in order to identify the various stress-inducing mechanisms. In situ stresses generated during Au-Ni and Au-Ag dealloying were investigated, and additionally correlated with the growth stresses. Finally, the surface area and electrocatalytic properties of NPG are characterized using a variety of electrochemical techniques. Potentiostatically electrodeposited Au1-x-Nix (x: 0--90at%) films form a continuous series of metastable solid solutions and exhibit a nanocrystalline morphology, with ˜10--20 nm grains, the size of which decreases with increasing Ni content. The formation of a metastable structure was interpreted in terms of the limited surface diffusivities of adatoms at the growing interface and atomic volume differences (˜15%). Internal stresses generated during ECD of Ni-rich films can be explained assuming a 3-D Volmer-Weber growth mode, where the stress is initially compressive, then transitions into tension

  8. Improved Efficiency of Silicon Nanoholes/Gold Nanoparticles/Organic Hybrid Solar Cells via Localized Surface Plasmon Resonance

    NASA Astrophysics Data System (ADS)

    Lu, Ronghua; Xu, Ling; Ge, Zhaoyun; Li, Rui; Xu, Jun; Yu, Linwei; Chen, Kunji

    2016-03-01

    Silicon is the most widely used material for solar cells due to its abundance, non-toxicity, reliability, and mature fabrication process. In this paper, we fabricated silicon nanoholes (SiNHS)/gold nanoparticles (AuNPS)/organic hybrid solar cells and investigated their spectral and opto-electron conversion properties. SiNHS nanocomposite films were fabricated by metal-assisted electroless etching (EE) method. Then, we modified the surface of the nanocomposite films by exposing the samples in the air. After that, polymer poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) blended with AuNPS were spin-coated on the surface of the SiNHS nanocomposite films as a hole-transporting layer. The external quantum efficiency (EQE) values of the solar cells with AuNPS are higher than that of the samples without AuNPS in the spectral region of 600-1000 nm, which were essential to achieve high performance photovoltaic cells. The power conversion efficiency (PCE) of the solar cells incorporating AuNPS exhibited an enhancement of 27 %, compared with that of the solar cells without AuNPS. We thought that the improved efficiency were attributed to localized surface plasmon resonance (LSPR) triggered by gold nanoparticles in SiNHS nanocomposite films.

  9. Chitosan-ceramide coating on gold nanorod to improve its physiological stability and reduce the lipid surface-related toxicity.

    PubMed

    Battogtokh, Gantumur; Gotov, Oyuntuya; Ko, Young Tag

    2017-03-01

    Gold nanoparticles are promising materials for many applications that include imaging, drug delivery, and photothermal therapy. However, AuNPs can be unstable and/or toxic. We purposed to improve the stability and reduce toxicity of gold nanorods (AuNR) upon coating with biocompatible polymer, chitosan-ceramide (CS-CE), without replacing the original layer, CTAB. CS-CE-coated AuNR was prepared by simple mixing for 24 h and purified by centrifugation. The coating was confirmed by UV-Vis absorption analysis and surface charge and size measurement. We prepared nanorods with CS or CS-CE coating at two different concentrations (5 and 10% AuNR), the resulting in larger nanorods with a more positive surface-charge than that of AuNR. We investigated the UV-absorption and protein adsorption of the polymer coated nanorods. Based on the protein adsorption, AuNR-CS-CE was found to be more stable under physiological conditions than AuNR-CS. The cell internalization assay revealed that Hela cells internalized higher amounts of AuNR-CS-CE than that of AuNR-CS. Cytotoxicity study revealed that AuNR-CS-CE has lower toxicity than AuNR against HeLa cells. The CS-CE coating improved the stability of AuNR under physiological conditions via the hydrophobic interactions between the AuNR lipid surface and the ceramide anchor in the CS backbone as well as.

  10. Investigating the extrinsic size effect of palladium and gold spherical nanoparticles

    NASA Astrophysics Data System (ADS)

    Rashidian Vaziri, M. R.; Omidvar, A.; Jaleh, B.; Partovi Shabestari, N.

    2017-02-01

    In many optical applications, knowing the variations of the plasmonic resonance wavelengths of a special kind of nanoparticles in terms of their size before the experiment began, can assist the users in selection of an appropriate preparation method for the optimum functionality. In this work, in order to show the role of the preparation method on the mean size and the size distribution of nanoparticles, two different chemical bottom-up and physical top-down methods were used for the synthesis of palladium and gold nanoparticles. Chemical reduction of metal salt and laser ablation in liquid media methods were respectively used for preparation of palladium and gold nanoparticles. It is shown that the chemical bottom-up method results in the formation of smaller particles with narrower size distribution. Optical properties and plasmonic resonance absorption of the prepared nanoparticles were investigated by UV-vis spectroscopy and their size distribution were determined by transmission electron microscopy (TEM) images. Using the measured size distribution of nanoparticles, their optical extinctions are modelled using the Mie theory of scattering. A comprehensive study on the extrinsic size effect of palladium and gold nanoparticles is performed and the dipolar and the quadrupolar Mie resonances in these nanoparticles are investigated in details. The reported results can be used for selecting the preparation method of these nanoparticles and for choosing the appropriate laser wavelength to excite stronger or weaker Mie resonances for specific applications.

  11. Investigation of gold nanoparticle radiosensitization mechanisms using a free radical scavenger and protons of different energies.

    PubMed

    Jeynes, J C G; Merchant, M J; Spindler, A; Wera, A-C; Kirkby, K J

    2014-11-07

    Gold nanoparticles (GNPs) have been shown to sensitize cancer cells to x-ray radiation, particularly at kV energies where photoelectric interactions dominate and the high atomic number of gold makes a large difference to x-ray absorption. Protons have a high cross-section for gold at a large range of relevant clinical energies, and so potentially could be used with GNPs for increased therapeutic effect.Here, we investigate the contribution of secondary electron emission to cancer cell radiosensitization and investigate how this parameter is affected by proton energy and a free radical scavenger. We simulate the emission from a realistic cell phantom containing GNPs after traversal by protons and x-rays with different energies. We find that with a range of proton energies (1-250 MeV) there is a small increase in secondaries compared to a much larger increase with x-rays. Secondary electrons are known to produce toxic free radicals. Using a cancer cell line in vitro we find that a free radical scavenger has no protective effect on cells containing GNPs irradiated with 3 MeV protons, while it does protect against cells irradiated with x-rays. We conclude that GNP generated free radicals are a major cause of radiosensitization and that there is likely to be much less dose enhancement effect with clinical proton beams compared to x-rays.

  12. New insights into colloidal gold flakes: structural investigation, micro-ellipsometry and thinning procedure towards ultrathin monocrystalline layers

    NASA Astrophysics Data System (ADS)

    Hoffmann, B.; Bashouti, M. Y.; Feichtner, T.; Mačković, M.; Dieker, C.; Salaheldin, A. M.; Richter, P.; Gordan, O. D.; Zahn, D. R. T.; Spiecker, E.; Christiansen, S.

    2016-02-01

    High-quality fabrication of plasmonic devices often relies on wet-chemically grown ultraflat, presumably single-crystalline gold flakes due to their superior materials properties. However, important details about their intrinsic structure and their optical properties are not well understood yet. In this study, we present a synthesis routine for large flakes with diameters of up to 70 μm and an in-depth investigation of their structural and optical properties. The flakes are precisely analyzed by transmission electron microscopy, electron backscatter diffraction and micro-ellipsometry. We found new evidence for the existence of twins extending parallel to the Au flake {111} surfaces which have been found to not interfere with the presented nanopatterning. Micro-Ellipsometry was carried out to determine the complex dielectric function and to compare it to previous measurements of bulk single crystalline gold. Finally, we used focused ion beam milling to prepare smooth crystalline layers and high-quality nanostructures with desired thickness down to 10 nm to demonstrate the outstanding properties of the flakes. Our findings support the plasmonics and nano optics community with a better understanding of this material which is ideally suited for superior plasmonic nanostructures.High-quality fabrication of plasmonic devices often relies on wet-chemically grown ultraflat, presumably single-crystalline gold flakes due to their superior materials properties. However, important details about their intrinsic structure and their optical properties are not well understood yet. In this study, we present a synthesis routine for large flakes with diameters of up to 70 μm and an in-depth investigation of their structural and optical properties. The flakes are precisely analyzed by transmission electron microscopy, electron backscatter diffraction and micro-ellipsometry. We found new evidence for the existence of twins extending parallel to the Au flake {111} surfaces which have

  13. Fabrication Localized Surface Plasmon Resonance sensor chip of gold nanoparticles and detection lipase-osmolytes interaction

    NASA Astrophysics Data System (ADS)

    Ghodselahi, T.; Hoornam, S.; Vesaghi, M. A.; Ranjbar, B.; Azizi, A.; Mobasheri, H.

    2014-09-01

    Co-deposition of RF-sputtering and RF-PECVD from acetylene gas and Au target were used to prepare sensor chip of gold nanoparticles (Au NPs). Deposition conditions were optimized to reach a Localized Surface Plasmon Resonance (LSPR) sensor chip of Au NPs with particle size less than 10 nm. The RF power was set at 180 W and the initial gas pressure was set at 0.035 mbar. Transmission Electron Microscopy (TEM) images and Atomic Force Microscopy (AFM) data were used to investigate particles size and surface morphology of LSPR sensor chip. The Au and C content of the LSPR sensor chip of Au NPs was obtained from X-ray photoelectron spectroscopy (XPS). The hydrogenated amorphous carbon (a-C:H) thin film was used as intermediate material to immobilize Au NPs on the SiO2 substrate. The interaction between two types of osmolytes, i.e. sorbitol and trehalose, with Pseudomonas cepacia lipase (PCL) were detected by the prepared LSPR biosensor chip. The detection mechanism is based on LSPR spectroscopy in which the wavelength of absorption peak is sensitive to the refractive index of the environment of the Au NPs. This mechanism eliminates the use of a probe or immobilization of PCL on the Au NPs of LSPR sensor chip. The interaction between PCL and osmolytes can change refractive index of the mixture or solution. We found that unlike to trehalose, sorbitol interacts with the PCL. This interaction increases refractive index of the PCL and sorbitol mixture. Refractive index of PCL in the presence of different concentration of sorbitol was obtained by Mie theory modeling of LSPR peaks. This modeling stated that the present LSPR sensor chip has sensitivity as high as wavelength shift of 175 nm per refractive index. Moreover, the detection of such weakly interaction between bio-molecules cannot be achieved by other analysis.

  14. Surface oxidation of gold nanoparticles supported on a glassy carbon electrode in sulphuric acid medium: contrasts with the behaviour of 'macro' gold.

    PubMed

    Wang, Ying; Laborda, Eduardo; Crossley, Alison; Compton, Richard G

    2013-03-07

    Consecutive electro-oxidation and reduction cycling of gold macroelectrodes in sulphuric acid medium is a widely-used cleaning and calibration procedure. In this paper this method is applied to electrodeposited nanoparticles revealing significant differences in the electro-oxidation process and the cleaning effectiveness. This suggests a higher density of surface defects on the nanoparticles.

  15. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    PubMed Central

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; Duchesne, Paul N.; Jiang, De-en; Mirkin, Chad A.; Zhang, Peng

    2015-01-01

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals. PMID:26153854

  16. The surface structure of silver-coated gold nanocrystals and its influence on shape control.

    PubMed

    Padmos, J Daniel; Personick, Michelle L; Tang, Qing; Duchesne, Paul N; Jiang, De-en; Mirkin, Chad A; Zhang, Peng

    2015-07-08

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver-chloride, silver-silver and silver-gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride-metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.

  17. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    SciTech Connect

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; Duchesne, Paul N.; Jiang, De-en; Mirkin, Chad A.; Zhang, Peng

    2015-07-08

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.

  18. The surface structure of silver-coated gold nanocrystals and its influence on shape control

    DOE PAGES

    Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; ...

    2015-07-08

    Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A uniquemore » approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.« less

  19. Surface modification of a gold-coated microcantilever and application in biomarker detection

    NASA Astrophysics Data System (ADS)

    Binh Pham, Van; Nhat Khoa Phan, Thanh; Nguyen, Thanh Trung; Pham, Xuan Thanh Tung; Thanh Tuyen Le, Thi; Chien Dang, Mau

    2015-12-01

    Biosensors have been rapidly developed recently. Biological receptors, such as antibodies, must be immobilized on these sensors’ surfaces to make the sensor capable of capturing a target analyte. In this research we studied how to modify a gold-coated surface of a microcantilever, a sensor with high potential in biological and medical applications. Thiol chemistry was adapted to create a cysteamine layer on a gold surface, and subsequently glutaraldehyde was used as a cross-linking agent to react with amine groups in receptors. In order to evaluate the efficiency of immobilizing protein on an Au surface and also whether the protein retains its biological activity, horseradish peroxidase enzyme (HRP) with its activity to catalyze a reaction between 2,2‧-azino-bis [3-ethylbenzothiazoline-6-sulphonic acid] (ABTS) and {{{H}}}2{{{{O}}}2}- was used as a testing protein. The result showed that HRP was immobilized successfully on cysteamine and glutaraldehyde layers and retained its activity. The cantilever’s tip deflection was also measured, and results showed that each layer created surface stress and made the cantilever bend—in particular, the cysteamine layer induced bending as high as 6 μm. An antibody of alpha-fetoprotein (AFP) was immobilized on the cantilever surface, and the measurement deflection showed that the sensor responded to solution containing AFP with concentration from 100 to 500 ng ml-1.

  20. Surface two-level state dissipation in single-crystalline gold nanomechanical resonators

    NASA Astrophysics Data System (ADS)

    Kim, Minjin; Kim, Jihwan; Kim, Jinhee; Shim, Seung-Bo; Kim, Bongsoo; Suh, Junho

    2017-02-01

    We study the intrinsic dissipation in nanomechanical resonators fabricated with synthetic singlecrystalline gold nanowires. Contrary to the etched nanostructures, the measured resonance frequencies and damping rates unambiguously demonstrate temperature dependence, as predicted by the standard two-level tunneling-state (TLS) theory. We compare the data to a model assuming a thin amorphous layer on the nanowire surface. The deduced TLS parameters are consistent with bulk poly(methyl methacrylate) (PMMA) data, confirming the presence of residual PMMA on the surface as the TLS host.

  1. Signal enhancement of surface plasmon resonance based on gold nanoparticle-antibody complex for immunoassay.

    PubMed

    Lee, Woochang; Oh, Byung-Keun; Kim, Yong-Wan; Choi, Jeong-Woo

    2006-11-01

    In the immunoassay based on surface plasmon resonance (SPR) system, the signal enhancement was done by means of the conjugate of gold (Au) nanoparticle-antibody fragment. Antibody fragment was prepared for the improved immobilization based on Au-thiol interaction. Through the ellipsometric analysis on surface, the conjugation between Au and antibody fragment was performed in the oriented manner. The optimal fabrication conditions such as concentration and incubation time were determined for the constant size of the fabricated nanoparticle-antibody conjugate. Through the plot of SPR angle difference versus antigen concentration, the linear correlation was achieved, of which the detection limit was 100 fg/ml.

  2. Finite-temperature properties of ultra-thin lead films on gold (110) surfaces

    NASA Astrophysics Data System (ADS)

    De'Bell, K.; Imeson, D.

    1997-07-01

    At low coverages, lead adatoms form a single layer on the gold (110) surface. However, if a critical coverage 0953-8984/9/27/005/img1 is exceeded, a second adlayer forms. At zero temperature, various properties such as the energy and atomic spacing of atoms in the first adlayer are discontinuous at 0953-8984/9/27/005/img1. The effects of temperature on the discontinuities and location of 0953-8984/9/27/005/img1 are reported. Results for clean Au(110) and Pb(110) surfaces are also reported.

  3. Surface Enhanced Raman Scattering (SERS) Studies of Gold and Silver Nanoparticles Prepared by Laser Ablation

    PubMed Central

    Herrera, Gloria M.; Padilla, Amira C.; Hernandez-Rivera, Samuel P.

    2013-01-01

    Gold and silver nanoparticles (NPs) were prepared in water, acetonitrile and isopropanol by laser ablation methodologies. The average characteristic (longer) size of the NPs obtained ranged from 3 to 70 nm. 4-Aminobenzebethiol (4-ABT) was chosen as the surface enhanced Raman scattering (SERS) probe molecule to determine the optimum irradiation time and the pH of aqueous synthesis of the laser ablation-based synthesis of metallic NPs. The synthesized NPs were used to evaluate their capacity as substrates for developing more analytical applications based on SERS measurements. A highly energetic material, TNT, was used as the target compound in the SERS experiments. The Raman spectra were measured with a Raman microspectrometer. The results demonstrate that gold and silver NP substrates fabricated by the methods developed show promising results for SERS-based studies and could lead to the development of micro sensors.

  4. Fabrication of gold nanorods with tunable longitudinal surface plasmon resonance peaks by reductive dopamine.

    PubMed

    Su, Gaoxing; Yang, Chi; Zhu, Jun-Jie

    2015-01-20

    Hydroxyphenol compounds are often used as reductants in controlling the growth of nanoparticles. Herein, dopamine was used as an effective reductant in seed-mediated synthesis of gold nanorods (GNRs). The as-prepared GNRs (83 × 16 nm) were monodisperse and had a high degree of purity. The conversion ratio from gold ions to GNRs was around 80%. In addition, dopamine worked as an additive. At a very low concentration of hexadecyltrimethylammonium bromide (CTAB; 0.025 M), thinner and shorter GNRs (60 × 9 nm) were successfully prepared. By regulating the concentration of silver ions, CTAB, seeds, and reductant, GNRs with longitudinal surface plasmon resonance (LSPR) peaks ranging from 680 to 1030 nm were synthesized. The growth process was tracked using UV-vis-NIR spectroscopy, and it was found that a slow growth rate was beneficial to the formation of GNRs.

  5. Probing the effect of surface chemistry on the electrical properties of ultrathin gold nanowire sensors.

    PubMed

    Kisner, Alexandre; Heggen, Marc; Mayer, Dirk; Simon, Ulrich; Offenhäusser, Andreas; Mourzina, Yulia

    2014-05-21

    Ultrathin metal nanowires are ultimately analytical tools that can be used to survey the interfacial properties of the functional groups of organic molecules immobilized on nanoelectrodes. The high ratio of surface to bulk atoms makes such ultrathin nanowires extremely electrically sensitive to adsorbates and their charge and/or polarity, although little is known about the nature of surface chemistry interactions on metallic ultrathin nanowires. Here we report the first studies about the effect of functional groups of short-chain alkanethiol molecules on the electrical resistance of ultrathin gold nanowires. We fabricated ultrathin nanowire electrical sensors based on chemiresistors using conventional microfabrication techniques, so that the contact areas were passivated to leave only the surface of the nanowires exposed to the environment. By immobilizing alkanethiol molecules with head groups such as -CH3, -NH2 and -COOH on gold nanowires, we examined how the charge proximity due to protonation/deprotonation of the functional groups affects the resistance of the sensors. Electrical measurements in air and in water only indicate that beyond the gold-sulfur moiety interactions, the interfacial charge due to the acid-base chemistry of the functional groups of the molecules has a significant impact on the electrical resistance of the wires. Our data demonstrate that the degree of dissociation of the corresponding functional groups plays a major role in enhancing the surface-sensitive resistivity of the nanowires. These results stress the importance of recognizing the effect of protonation/deprotonation of the surface chemistry on the resulting electrical sensitivity of ultrathin metal nanowires and the applicability of such sensors for studying interfacial properties using electrodes of comparable size to the electrochemical double layer.

  6. Investigation of Sub-100 nm Gold Nanoparticles for Laser-Induced Thermotherapy of Cancer

    PubMed Central

    Leung, Jennifer P.; Wu, Sherry; Chou, Keng C.; Signorell, Ruth

    2013-01-01

    Specialized gold nanostructures are of interest for the development of alternative treatment methods in medicine. Photothermal therapy combined with gene therapy that supports hyperthermia is proposed as a novel multimodal treatment method for prostate cancer. In this work, photothermal therapy using small (<100 nm) gold nanoparticles and near-infrared (NIR) laser irradiation combined with gene therapy targeting heat shock protein (HSP) 27 was investigated. A series of nanoparticles: nanoshells, nanorods, core-corona nanoparticles and hollow nanoshells, were synthesized and examined to compare their properties and suitability as photothermal agents. In vitro cellular uptake studies of the nanoparticles into prostate cancer cell lines were performed using light scattering microscopy to provide three-dimensional (3D) imaging. Small gold nanoshells (40 nm) displayed the greatest cellular uptake of the nanoparticles studied and were used in photothermal studies. Photothermal treatment of the cancer cell lines with laser irradiation at 800 nm at 4 W on a spot size of 4 mm (FWHM) for 6 or 10 min resulted in an increase in temperature of ~12 °C and decrease in cell viability of up to 70%. However, in vitro studies combining photothermal therapy with gene therapy targeting HSP27 did not result in additional sensitization of the prostate cancer cells to hyperthermia.

  7. Below melting point photothermal reshaping of single gold nanorods driven by surface diffusion.

    PubMed

    Taylor, Adam B; Siddiquee, Arif M; Chon, James W M

    2014-12-23

    Plasmonic gold nanorod instability and reshaping behavior below melting points are important for many future applications but are yet to be fully understood, with existing nanoparticle melting theories unable to explain the observations. Here, we have systematically studied the photothermal reshaping behavior of gold nanorods irradiated with femtosecond laser pulses to report that the instability is driven by curvature-induced surface diffusion rather than a threshold melting process, and that the stability dramatically decreases with increasing aspect ratio. We successfully utilized the surface diffusion model to explain the observations and found that the activation energy for surface diffusion was dependent on the aspect ratio of the rods, from 0.6 eV for aspect ratio of 5 to 1.5 eV for aspect ratio less than 3. This result indicates that the surface atoms are much easier to diffuse around in larger aspect ratio rods than in shorter rods and can induce reshaping at any given temperature. Current plasmonics and nanorod applications with the sharp geometric features used for greater field enhancement will therefore need to consider surface diffusion driven shape change even at low temperatures.

  8. Light wavelength influence on surface plasmon resonance in citrate-gold nanosystems

    NASA Astrophysics Data System (ADS)

    Lupusoru, Raoul-Vasile; Pricop, Daniela A.; Andries, Maria; Creanga, Dorina

    2016-12-01

    Citrate-gold particles were yielded according to classical method of auric salt reduction in two different synthesis media aiming to use them further applications in biomedical and environmental domains. The analysis of citrate-gold interaction was done through UV-vis and IR spectroscopy as well as by Transmission Electron Microscopy (TEM) and Dark Field (DF) Microscopy. Average particle size was higher for citrate-gold NPs synthesized with NaOH (32.5 nm) than for NPs synthesized with NaCl (15 nm). Dimensional histograms of one year aged colloidal suspensions presented mean size of 29 nm and respectively 18 nm. The influence of 90 min light exposure, analyzed by UV-vis, evidenced that for both NaOH synthesis protocol and NaCl protocol, plasmon band maxima at 528 nm and respectively 538 nm didn't changed, neither for white nor for green light. For one year aged samples this band shifted to 540 nm for green light irradiation in the case of citrate-gold NPs synthesized with NaOH. Also, for these NPs, both green and white light exposures resulted in plasmon band intensity changes for native as well as for aged samples. FTIR investigation showed also different changes at the level of the intensity of main vibration bands of citrate-gold after exposure to light, suggesting stronger adsorption of citrate in the case of NaCl addition in the initial reaction medium than in the case of NaOH. Finally, the utilization of NaCl in the synthesis protocol seems to favor the synthesis of more stable and lower toxicity colloidal suspensions, both during time and under the light irradiation.

  9. Location and identification of colloidal gold particles on the cell surface with a scanning electron microscope and energy dispersive analyzer

    SciTech Connect

    Eskelinen, S.; Peura, R.

    1988-09-01

    The use of colloidal gold particles for locating cell surface components by scanning electron microscopy (SEM) has been restricted due to difficulties in the identification of these gold particles under SEM. It is shown here how the gold particles bound to cell surfaces can be located and identified under SEM using the secondary electron imaging (SEI) mode with an energy dispersive X-ray microanalyzer (EDS). This enables reliable identification of gold particles and good quality micrographs of the cells to be achieved at the same time. The distribution of receptors for two lectins, concanavalin A (ConA) and wheat germ agglutinin (WGA), on the surface of cultured Raji cells and human erythrocytes is presented as an example. Raji cells and erythrocytes were fixed with glutaraldehyde, post-fixed with a glutaraldehyde-tannic acid mixture and then incubated with ConA- or WGA-coated gold particles. After dehydration and critical point drying, the specimen filters were mounted on copper stubs and coated with carbon. The cells were examined on a JEOL TEMSCAN 100CX II electron microscope. The gold particles could be identified with the EDS analyzer, which was able to detect the Au spectrum when the electron beam was focused on single gold particles using a magnification of 100,000 or more. High-resolution photographs of the same cells were obtained up to the same magnification of 100,000.

  10. Extreme ultraviolet reflection efficiencies of diamond-turned aluminum, polished nickel, and evaporated gold surfaces. [for telescope mirrors

    NASA Technical Reports Server (NTRS)

    Malina, R. F.; Cash, W.

    1978-01-01

    Measured reflection efficiencies are presented for flat samples of diamond-turned aluminum, nickel, and evaporated gold surfaces fabricated by techniques suited for EUV telescopes. The aluminum samples were 6.2-cm-diameter disks of 6061-T6, the electroless nickel samples were formed by plating beryllium disks with 7.5-microns of Kanigen. Gold samples were produced by coating the aluminum and nickel samples with 5 strips of evaporated gold. Reflection efficiencies are given for grazing angles in the 5-75 degree range. The results indicate that for wavelengths over about 100 A, the gold-coated nickel samples yield highest efficiencies. For shorter wavelengths, the nickel samples yield better efficiencies. 500 A is found to be the optimal gold thickness.

  11. High relaxivity Gd(III)-DNA gold nanostars: investigation of shape effects on proton relaxation.

    PubMed

    Rotz, Matthew W; Culver, Kayla S B; Parigi, Giacomo; MacRenaris, Keith W; Luchinat, Claudio; Odom, Teri W; Meade, Thomas J

    2015-03-24

    Gadolinium(III) nanoconjugate contrast agents (CAs) have distinct advantages over their small-molecule counterparts in magnetic resonance imaging. In addition to increased Gd(III) payload, a significant improvement in proton relaxation efficiency, or relaxivity (r1), is often observed. In this work, we describe the synthesis and characterization of a nanoconjugate CA created by covalent attachment of Gd(III) to thiolated DNA (Gd(III)-DNA), followed by surface conjugation onto gold nanostars (DNA-Gd@stars). These conjugates exhibit remarkable r1 with values up to 98 mM(-1) s(-1). Additionally, DNA-Gd@stars show efficient Gd(III) delivery and biocompatibility in vitro and generate significant contrast enhancement when imaged at 7 T. Using nuclear magnetic relaxation dispersion analysis, we attribute the high performance of the DNA-Gd@stars to an increased contribution of second-sphere relaxivity compared to that of spherical CA equivalents (DNA-Gd@spheres). Importantly, the surface of the gold nanostar contains Gd(III)-DNA in regions of positive, negative, and neutral curvature. We hypothesize that the proton relaxation enhancement observed results from the presence of a unique hydrophilic environment produced by Gd(III)-DNA in these regions, which allows second-sphere water molecules to remain adjacent to Gd(III) ions for up to 10 times longer than diffusion. These results establish that particle shape and second-sphere relaxivity are important considerations in the design of Gd(III) nanoconjugate CAs.

  12. Functionalization of gold and graphene electrodes by p-maleimido-phenyl towards thiol-sensing systems investigated by EQCM and IR ellipsometric spectroscopy

    NASA Astrophysics Data System (ADS)

    Neubert, Tilmann Joachim; Rösicke, Felix; Sun, Guoguang; Janietz, Silvia; Gluba, Marc A.; Hinrichs, Karsten; Nickel, Norbert H.; Rappich, Jörg

    2017-01-01

    Electrografting of gold and graphene surfaces by functional p-(N-maleimido)phenyl groups was performed by reduction of p-(N-maleimido)phenyldiazonium tetrafluoroborate. The reduction was carried out using cyclo voltammetry coupled with micro-gravimetric measurements by means of electrochemical quartz crystal microbalance (EQCM). The overall deposited mass on gold was higher than on graphene. However, the Faradaic efficiency was lower on Au (14%) compared to graphene (22%) after the first potential scan. Subsequently, the maleimide functional groups have been tested for immobilization of terminal thiols using 2-(4-nitrobenzene)-ethane-thiol for the functionalized graphene surface and a cysteine-modified peptide for the functionalized gold surface. The functionalization by p-(N-maleimido)phenyl groups and the following thiol coupling of the particular surface was proven by infrared spectroscopic ellipsometry (IRSE). In addition, the interaction of the tetrabutylammonium and tetrafluoroborate ions present in the electrolyte with the Au and graphene electrodes was investigated by EQCM and revealed less electrostatic interaction of graphene with these ions in solution compared to the metal (Au) surface.

  13. Controlling the density and site of attachment of gold nanoparticles onto the surface of carbon nanotubes.

    PubMed

    Kumar, Suresh; Kaur, Inderpreet; Dharamvir, Keya; Bharadwaj, Lalit M

    2012-03-01

    A facile method for controlling the density and site of attachment of gold nanoparticles onto the surface of carbon nanotubes is demonstrated. Nitric acid based oxidation was carried out to create carboxylic groups exclusively at the ends of carbon nanotubes, whereas oxidation using a mixture of nitric and sulfuric acid with varied reaction time was carried out to control the population of carboxylic groups on the side walls of nanotubes. In turn, 4-aminothiophenol modified gold nanoparticles were covalently interfaced to these carboxylated multi-walled carbon nanotubes in the presence of a zero length cross-linker, 1-ethylene-3-(3-dimethylaminopropyl) carbodiimide. Raman spectroscopic results showed increase in height of disorder band with each of these successive steps, indicating the increase in degree of functionalization of the carbon nanotubes. Fourier transformed infrared spectroscopic analysis affirmed the functionalization of nanostructures and the formation of nanohybrid. Transmission electron and field emission scanning electron microscopic analysis ascertained the attachment of gold nanoparticles to the ends and side walls of the multi-walled carbon nanotubes. The new hybrid nanostructures may find applications in electronic, optoelectronic, and sensing devices.

  14. Charge carrier dynamics and surface plasmon interaction in gold nanorod-blended organic solar cell

    NASA Astrophysics Data System (ADS)

    Rana, Aniket; Gupta, Neeraj; Lochan, Abhiram; Sharma, G. D.; Chand, Suresh; Kumar, Mahesh; Singh, Rajiv K.

    2016-08-01

    The inclusion of plasmonic nanoparticles into organic solar cell enhances the light harvesting properties that lead to higher power conversion efficiency without altering the device configuration. This work defines the consequences of the nanoparticle overloading amount and energy transfer process between gold nanorod and polymer (active matrix) in organic solar cells. We have studied the hole population decay dynamics coupled with gold nanorods loading amount which provides better understanding about device performance limiting factors. The exciton and plasmon together act as an interacting dipole; however, the energy exchange between these two has been elucidated via plasmon resonance energy transfer (PRET) mechanism. Further, the charge species have been identified specifically with respect to their energy levels appearing in ultrafast time domain. The specific interaction of these charge species with respective surface plasmon resonance mode, i.e., exciton to transverse mode of oscillation and polaron pair to longitudinal mode of oscillations, has been explained. Thus, our analysis reveals that PRET enhances the carrier population density in polymer via non-radiative process beyond the concurrence of a particular plasmon resonance oscillation mode and polymer absorption range. These findings give new insight and reveal specifically the factors that enhance and control the performance of gold nanorods blended organic solar cells. This work would lead in the emergence of future plasmon based efficient organic electronic devices.

  15. Surface chemistry and structures of 1,4-phenylene diisocyanide on gold films from solution

    NASA Astrophysics Data System (ADS)

    Abuflaha, Rasha; Olson, Dustin; Bennett, Dennis W.; Tysoe, Wilfred T.

    2016-07-01

    The adsorption of 1,4-phenylene diisocyanide (PDI) is studied on gold films as a function of PDI exposure from benzene solution by a combination of attenuated total internal reflection infrared (ATR-IR) spectroscopy and conductivity measurements. The infrared spectrum found for low PDI doses exhibits a single isocyanide vibrational peak consistent with the formation of -(Au-PDI)- oligomer chains that have been identified previously on a Au(111) surface dosed in ultrahigh vacuum. Larger solution doses cause the isocyanide peaks to split into two, with the lower-frequency vibrations corresponding to a free isocyanide mode, indicating the formation of a perpendicular, vertically bonded PDI molecule. This observation also rationalizes the apparent disparity between studies of the chemistry of PDI on gold in ultrahigh vacuum and with solution dosing. Since it has been shown previously that the -(Au-PDI)- oligomer chains are capable of providing conductive linkages between gold nanoparticles on an insulating mica substrate, it was proposed that higher PDI doses from solution should cause a decrease in conductivity due to chain disruption. This effect was found experimentally, thereby providing corroborative evidence for the above conclusions.

  16. Application of Ru(bpy) 32+ in control and formation of gold surface nanostructure through oxidation-reduction cycling

    NASA Astrophysics Data System (ADS)

    Bin, Qi; Zheng, Zhikun; Yang, Xiurong

    2007-03-01

    It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy) 32+ with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy) 32+, and the surface roughness was decreasing with the increasing of Ru(bpy) 32+ concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

  17. The optical, photothermal, and facile surface chemical properties of gold and silver nanoparticles in biodiagnostics, therapy, and drug delivery

    PubMed Central

    Austin, Lauren A.; Mackey, Megan A.; Dreaden, Erik C.

    2014-01-01

    Nanotechnology is a rapidly growing area of research in part due to its integration into many biomedical applications. Within nanotechnology, gold and silver nanostructures are some of the most heavily utilized nanomaterial due to their unique optical, photothermal, and facile surface chemical properties. In this review, common colloid synthesis methods and biofunctionalization strategies of gold and silver nanostructures are highlighted. Their unique properties are also discussed in terms of their use in biodiagnostic, imaging, therapeutic, and drug delivery applications. Furthermore, relevant clinical applications utilizing gold and silver nanostructures are also presented. We also provide a table with reviews covering related topics. PMID:24894431

  18. Ultra-strong surface plasmon amplification characteristic of a spaser based on gold-silver core-shell nanorods

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Zhou, Jun; Zhang, Haopeng; Jiang, Tao; Lou, Cibo

    2015-03-01

    We proposed an efficient spaser based on gold-silver core-shell nanorods (NRs) encapsulated by an outer silica shell doped with a gain medium. The optical characteristics of the spaser were numerically simulated based on the finite element method (FEM). The results showed that the localized surface plasmon resonance (LSPR) amplification characteristics of the spaser strongly depend on the thickness of silver shell, the aspect ratio of the inner gold NRs, and the polarization direction of the incident light. And, the maximum absolute value of optical cross-section of the spaser can reach 21,824 μm2, which is about 1115, 523, and 18 times higher than that of spasers based on the gold NRs, the silver NRs, and the silver-gold core-shell NRs, respectively. The ultra-strong surface plasmon amplification characteristics of the spaser have potential applications in optical information storage, high sensitivity biochemical sensing, and medical engineering.

  19. Investigating the Toxicity, Uptake, Nanoparticle Formation and Genetic Response of Plants to Gold

    PubMed Central

    Taylor, Andrew F.; Rylott, Elizabeth L.; Anderson, Christopher W. N.; Bruce, Neil C.

    2014-01-01

    We have studied the physiological and genetic responses of Arabidopsis thaliana L. (Arabidopsis) to gold. The root lengths of Arabidopsis seedlings grown on nutrient agar plates containing 100 mg/L gold were reduced by 75%. Oxidized gold was subsequently found in roots and shoots of these plants, but gold nanoparticles (reduced gold) were only observed in the root tissues. We used a microarray-based study to monitor the expression of candidate genes involved in metal uptake and transport in Arabidopsis upon gold exposure. There was up-regulation of genes involved in plant stress response such as glutathione transferases, cytochromes P450, glucosyl transferases and peroxidases. In parallel, our data show the significant down-regulation of a discreet number of genes encoding proteins involved in the transport of copper, cadmium, iron and nickel ions, along with aquaporins, which bind to gold. We used Medicago sativa L. (alfalfa) to study nanoparticle uptake from hydroponic culture using ionic gold as a non-nanoparticle control and concluded that nanoparticles between 5 and 100 nm in diameter are not directly accumulated by plants. Gold nanoparticles were only observed in plants exposed to ionic gold in solution. Together, we believe our results imply that gold is taken up by the plant predominantly as an ionic form, and that plants respond to gold exposure by up-regulating genes for plant stress and down-regulating specific metal transporters to reduce gold uptake. PMID:24736522

  20. Gold-surface binding of molecular switches studied by Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Homenya, Patrick; Messerschmidt, Markus; Tahir, Muhammad Nawaz; Martinez, Victor; Cheng, Yajun; Gutmann, Jochen S.; Klein, Michael; Jung, Stefan; Wolff, Morris; Saadat, Reza; Nariaki, Driss; Boča, Roman; Klingelhöfer, Göstar; Tremel, Wolfgang; Renz, Franz

    2012-03-01

    The nonanuclear coordination compound [MoIV{(CN)FeIII(3-methyl-saldptn)}8]Cl4 exhibits multiple spin transitions (3-methyl-saldptn = N,N'-bis(3''-methyl-2''-hydroxy-benzyliden)-1,7-diamino-4-azaheptane). This spin crossover cluster is bound via a self-assembled monolayer onto a two dimensional array gold surface. Mössbauer spectroscopy indicates that the thermally and optically induced spin crossover of the compound is maintained. Thereby, the foundation for its potential practical application (e.g. in the field of information storage) was laid.

  1. Glycine crystallization in solution by CW laser-induced microbubble on gold thin film surface.

    PubMed

    Uwada, Takayuki; Fujii, Sho; Sugiyama, Teruki; Usman, Anwar; Miura, Atsushi; Masuhara, Hiroshi; Kanaizuka, Katsuhiko; Haga, Masa-aki

    2012-03-01

    We have developed a novel laser-induced crystallization method utilizing local heat-induced bubble/water interface. Continuous laser beam of 1064 nm is focused on a gold nanoparticles thin film surface covered with glycine supersaturated aqueous solution. Light absorption of the film due to localized plasmon resonance caused local heating at the focal position and produced a single thermal vapor microbubble, which generated thermal gradient followed by convection flow around the bubble and eventually induced glycine crystallization and growth. The crystallization mechanism is discussed by considering gathering and accumulating molecules around the bubble/water interface assisted by convection flow and temperature jump.

  2. Cytotoxicity of gold nanoparticles with different structures and surface-anchored chiral polymers.

    PubMed

    Deng, Jun; Yao, Mengyun; Gao, Changyou

    2017-02-15

    Nanoparticles (NPs) can have profound effects on cell biology. However, the potential adverse effects of gold nanoparticles (AuNPs) with different surface chirality and structures have not been elucidated. In this study, monolayers of poly(acryloyl-l(d)-valine (l(d)-PAV) chiral molecules were anchored on the surfaces of gold nanocubes (AuNCs) and nanooctahedras (AuNOs), respectively. The l-PAV-AuNCs and d-PAV-AuNCs, or the l-PAV-AuNOs and d-PAV-AuNOs, had identical physicochemical properties in terms of size, morphology and ligand density except of the reverse molecular chirality on the particle surfaces, respectively. The l-PAV capped AuNCs and AuNOs exhibited larger cytotoxicity to A549 cells than the D-PAV coated ones, and the PAV-AuNOs had larger cytotoxicity than PAV-AuNCs when being capped with the same type of enantiomers, respectively. The cytotoxicity was positively correlated with the cellular uptake amount, and thereby the production of intracellular reactive oxygen species (ROS).

  3. Stability of reference masses V: UV/ozone treatment of gold and platinum surfaces

    NASA Astrophysics Data System (ADS)

    Cumpson, Peter; Sano, Naoko

    2013-02-01

    The stability of reference masses has been a long-standing concern within the SI. More recently the requirements of potential non-artefact realizations of the kilogram have added gold and its alloys to the platinum alloys that have historically been the focus of attention. Previously we proposed UV/ozone cleaning of standard-mass surfaces to improve stability with respect to carbonaceous contamination. Since then both NPL and BIPM have constructed prototypes of UV/ozone apparatus for cleaning kilogram standards. We have therefore tested a combined solvent wash and UV/ozone procedure, UVOPS or ‘UV/ozone with pre-wash and stabilization’, on both platinum and gold surfaces. X-ray photoelectron spectroscopy (XPS) shows this to be very successful in removing even gross contamination from these noble metal surfaces. Oxidation is negligible, limited to the outermost layer of noble metal atoms, and terminates at a level that is within the uncertainty of mass comparisons at the 1 kg level. This oxide has been seen in some earlier XPS studies but not others—we show that decomposition of the oxide by x-rays at XPS energies may be responsible for this disparity.

  4. Terahertz conductivity engineering in surface decorated carbon nanotube films by gold nanoparticles.

    PubMed

    Polley, Debanjan; Patra, Animesh; Barman, Anjan; Mitra, Rajib Kumar

    2017-02-01

    We report the controllable conductivity of single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes with their surface walls decorated by gold nanoparticles (Au NPs) with varying concentration in terahertz (THz) frequency range. Colloidal Au NPs of nominal diameter ∼15  nm are synthesized by the reduction of gold chloride solution using tri-sodium citrate. A simple chemical route is followed to attach Au NPs on the surfaces of both types of carbon nanotubes (CNTs). The attachment of Au NPs on the sidewalls of CNTs is confirmed by UV-visible spectroscopy and scanning electron microscope images. THz spectroscopic measurements are carried out at room temperature in transmission geometry in the frequency range of 0.3-2.0 THz. It is found that the THz conductivity of the surface decorated SWNT composites can either be increased or decreased by ±15% than that of the as-prepared SWNT composites by carefully choosing the Au NP concentration. The conductivity variation is qualitatively explained in terms of carrier trapping potential for low Au NP density, and alternative carrier conduction pathways at higher Au NP density and analyzed with the help of a modified universal dielectric relaxation model.

  5. Gold-film coating assisted femtosecond laser fabrication of large-area, uniform periodic surface structures.

    PubMed

    Feng, Pin; Jiang, Lan; Li, Xin; Rong, Wenlong; Zhang, Kaihu; Cao, Qiang

    2015-02-20

    A simple, repeatable approach is proposed to fabricate large-area, uniform periodic surface structures by a femtosecond laser. 20 nm gold films are coated on semiconductor surfaces on which large-area, uniform structures are fabricated. In the case study of silicon, cross-links and broken structures of laser induced periodic surface structures (LIPSSs) are significantly reduced on Au-coated silicon. The good consistency between the scanning lines facilitates the formation of large-area, uniform LIPSSs. The diffusion of hot electrons in the Au films increases the interfacial carrier densities, which significantly enhances interfacial electron-phonon coupling. High and uniform electron density suppresses the influence of defects on the silicon and further makes the coupling field more uniform and thus reduces the impact of laser energy fluctuations, which homogenizes and stabilizes large-area LIPSSs.

  6. 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

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

    SciTech Connect

    Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M.; Lein, Pamela J.; Seker, Erkin

    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 interaction 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.

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

    PubMed Central

    Chapman, Christopher A. R.; Chen, Hao; Stamou, Marianna; Biener, Juergen; Biener, Monika M.; Lein, Pamela J.; Seker, Erkin

    2015-01-01

    Designing neural-electrode interfaces that maintain close physical coupling of neurons to the 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 interaction with cortical neuron-glia co-cultures, we demonstrate that the nanostructure of np-Au is achieving close physical coupling of neurons through 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 of the dealloying conditions. Our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage, and may enhance the neuron-electrode coupling through nanostructure-mediated suppression of scar tissue formation. PMID:25706691

  9. Gold sputtered Blu-Ray disks as novel and cost effective sensors for surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nieuwoudt, Michél. K.; Martin, Jacob W.; Oosterbeek, Reece N.; Novikova, Nina I.; Wang, Xindi; Malmström, Jenny; Williams, David E.; Simpson, M. C.

    2015-03-01

    Surface Enhanced Raman spectroscopy (SERS) offers sensitive and non-invasive detection of a variety of compounds as well as unparalleled information for establishing the molecular identity of both inorganic and organic compounds, not only in biological fluids but in all other aqueous and non-aqueous media. The localized hotspots produced through SERS at the solution/nanostructure interface of clustered gold or silver nano-particles enables detection levels of parts per trillion. Recent developments in advanced fabrication methods have enabled the manufacture of SERS substrates with repeatable surface nanostructures which provide reproducible quantitative analysis, historically a weakness of the SERS technique. In this paper we describe the novel use of gold sputtered Blu-Ray surfaces as SERS substrates. Blu-Ray disks provide ideal surfaces of SERS substrates with their repeatable and regular nano-gratings. We show that the unique surface features and composition of the recording surface enables the formation of gold nano-islands with nanogaps, simply through gold sputtering, and relate this to a 600 fold signal increase of the melamine Raman signal in aqueous solutions and detection to 68 ppb. Melamine is a triazine compound and appears not only as environmental contaminant in environmental groundwater but also as an adulterant in foods due to its high nitrogen content. We have shown significant SERS signal enhancements for spectra of melamine using gold-sputtered Blu-Ray disk surfaces, with reproducibility of 12%. Blu-Ray disks have a unique combination of design, surface features and composition of the recording surface which makes them ideal for preparation of SERS substrates by gold sputter-coating.

  10. Surface-Enhanced Raman Spectroscopy Study of 4-ATP on Gold Nanoparticles for Basal Cell Carcinoma Fingerprint Detection

    NASA Astrophysics Data System (ADS)

    Quynh, Luu Manh; Nam, Nguyen Hoang; Kong, K.; Nhung, Nguyen Thi; Notingher, I.; Henini, M.; Luong, Nguyen Hoang

    2016-05-01

    The surface-enhanced Raman signals of 4-aminothiophenol (4-ATP) attached to the surface of colloidal gold nanoparticles with size distribution of 2 to 5 nm were used as a labeling agent to detect basal cell carcinoma (BCC) of the skin. The enhanced Raman band at 1075 cm-1 corresponding to the C-S stretching vibration in 4-ATP was observed during attachment to the surface of the gold nanoparticles. The frequency and intensity of this band did not change when the colloids were conjugated with BerEP4 antibody, which specifically binds to BCC. We show the feasibility of imaging BCC by surface-enhanced Raman spectroscopy, scanning the 1075 cm-1 band to detect the distribution of 4-ATP-coated gold nanoparticles attached to skin tissue ex vivo.

  11. Investigation of phase separation behavior and formation of plasmonic nanocomposites from polypeptide-gold nanorod nanoassemblies.

    PubMed

    Huang, Huang-Chiao; Nanda, Alisha; Rege, Kaushal

    2012-04-24

    Genetically engineered elastin-like polypeptides (ELP) can be interfaced with cetyltrimethyl ammonium bromide (CTAB)-stabilized gold nanorods (GNRs) resulting in the formation of stable dispersions (nanoassemblies). Increasing the dispersion temperature beyond the ELP transition temperature results in phase separation and formation of solid-phase ELP-GNR matrices (nanocomposites). Here, we investigated different physicochemical conditions that influence nanocomposite formation from temperature-induced phase separation of ELP-GNR nanoassemblies. The presence of cetyltrimethyl ammonium bromide (CTAB), used to template the formation of gold nanorods, plays a significant role in the phase separation behavior, with high concentrations of the surfactant leading to dramatic enhancements in ELP transition temperature. Nanocomposites could be generated at 37 °C in the presence of low CTAB concentrations (<1.5 mM); higher concentrations of CTAB necessitated higher temperatures (60 °C) due to elevated transition temperatures. The concentration of gold nanorods, however, had minimal influence on the phase separation behavior and nanocomposite formation. Further analysis of the kinetics of nanocomposite formation using a mathematical model indicated that CTAB largely influenced the early event of coacervation of ELP-GNR nanoassemblies leading to nanocomposites, but had minimal effect on nanocomposite maturation, which is a later-stage longer event. Finally, nanocomposites prepared in the presence of low CTAB concentrations demonstrated a superior photothermal response following laser irradiation compared to those generated using higher CTAB concentrations. Our results on understanding the formation of plasmonic/photothermal ELP-GNR nanocomposites have significant implications for tissue engineering, regenerative medicine, and drug delivery.

  12. Numerical investigation of thermal response of laser-irradiated biological tissue phantoms embedded with gold nanoshells.

    PubMed

    Phadnis, Akshay; Kumar, Sumit; Srivastava, Atul

    2016-10-01

    The work presented in this paper focuses on numerically investigating the thermal response of gold nanoshells-embedded biological tissue phantoms with potential applications into photo-thermal therapy wherein the interest is in destroying the cancerous cells with minimum damage to the surrounding healthy cells. The tissue phantom has been irradiated with a pico-second laser. Radiative transfer equation (RTE) has been employed to model the light-tissue interaction using discrete ordinate method (DOM). For determining the temperature distribution inside the tissue phantom, the RTE has been solved in combination with a generalized non-Fourier heat conduction model namely the dual phase lag bio-heat transfer model. The numerical code comprising the coupled RTE-bio-heat transfer equation, developed as a part of the current work, has been benchmarked against the experimental as well as the numerical results available in the literature. It has been demonstrated that the temperature of the optical inhomogeneity inside the biological tissue phantom embedded with gold nanoshells is relatively higher than that of the baseline case (no nanoshells) for the same laser power and operation time. The study clearly underlines the impact of nanoshell concentration and its size on the thermal response of the biological tissue sample. The comparative study concerned with the size and concentration of nanoshells showed that 60nm nanoshells with concentration of 5×10(15)mm(-3) result into the temperature levels that are optimum for the irreversible destruction of cancer infected cells in the context of photo-thermal therapy. To the best of the knowledge of the authors, the present study is one of the first attempts to quantify the influence of gold nanoshells on the temperature distributions inside the biological tissue phantoms upon laser irradiation using the dual phase lag heat conduction model.

  13. Experimental Characterization of the Order-Disorder Transition of a Gold-Rich COPPER(3)-GOLD(100) Surface

    NASA Astrophysics Data System (ADS)

    Rivers, Steven B.

    The order-disorder transition of a Au-rich Cu _3Au{001 } surface has been characterized using synchrotron x-ray scattering. Cu_3Au is a prototypical system for ordering alloys which undergo a first-order bulk phase transition. The specific bulk composition of our sample is CU_{72.1}AU _{27.9}. An important advantage of x-ray scattering is that it can be used to investigate both the bulk and the near-surface region. The disorder-to-order-transformation at the surface occurs at a temperature about 15^circ C above the bulk transition temperature as revealed by x-ray measurements. Recently Lipowsky proposed a Landau -Ginzburg type model that addresses the issue of surface -induced order and disorder. The language developed in this model is useful for describing our results. However, the Hamiltonian is not general enough to treat nonstoichiometric compositions and therefore no quantitative description is possible. Antiphase domain boundaries are found to form parallel to the surface in a long-range periodic structure. This structure produces satellites in the superstructure diffraction line shapes. We analyze this phenomenon in terms of several models including the formation of a new phase, a two-phase mixture, and the interaction between the Fermi surface and the Brillouin Zone. The time dependence of the growth of the ordered domains from 10^3 to 10 ^5 seconds was investigated through the measurement of the superstructure beam profile following a quench from the disordered state to final temperatures below both the surface and bulk transition temperatures. Quenches to temperatures below the surface transition temperature resulted in power law growth. However, quenches below the bulk transition temperature resulted in domain growth that could not be described by a power law even for the longest times studied. In both cases the kinetics of the domain growth was substantially slower than that previously reported for the bulk, which is known to follow a power law with a

  14. How surface reparation prevents catalytic oxidation of carbon monoxide on atomic gold at defective magnesium oxide surfaces.

    PubMed

    Töpfer, Kai; Tremblay, Jean Christophe

    2016-07-21

    In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F(0) and F(2+) defects but not at F(1+) sites, (2) electron redistribution from the F(0) vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F(0) type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F(0), and (5) the moderate adsorption energy of the gold atom on the F(0) defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step.

  15. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

    2017-02-01

    The Huisgen cycloaddition reaction ("click" chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  16. Enhanced magneto-optical properties of semiconductor EuS nanocrystals assisted by surface plasmon resonance of gold nanoparticles.

    PubMed

    Kawashima, Akira; Nakanishi, Takayuki; Shibayama, Tamaki; Watanabe, Seiichi; Fujita, Koji; Tanaka, Katsuhisa; Koizumi, Hitoshi; Fushimi, Koji; Hasegawa, Yasuchika

    2013-10-18

    Remarkable magneto-optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS-Au nanosystem), has been demonstrated for a future photo-information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto-optical properties of the EuS nanocrystals. To construct the EuS-Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2-ethanedithiol (EDT), 1,6-hexanedithiol (HDT), 1,10-decanedithiol (DDT), 1,4-bisethanethionaphthalene (NpEDT), or 1,4-bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto-optical properties of the EuS-Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS-Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS-Au nanosystems was observed. The spin configuration in the excited state of the EuS-Au nanosystem was also investigated using photo-assisted electron paramagnetic resonance.

  17. Surface-enhanced terahertz spectroscopy using gold rod structures resonant with terahertz waves.

    PubMed

    Ueno, Kosei; Nozawa, Sho; Misawa, Hiroaki

    2015-11-02

    Terahertz (THz) spectroscopy is a promising method to measure the spectrum of low-frequency modes of molecules or ensembles, such as crystals and polymers, including proteins. However, the main drawback of THz spectroscopy is its extremely low sensitivity. In the present study, we report on signal enhancement in THz spectroscopy achieved by depositing amino acid molecules or their derivatives on a gold rod structured silicon substrate whose localized surface plasmon resonance is exhibited in the THz frequency region. The distinct peaks derived from the enhancement of the inherent spectrum based on a molecular crystal were clearly observed when a longitudinal plasmon resonance mode of the gold rod structure was excited and the plasmon resonance band overlapped the molecular/intermolecular vibrational mode. We discuss the mechanism by which surface-enhanced THz spectroscopy was induced from the viewpoint of the enhancement of light-matter coupling due to plasmon excitation and the modulation of the plasmon band by dipole coupling between the plasmon dipole and molecular/intermolecular vibrational modes.

  18. Measurement of surface mercury fluxes at active industrial gold mines in Nevada (USA).

    PubMed

    Eckley, C S; Gustin, M; Marsik, F; Miller, M B

    2011-01-01

    Mercury (Hg) may be naturally associated with the rock units hosting precious and base metal deposits. Active gold mines are known to have point source releases of Hg associated with ore processing facilities. The nonpoint source release of Hg to the air from the large area (hundreds to thousands of hectares) of disturbed and processed material at industrial open pit gold mines has not been quantified. This paper describes the field data collected as part of a project focused on estimating nonpoint source emissions of Hg from two active mines in Nevada, USA. In situ Hg flux data were collected on diel and seasonal time steps using a dynamic flux chamber from representative mine surfaces. Hg fluxes ranged from <1500 ng m(-2) day(-1) for waste rock piles (0.6-3.5 μg g(-1)) to 684,000 ng m(-2) day(-1) for tailings (2.8-58 μg g(-1)). Releases were positively correlated with material Hg concentrations, surface grain size, and moisture content. Highest Hg releases occurred from materials under active cyanide leaching and from tailings impoundments containing processed high-grade ore. Data collected indicate that as mine sites are reclaimed and material disturbance ceases, emissions will decline. Additionally local cycling of atmospheric Hg (deposition and re-emission) was found to occur.

  19. Preparing metal-complex surfaces based on self-assembled monolayers of thiols and disulfides on gold

    NASA Astrophysics Data System (ADS)

    Dolzhikova, V. D.; Bogdanova, Yu. G.; Majouga, A. G.; Beloglazkina, E. K.; Kudrinsky, A. A.

    2017-02-01

    The complexation of monolayers of sulfur-containing ligands self-assembled on surface of gold with Co(II) and Cu(II) ions is studied using quartz crystal microbalance (QCM) and wetting measurements. The optimum conditions for obtaining metal-complex surfaces and the compositions of the resulting monolayers are determined.

  20. Development of Lateral Flow Assay Based on Size-Controlled Gold Nanoparticles for Detection of Hepatitis B Surface Antigen

    PubMed Central

    Kim, Dong Seok; Kim, Yong Tae; Hong, Seok Bok; Kim, Jinwoon; Heo, Nam Su; Lee, Moon-Keun; Lee, Seok Jae; Kim, Byeong Il; Kim, In Soo; Huh, Yun Suk; Choi, Bong Gill

    2016-01-01

    In this study, we developed lateral flow assay (LFA) biosensors for the detection of hepatitis B surface antigens using well-controlled gold nanoparticles (AuNPs). To enhance colorimetric signals, a seeded growth method was used for the preparation of size-controlled AuNPs with a narrow size distribution. Different sizes of AuNPs in the range of 342–137.8 nm were conjugated with antibodies and then optimized for the efficient detection of LFA biosensors. The conjugation stability was investigated by UV-vis spectroscopy of AuNP dispersion at various pH values and concentrations of antibody. Based on optimized conjugation conditions, the use of 42.7 ± 0.8 nm AuNPs exhibited superior performance for the detection of LFAs relative to other sizes of AuNPs. PMID:27999291

  1. (90377) Sedna: Investigation of Surface Compositional Variation

    NASA Astrophysics Data System (ADS)

    Barucci, M. A.; Morea Dalle Ore, C.; Alvarez-Candal, A.; de Bergh, C.; Merlin, F.; Dumas, C.; Cruikshank, D.

    2010-12-01

    The dwarf planet (90377) Sedna is one of the most remote solar system objects accessible to investigations. To better constrain its surface composition and to investigate the possible heterogeneity of the surface of Sedna, several observations have been carried out at ESO-VLT with the powerful spectrometer SINFONI observing simultaneously the H and K bands. The analyzed spectra (obtained in 2005, 2007, and 2008) show a non-uniform spectral signature, particularly in the K band. Spectral modeling using the Shkuratov radiative transfer code for surface scattering has been performed using the various sets of data, including previous observations at visible wavelengths and photometry at 3.6 and 4.5 μm by the Spitzer Space Telescope. The visible and near-infrared spectra can be modeled with organic materials (triton and titan tholin), serpentine, and H2O ice in fairly significant amounts, and CH4, N2, and C2H6 in varying trace amounts. One of the spectra obtained in 2005 October shows a different signature in the K band and is best modeled with CH3OH in place of CH4, with reduced amounts of serpentine and with the addition of olivine. The compositional surface heterogeneity can give input on the past history as well clues to the origin of this peculiar, distant object. Based on observations obtained at the VLT Observatory Cerro Paranal of European Southern Observatory, ESO, Chile, in the framework of proposal 275.C-5055 and Large Program 178-C-0036/0867.

  2. (90377) SEDNA: INVESTIGATION OF SURFACE COMPOSITIONAL VARIATION

    SciTech Connect

    Barucci, M. A.; De Bergh, C.; Merlin, F.; Morea Dalle Ore, C.; Cruikshank, D.; Alvarez-Candal, A.; Dumas, C.

    2010-12-15

    The dwarf planet (90377) Sedna is one of the most remote solar system objects accessible to investigations. To better constrain its surface composition and to investigate the possible heterogeneity of the surface of Sedna, several observations have been carried out at ESO-VLT with the powerful spectrometer SINFONI observing simultaneously the H and K bands. The analyzed spectra (obtained in 2005, 2007, and 2008) show a non-uniform spectral signature, particularly in the K band. Spectral modeling using the Shkuratov radiative transfer code for surface scattering has been performed using the various sets of data, including previous observations at visible wavelengths and photometry at 3.6 and 4.5 {mu}m by the Spitzer Space Telescope. The visible and near-infrared spectra can be modeled with organic materials (triton and titan tholin), serpentine, and H{sub 2}O ice in fairly significant amounts, and CH{sub 4}, N{sub 2}, and C{sub 2}H{sub 6} in varying trace amounts. One of the spectra obtained in 2005 October shows a different signature in the K band and is best modeled with CH{sub 3}OH in place of CH{sub 4}, with reduced amounts of serpentine and with the addition of olivine. The compositional surface heterogeneity can give input on the past history as well clues to the origin of this peculiar, distant object.

  3. High Relaxivity Gd(III)–DNA Gold Nanostars: Investigation of Shape Effects on Proton Relaxation

    PubMed Central

    Rotz, Matthew W.; Culver, Kayla S. B.; Parigi, Giacomo; MacRenaris, Keith W.; Luchinat, Claudio; Odom, Teri W.; Meade, Thomas J.

    2015-01-01

    Gadolinium(III) nanoconjugate contrast agents (CAs) have distinct advantages over their small-molecule counterparts in magnetic resonance imaging. In addition to increased Gd(III) payload, a significant improvement in proton relaxation efficiency, or relaxivity (r1), is often observed. In this work, we describe the synthesis and characterization of a nanoconjugate CA created by covalent attachment of Gd(III) to thiolated DNA (Gd(III)–DNA), followed by surface conjugation onto gold nanostars (DNA–Gd@stars). These conjugates exhibit remarkable r1 with values up to 98 mM−1 s−1. Additionally, DNA–Gd@stars show efficient Gd(III) delivery and biocompatibility in vitro and generate significant contrast enhancement when imaged at 7 T. Using nuclear magnetic relaxation dispersion analysis, we attribute the high performance of the DNA–Gd@stars to an increased contribution of second-sphere relaxivity compared to that of spherical CA equivalents (DNA–Gd@spheres). Importantly, the surface of the gold nanostar contains Gd(III)–DNA in regions of positive, negative, and neutral curvature. We hypothesize that the proton relaxation enhancement observed results from the presence of a unique hydrophilic environment produced by Gd(III)–DNA in these regions, which allows second-sphere water molecules to remain adjacent to Gd(III) ions for up to 10 times longer than diffusion. These results establish that particle shape and second-sphere relaxivity are important considerations in the design of Gd(III) nanoconjugate CAs. PMID:25723190

  4. Facile synthesis of thermally stable poly(N-vinylpyrrolidone)-modified gold surfaces by surface-initiated atom transfer radical polymerization.

    PubMed

    Liu, Xiaoli; Sun, Kai; Wu, Zhaoqiang; Lu, Jianhong; Song, Bo; Tong, Weifang; Shi, Xiujuan; Chen, Hong

    2012-06-26

    Well-controlled polymerization of N-vinylpyrrolidone (NVP) on Au surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out at room temperature by a silanization method. Initial attempts to graft poly(N-vinylpyrrolidone) (PVP) layers from initiators attached to alkanethiol monolayers yielded PVP films with thicknesses less than 5 nm. The combined factors of the difficulty in the controllable polymerization of NVP and the instability of alkanethiol monolayers led to the difficulty in the controlled polymerization of NVP on Au surfaces. Therefore, the silanization method was employed to form an adhesion layer for initiator attachment. This method allowed well-defined ATRP polymerization to occur on Au surfaces. Water contact angle, X-ray photoelectron spectroscopy (XPS), and reflectance Fourier transform infrared (reflectance FTIR) spectroscopy were used to characterize the modified surfaces. The PVP-modified gold surface remained stable at 130 °C for 3 h, showing excellent thermal stability. Thus, postfunctionalization of polymer brushes at elevated temperatures is made possible. The silanization method was also applied to modify SPR chips and showed potential applications in biosensors and biochips.

  5. Nanoparticle-protein interactions: a thermodynamic and kinetic study of the adsorption of bovine serum albumin to gold nanoparticle surfaces.

    PubMed

    Boulos, Stefano P; Davis, Tyler A; Yang, Jie An; Lohse, Samuel E; Alkilany, Alaaldin M; Holland, Lisa A; Murphy, Catherine J

    2013-12-03

    Investigating the adsorption process of proteins on nanoparticle surfaces is essential to understand how to control the biological interactions of functionalized nanoparticles. In this work, a library of spherical and rod-shaped gold nanoparticles (GNPs) was used to evaluate the process of protein adsorption to their surfaces. The binding of a model protein (bovine serum albumin, BSA) to GNPs as a function of particle shape, size, and surface charge was investigated. Two independent comparative analytical methods were used to evaluate the adsorption process: steady-state fluorescence quenching titration and affinity capillary electrophoresis (ACE). Although under favorable electrostatic conditions kinetic analysis showed a faster adsorption of BSA to the surface of cationic GNPs, equilibrium binding constant determinations indicated that BSA has a comparable binding affinity to all of the GNPs tested, regardless of surface charge. BSA was even found to adsorb strongly to GNPs with a pegylated/neutral surface. However, these fluorescence titrations suffer from significant interference from the strong light absorption of the GNPs. The BSA-GNP equilibrium binding constants, as determined by the ACE method, were 10(5) times lower than values determined using spectroscopic titrations. While both analytical methods could be suitable to determine the binding constants for protein adsorption to NP surfaces, both methods have limitations that complicate the determination of protein-GNP binding constants. The optical properties of GNPs interfere with Ka determinations by static fluorescence quenching analysis. ACE, in contrast, suffers from material compatibility issues, as positively charged GNPs adhere to the walls of the capillary during analysis. Researchers seeking to determine equilibrium binding constants for protein-GNP interactions should therefore utilize as many orthogonal techniques as possible to study a protein-GNP system.

  6. Mechanistic investigations and molecular medicine applications of gold nanoparticle mediated (GNOME) laser transfection

    NASA Astrophysics Data System (ADS)

    Schomaker, M.; Heinemann, D.; Kalies, S.; Willenbrock, S.; Murua Escobar, H.; Buch, A.; Sodeik, B.; Ripken, T.; Meyer, H.

    2014-03-01

    Alternative high throughput transfection methods are required to understand the molecular network of the cell, which is linked to the evaluation of target genes as therapeutic agents. Besides diagnostic purposes, the transfection of primary- and stem cells is of high interest for therapeutic use. Here, the cell release of trans- or exogene proteins is used to develop immune cancer therapies. The basic requirement to accomplish manipulation of cells is an efficient and gentle transfection method. Therefore, we developed an automatized cell manipulation platform providing high throughput by using GNOME laser transfection. Herein, the interaction of moderately focused laser pulses with gold nanoparticles in close vicinity to the cell membrane mediate transient membrane permeabilization. The exact nature of the involved permeabilization effects depends on the applied particles and laser parameters. Hereinafter, we describe investigations considering the parameter regime, the permeabilization mechanism and the safety profile of GNOME laser transfection. The experimental and calculated results imply a combined permeabilization mechanism consisting of both photochemical and photothermal effects. Furthermore, paramount spatial control achieved either by laser illumination with micrometer precision or targeted gold nanoparticle binding to the cells was demonstrated, allowing selective cell manipulation and destruction. Additionally, the possibility to manipulate difficult to transfect primary cells (neurons) is shown. These results give insights in the basic mechanisms involved in GNOME laser transfection and serve as a strong basis to deliver different molecules for therapeutic (e.g. proteins) and diagnostic (siRNA) use.

  7. Setup for investigating gold nanoparticle penetration through reconstructed skin and comparison to published human skin data

    NASA Astrophysics Data System (ADS)

    Labouta, Hagar I.; Thude, Sibylle; Schneider, Marc

    2013-06-01

    Owing to the limited source of human skin (HS) and the ethical restrictions of using animals in experiments, in vitro skin equivalents are a possible alternative for conducting particle penetration experiments. The conditions for conducting penetration experiments with model particles, 15-nm gold nanoparticles (AuNP), through nonsealed skin equivalents are described for the first time. These conditions include experimental setup, sterility conditions, effective applied dose determination, skin sectioning, and skin integrity check. Penetration at different exposure times (two and 24 h) and after tissue fixation (fixed versus unfixed skin) are examined to establish a benchmark in comparison to HS in an attempt to get similar results to HS experiments presented earlier. Multiphoton microscopy is used to detect gold luminescence in skin sections. λex=800 nm is used for excitation of AuNP and skin samples, allowing us to determine a relative index for particle penetration. Despite the observed overpredictability of penetration into skin equivalents, they could serve as a first fast screen for testing the behavior of nanoparticles and extrapolate their penetration behavior into HS. Further investigations are required to test a wide range of particles of different physicochemical properties to validate the skin equivalent-human skin particle penetration relationship.

  8. Elevated gold ellipse nanoantenna dimers as sensitive and tunable surface enhanced Raman spectroscopy substrates

    NASA Astrophysics Data System (ADS)

    Jubb, A. M.; Jiao, Y.; Eres, G.; Retterer, S. T.; Gu, B.

    2016-03-01

    We demonstrate large area arrays of elevated gold ellipse dimers with precisely controlled gaps for use as sensitive and highly controllable surface enhanced Raman scattering (SERS) substrates. The enhanced Raman signal observed with SERS arises from both localized and long range plasmonic effects. By controlling the geometry of a SERS substrate, in this case the size and aspect ratio of individual ellipses, the plasmon resonance can be tuned in a broad wavelength range, providing a method for designing the response of SERS substrates at different excitation wavelengths. Plasmon effects exhibited by the elevated gold ellipse dimer substrates are also demonstrated and confirmed through finite difference time domain (FDTD) simulations. A plasmon resonance red shift with an increase of the ellipse aspect ratio is observed, allowing systematic control of the resulting SERS signal intensity. Optimized elevated ellipse dimer substrates with 10 +/- 2 nm gaps exhibit uniform SERS enhancement factors on the order of 109 for adsorbed p-mercaptoaniline molecules.We demonstrate large area arrays of elevated gold ellipse dimers with precisely controlled gaps for use as sensitive and highly controllable surface enhanced Raman scattering (SERS) substrates. The enhanced Raman signal observed with SERS arises from both localized and long range plasmonic effects. By controlling the geometry of a SERS substrate, in this case the size and aspect ratio of individual ellipses, the plasmon resonance can be tuned in a broad wavelength range, providing a method for designing the response of SERS substrates at different excitation wavelengths. Plasmon effects exhibited by the elevated gold ellipse dimer substrates are also demonstrated and confirmed through finite difference time domain (FDTD) simulations. A plasmon resonance red shift with an increase of the ellipse aspect ratio is observed, allowing systematic control of the resulting SERS signal intensity. Optimized elevated ellipse

  9. Electro-optically modulated localized surface plasmon resonance biosensors with gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Tzyy-Jiann; Lin, Wen-Shao

    2006-10-01

    An integrated-optic biosensor based on electro-optically modulated localized surface plasmon resonance (LSPR) is demonstrated. This biosensor utilizes the electro-optic effect to modulate the wave vector of incident lightwave used to excite localized surface plasmons. Electro-optically modulated LSPR results in the analyte-dependent variation of output intensity with the applied voltage. The linear regression slope of this relation is used to determine the analyte concentration. On the sensing region of LSPR biosensor, human serum albumin is self-assembled on gold nanoparticles in order to sense the beta-blocker concentration. The use of the presented biosensor has the features of no intensity drift problem, no absorption diversity problem in different sample media, and noise reduction by linear regression analysis.

  10. Boron Nitride Nanosheet-Veiled Gold Nanoparticles for Surface-Enhanced Raman Scattering.

    PubMed

    Cai, Qiran; Mateti, Srikanth; Watanabe, Kenji; Taniguchi, Takashi; Huang, Shaoming; Chen, Ying; Li, Lu Hua

    2016-06-22

    Atomically thin boron nitride (BN) nanosheets have many properties desirable for surface-enhanced Raman spectroscopy (SERS). BN nanosheets have a strong surface adsorption capability toward airborne hydrocarbon and aromatic molecules. For maximized adsorption area and hence SERS sensitivity, atomically thin BN nanosheet-covered gold nanoparticles have been prepared for the first time. When placed on top of metal nanoparticles, atomically thin BN nanosheets closely follow their contours so that the plasmonic hot spots are retained. Electrically insulating BN nanosheets also act as a barrier layer to eliminate metal-induced disturbances in SERS. Moreover, the SERS substrates veiled by BN nanosheets show an outstanding reusability in the long term. As a result, the sensitivity, reproducibility, and reusability of SERS substrates can be greatly improved. We also demonstrate that large BN nanosheets produced by chemical vapor deposition can be used to scale up the proposed SERS substrate for practical applications.

  11. Localized surface plasmon resonance and refractive index sensitivity of vacuum-evaporated nanostructured gold thin films

    NASA Astrophysics Data System (ADS)

    Rai, V. N.; Srivastava, A. K.; Mukherjee, C.; Deb, S. K.

    2016-01-01

    Plasmonic properties of vacuum-evaporated nanostructured gold thin films having different types of nanoparticles are presented. The films with thickness ≥6 nm show the presence of nanorods having non-cylindrical shape with triangular base. Two characteristic plasmon bands have been recorded in absorption spectra. First one occurs below 500 nm and the other one at higher wavelength side. Both the peaks show dependence on the dielectric property of surroundings. The higher wavelength localized surface plasmon resonance peak shifts to higher wavelength with an increase in the nanoparticle size, surface roughness and refractive index of the surrounding (methylene blue dye coating). This shows that such thin films can be used as sensor for organic molecules with a refractive index sensitivity ranging from 250 to 305 nm/RIU (refractive index unit).

  12. An experimental and theoretical approach to investigate the effect of chain length on aminothiol adsorption and assembly on gold.

    PubMed

    Bedford, Erin; Humblot, Vincent; Méthivier, Christophe; Pradier, Claire-Marie; Gu, Frank; Tielens, Frederik; Boujday, Souhir

    2015-10-05

    Despite the numerous studies on the self-assembled monolayers (SAMs) of alkylthiols on gold, the mechanisms involved, especially the nature and influence of the thiol-gold interface are still under debate. In this work the adsorption of aminothiols on Au(111) surfaces has been studied by using surface IR and X-ray photoelectron spectroscopy (XPS) as well as by density functional theory (DFT) modeling. Two aminothiols were used, cysteamine (CEA) and mercaptoundecylamine (MUAM), which contain two and eleven carbon atoms, respectively. By combining experimental and theoretical methods, it was possible to draw a molecular picture of the thiol-gold interface. The long-chain aminothiol produced better ordered SAMs, but, interestingly, the XPS data showed different sulfur binding environments depending on the alkyl chain length; an additional peak at low binding energy was observed upon CEA adsorption, which indicates the presence of sulfur in a different environment. DFT modeling showed that the positions of the sulfur atoms in the SAMs on gold with similar unit cells [(2√3×2√3)R30°] depended on the length of the alkyl chain. Short-chain alkylthiol SAMs were adsorbed more strongly than long-chain thiol SAMs and were shown to induce surface reconstruction by extracting atoms from the surface, possibly forming adatom/vacancy combinations that lead to the additional XPS peak. In the case of short alkylthiols, the thiol-gold interface governs the layer, CEA adsorbs strongly, and the mechanism is closer to single-molecule adsorption than self-assembly, whereas for long chains, interactions between alkyl chains drive the system to self-assembly, leading to a higher level of SAM organization and restricting the influence of the sulfur-gold interface.

  13. Modified titanium surface with gelatin nano gold composite increases osteoblast cell biocompatibility

    NASA Astrophysics Data System (ADS)

    Lee, Young-Hee; Bhattarai, Govinda; Aryal, Santosh; Lee, Nan-Hee; Lee, Min-Ho; Kim, Tae-Gun; Jhee, Eun-Chung; Kim, Hak-Yong; Yi, Ho-Keun

    2010-08-01

    This study examined the gelatin nano gold (GnG) composite for surface modification of titanium in addition to insure biocompatibility on dental implants or biomaterials. The GnG composite was constructed by gelatin and hydrogen tetrachloroaurate in presence of reducing agent, sodium borohydrate (NabH 4). The GnG composite was confirmed by UV-VIS spectroscopy and transmission electron microscopy (TEM). A dipping method was used to modify the titanium surface by GnG composite. Surface was characterized by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). The MC-3T3 E1 cell viability was assessed by trypan blue and the expression of proteins to biocompatibility were analyzed by Western blotting. The GnG composite showed well dispersed character, the strong absorption at 530 nm, roughness, regular crystal and clear C, Na, Cl, P, and Au signals onto titanium. Further, this composite allowed MC-3T3 E1 growth and viability compared to gelatin and pure titanium. It induced ERK activation and the expression of cell adherent molecules, FAK and SPARC, and growth factor, VEGF. However, GnG decreased the level of SAPK/JNK. This shows that GnG composite coated titanium surfaces have a good biocompatibility for osteoblast growth and attachment than in intact by simple and versatile dipping method. Furthermore, it offers good communication between cell and implant surfaces by regulating cell signaling and adherent molecules, which are useful to enhance the biocompatibility of titanium surfaces.

  14. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt{sub 3}M (where M = 3d transition metals) alloy catalyst from first-principles

    SciTech Connect

    Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius E-mail: hchahm@kist.re.kr; Ham, Hyung Chul E-mail: hchahm@kist.re.kr

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt{sub 3}M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt{sub 3}M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt{sub 3}M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt{sub 3}M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

  15. Adsorption kinetics of an engineered gold binding Peptide by surface plasmon resonance spectroscopy and a quartz crystal microbalance.

    PubMed

    Tamerler, Candan; Oren, Ersin Emre; Duman, Memed; Venkatasubramanian, Eswaranand; Sarikaya, Mehmet

    2006-08-29

    The adsorption kinetics of an engineered gold binding peptide on gold surface was studied by using both quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) spectroscopy systems. The gold binding peptide was originally selected as a 14-amino acid sequence by cell surface display and then engineered to have a 3-repeat form (3R-GBP1) with improved binding characteristics. Both sets of adsorption data for 3R-GBP1 were fit to Langmuir models to extract kinetics and thermodynamics parameters. In SPR, the adsorption onto the surface shows a biexponential behavior and this is explained as the effect of bimodal surface topology of the polycrystalline gold substrate on 3R-GBP1 binding. Depending on the concentration of the peptide, a preferential adsorption on the surface takes place with different energy levels. The kinetic parameters (e.g., K(eq) approximately 10(7) M(-1)) and the binding energy (approximately -8.0 kcal/mol) are comparable to synthetic-based self-assembled monolayers. The results demonstrate the potential utilization of genetically engineered inorganic surface-specific peptides as molecular substrates due to their binding specificity, stability, and functionality in an aqueous-based environment.

  16. Molecular structure of cysteamine monolayers on silver and gold substrates. Comparative studies by surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Michota, Agnieszka; Kudelski, Andrzej; Bukowska, Jolanta

    2002-04-01

    Monolayers of cysteamine (2-aminoethanethiol) frequently work as linkage layers for adsorption of other molecules on metal surfaces. We compared the structure of cysteamine monolayers formed on gold and silver and the influence of various electrolytes on the structure of monolayers formed on both substrates. The monolayers formed on silver contain significantly higher portion of a trans conformer than monolayers on gold. Probably monolayers on silver are self-assembled in such a way that higher portion of the amino groups is unbonded to the surface, thus being available for attaching other molecules. The structure of cysteamine monolayers formed on gold is considerably more stable and resistive to the influence of electrolytes as compared to the silver substrate. The greater stability of the monolayers on Au surface was ascribed to the strong affinity of the amine groups toward this metal.

  17. Potential-dependent adsorption/desorption behavior of perfluorosulfonated ionomer on a gold electrode surface studied by cyclic voltammetry, electrochemical quartz microbalance, and electrochemical atomic force microscopy.

    PubMed

    Masuda, Takuya; Ikeda, Kota; Uosaki, Kohei

    2013-02-19

    Potential-dependent adsorption/desorption behavior of perfluorosulfonated ionomer (PFSI) on a gold electrode was investigated by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), and electrochemical atomic force microscopy (EC-AFM) in a Nafion (i.e., PFSI) dispersed aqueous solution without any other electrolyte. It was found that PFSI serves as an electrolyte and that electrochemical measurements can be performed in this solution without any significant IR drop. PFSI molecules were adsorbed on the Au surface in the lying-down configuration in the potential range between 0 and 0.45 V, the amount of adsorbed PFSI increased when the potential was made more positive than 0.75 V, and the adsorbed PFSI fully desorbed from the surface at potentials more positive than 1.4 V where gold oxide was formed. Once the gold oxide had been reduced, PFSI readsorbed on the surface, albeit slowly. PFSI desorbed from the surface as the potential was made more negative than 0 V. These processes took place reversibly.

  18. Use of graphene and gold nanorods as substrates for the detection of pesticides by surface enhanced Raman spectroscopy.

    PubMed

    Nguyen, Trang H D; Zhang, Zhong; Mustapha, Azlin; Li, Hao; Lin, Mengshi

    2014-10-29

    This study aimed to use gold nanorods and graphene as key materials to fabricate high-performance substrates for the detection of pesticides by surface enhanced Raman spectroscopy (SERS). Three types of pesticides (azinphos-methyl, carbaryl, and phosmet) were selected. Gold nanorods have great potential to be used as a SERS substrate because it is easy to tune the surface plasmon resonance of the nanorods to the laser excitation wavelength of Raman spectroscopy. Graphene is a promising nanoscale material that can be used for supporting metal nanostructures. Three types of novel SERS substrates were fabricated, including graphene-gold film-gold nanorod (G-Au-AuNR) substrate, gold film-gold nanorod (Au-AuNR) substrate, and graphene coupled with gold nanorods (G-AuNR). The results demonstrate that G-Au-AuNR substrates exhibited the strongest Raman signals of the selected pesticides, followed by the Au-AuNR substrates. G-AuNR exhibited the weakest Raman signals, and no characteristic spectral features of the analytes were obtained. A partial least-squares method was used to develop quantitative models for the analysis of spectral data (R = 0.94, 0.87, and 0.86 for azinphos-methyl, carbaryl, and phosmet, respectively). The G-Au-AuNRs substrate was able to detect all three types of pesticides at the parts per million level with limits of detection at around 5, 5, and 9 ppm for azinphos-methyl, carbaryl, and phosmet, respectively. These results indicate that combining gold nanorods and graphene has great potential in the fabrication of sensitive, lightweight, and flexible substrates for SERS applications to improve food safety.

  19. Global Transcriptomic Analysis of Model Human Cell Lines Exposed to Surface-Modified Gold Nanoparticles: The Effect of Surface Chemistry

    PubMed Central

    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. PMID:25491924

  20. Investigating the surface chemistry of Mars

    SciTech Connect

    Grunthaner, F.J.; Ricco, A.J.; Butler, A.M.; Lane, A.L.; McKay, C.P.; Zent, A.P.; Quinn, R.C.; Murray, B.; Klein, H.P.; Levin, G.V.; Terhune, R.W.; Homer, M.L.; Ksendzov, A.; Niedermann, P.

    1995-10-01

    One of the primary objectives of the Viking missions to Mars in the 1970s was to search for life. Numerous theories were put forth to explain the Viking data, most of which involved an oxidizing species in the Martian surface material. In December 1992, the Mars Oxidant Experiment (MOx) was selected as the U.S. contribution to the Russian Mars 96 mission. Two landers are scheduled for launch in November 1996 and should arrive at Mars in September 1997. The MOx instrument on the Russian lander is designed to investigate the chemical nature of the Martian surface material, with particular emphasis on its oxidative character. The instrument uses fiber-optic technology to monitor real-time physicochemical changes in a suite of chemically sensitive thin-film materials. This report describes the scientific rationale and basis for the MOx instrument, along with the details of its design and construction. 15 refs., 4 figs., 1 tab.

  1. Theoretical investigation on DNA/RNA base pairs mediated by copper, silver, and gold cations.

    PubMed

    Marino, Tiziana; Russo, Nino; Toscano, Marirosa; Pavelka, Matej

    2012-02-14

    B3LYP density functional based computations were performed in order to characterize the interactions present in some Cu(+), Ag(+), and Au(+) metal ion-mediated DNA and RNA base pairs from both structural and electronic points of view. Examined systems involve as ligands canonical Watson-Crick, Hoogsteen and Wobble base pairs. Two artificial Hoogsteen base pairs were also taken into account. Binding energy values indicate that complexes involving silver cations are less stable than those in which copper or gold are present, and propose a similar behaviour for these two latter ions. The nature of the bond linking metal ions and bases was described by the NBO analysis that suggests metal coordinative interactions to be covalent. An evaluation of the dispersion contributions for the investigated systems was performed with the B3LYP-D3 functional.

  2. Electrical characterization of gold and platinum thin film electrodes with polyaniline modified surfaces

    NASA Astrophysics Data System (ADS)

    Aggas, John Richard

    Recent studies into soft organic electronics have burgeoned as a result of discoveries of conducting polymers such as polyaniline, polythiophene, and polypyrrole. However, in order to make these conducting polymers suitable for in vivo soft organic electronics, they must be developed so that they can be biocompatible and provide accurate sensing. Chitosan, a naturally occurring polymer structure found in exoskeletons of crustaceans, has been studied for its biocompatible properties. Composites of polyaniline (PAn), an intrinsically conductive polymer (ICP) and chitosan (Chi), a biopolymer, were developed and applied to gold and platinum Thin Film Electrode (TFE) devices. Electropolymerization and drop cast deposition were utilized to modify TFEs with a thin film of PAn or PAn-Chi composite. The impedance response over a spectrum of frequencies was studied for blank control TFEs, platinized TFEs, and platinized TFEs with various polyaniline coatings. Impedance measurements were taken in dry environments, DI Water, and in buffers such as PBS, and HEPES. Current-Voltage (I-V) characterization was used to study the current response and SEM imaging was used to study the surface topography. Resistance was measured for PAn modified unplatinized gold TFEs with varying amounts of incorporated chitosan. Impedance measurements of control and platinized TFEs yielded results similar to a low pass filter. Due to the conductive nature of polyaniline, the impedance of TFEs decreased substantially after poylaniline deposition. Measured resistance values for polyaniline and chitosan composites on TFEs revealed a window of concentrations of incorporated chitosan to lower resistance.

  3. High resolution fiber optic surface plasmon resonance sensors with single-sided gold coatings.

    PubMed

    Feng, Dingyi; Zhou, Wenjun; Qiao, Xueguang; Albert, Jacques

    2016-07-25

    The surface plasmon resonance (SPR) performance of gold coated tilted fiber Bragg gratings (TFBG) at near infrared wavelengths is evaluated as a function of the angle between the tilt plane orientation and the direction of single- and double-sided, nominally 50 nm-thick gold metal depositions. Scanning electron microscope images show that the coating are highly non-uniform around the fiber circumference, varying between near zero and 50 nm. In spite of these variations, the experimental results show that the spectral signature of the TFBG-SPR sensors is similar to that of simulations based on perfectly uniform coatings, provided that the depositions are suitably oriented along the tilt plane direction. Furthermore, it is shown that even a (properly oriented) single-sided coating (over only half of the fiber circumference) is sufficient to provide a theoretically perfect SPR response with a bandwidth under 5 nm, and 90% attenuation. Finally, using a pair of adjacent TFBG resonances within the SPR response envelope, a power detection scheme is used to demonstrate a limit of detection of 3 × 10-6 refractive index units.

  4. Bone char surface modification by nano-gold coating for elemental mercury vapor removal

    NASA Astrophysics Data System (ADS)

    Assari, Mohamad javad; Rezaee, Abbas; Rangkooy, Hossinali

    2015-07-01

    The present work was done to develop a novel nanocomposite using bone char coated with nano-gold for capture of elemental mercury (Hg0) from air. The morphologies, structures, and chemical constitute of the prepared nanocomposite were evaluated by UV-VIS-NIR, dynamic light-scattering (DLS), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infra-red (FTIR) spectroscopy, and energy dispersive X-ray spectroscopy (EDS). The capture performance of nanocomposite was evaluated in a needle trap for mercury vapor. An on-line setup based on cold vapor atomic absorption spectrometry (CVAAS) was designed for Hg0 determination. Dynamic capacity of nanocomposite for Hg0 was shown high efficient operating capacity of 586.7 μg/g. As temperature increases, the dynamic adsorption capacity of the nanocomposite was decreased, which are characteristics of physicosorption processes. It was found that the surface modification of bone char with nano-gold has various advantages such as high operating dynamic adsorption capacity and low cost preparation. It was also demonstrated that the developed nanocomposite is suitable for on-line monitoring of Hg0. It could be applied for the laboratory and field studies.

  5. Tuned longitudinal surface plasmon resonance and third-order nonlinear optical properties of gold nanorods.

    PubMed

    Tsutsui, Yushi; Hayakawa, Tomokatsu; Kawamura, Go; Nogami, Masayuki

    2011-07-08

    In order to elucidate the relationship for third-order nonlinear optical properties of anisotropic metal nanoparticles between the incident laser wavelength and surface plasmon resonance (SPR) wavelength, gold nanorods (GNRs) with a tuned longitudinal SPR mode in frequency were prepared by seed-mediated methods with two different surfactants, cetyltrimethylammonium bromide (CTAB) and benzyldimethylammonium chloride (BDAC). The real and imaginary parts of the third-order nonlinear optical susceptibilities χ(3) were examined by near-infrared (800 nm) femtosecond Z-scan and I-scan techniques for various gold sols with SPR wavelengths of 530 nm (spheres), 800 nm (nanorods) and 1000 nm (nanorods), named as 530GNSs, 800GNRs and 1000GNRs, respectively. All the samples showed intrinsically third-order nonlinear optical refractive responses. However, as for the real part of χ(3) for one particle, 800GNRs whose plasmon peak was tuned to the incident laser wavelength exhibited a Reχ(3) value 45 times stronger than 530GNSs. More interestingly, the imaginary part of χ(3) was more greatly influenced at the tuned SPR wavelength. Here we first demonstrate that 800GNRs showed plasmon-enhanced saturable absorption (SA) due to a longitudinal SPR tuned to the incident laser wavelength.

  6. High specific surface gold electrode on polystyrene substrate: Characterization and application as DNA biosensor.

    PubMed

    Yang, Zhiliu; Liu, Yichen; Lu, Wei; Yuan, Qingpan; Wang, Wei; Pu, Qiaosheng; Yao, Bo

    2016-05-15

    In the past decades, many efforts have been made to improve the sensitivity and specificity of electrochemical DNA biosensors. However, it is still strongly required to develop disposable and reliable DNA biosensors for wide and practical application. In this article, we reported superior electrochemical properties of an integrated plastic-gold electrode (PGE) fabricated in-house by chemical plating on polystyrene substrate. PGEs were found having extremely high capacity of DNA immobilization compared with gold electrodes fabricated by standard sputtering based photolithography. Unique nano-structured surface was observed on PGEs through morphology techniques, which would to some extend give an explanation to higher capacity of DNA immobilization on PGEs. A probable mechanism of carboxylic acid produced on polystyrene substrate after exposure to UV irradiation was proposed and discussed for the first time. This biosensor was applied to detection and manipulate of DNA hybridization. Detection limit of 7.2×10(-11) M and 1-500 nM of linearity range was obtained.

  7. Modulating the physicochemical and structural properties of gold-functionalized protein nanotubes through thiol surface modification.

    PubMed

    Carreño-Fuentes, Liliana; Plascencia-Villa, Germán; Palomares, Laura A; Moya, Sergio E; Ramírez, Octavio T

    2014-12-16

    Biomolecules are advantageous scaffolds for the synthesis and ordering of metallic nanoparticles. Rotavirus VP6 nanotubes possess intrinsic affinity to metal ions, a property that has been exploited to synthesize gold nanoparticles over them. The resulting nanobiomaterials have unique properties useful for novel applications. However, the formed nanobiomaterials lack of colloidal stability and flocculate, limiting their functionality. Here we demonstrate that it is possible to synthesize thiol-protected gold nanoparticles over VP6 nanotubes, which resulted in soluble nanobiomaterials. With this strategy, it was possible to modulate the size, colloidal stability, and surface plasmon resonance of the synthesized nanoparticles by controlling the content of the thiolated ligands. Two types of water-soluble ligands were tested, a small linear ligand, sodium 3-mercapto-1-propanesulfonate (MPS), and a bulky ligand, 5-mercaptopentyl β-D-glucopyranoside (GlcC5SH). The synthesized nanobiomaterials had a higher stability in suspension, as determined by Z-potential measurements. To the extent of our knowledge, this is the first time that a rational strategy is developed to modulate the particular properties of metal nanoparticles in situ synthesized over a protein bioscaffold through thiol coating, achieving a high spatial and structural organization of nanoparticles in a single integrative hybrid structure.

  8. Elevated gold ellipse nanoantenna dimers as sensitive and tunable surface enhanced Raman spectroscopy substrates

    DOE PAGES

    Jubb, A. M.; Jiao, Y.; Eres, Gyula; ...

    2016-02-15

    Here we demonstrate large area arrays of elevated gold ellipse dimers with precisely controlled gaps for use as sensitive and highly controllable surface enhanced Raman scattering (SERS) substrates. The significantly enhanced Raman signal observed with SERS arises from both localized and long range plasmonic effects. By controlling the geometry of a SERS substrate, in this case the size and aspect ratio of individual ellipses, the plasmon resonance can be tuned in a broad wavelength range, providing a method for designing the response of SERS substrates at different excitation wavelengths. Plasmon effects exhibited by the elevated gold ellipse dimer substrates aremore » also demonstrated and confirmed through finite difference time domain (FDTD) simulations. A plasmon resonance red shift with an increase of the ellipse aspect ratio is observed, allowing systematic control of the resulting SERS signal intensity. Optimized elevated ellipse dimer substrates with 10±2 nm gaps exhibit uniform SERS enhancement factors on the order of 109 for adsorbed p-mercaptoaniline molecules.« less

  9. DNA origami based assembly of gold nanoparticle dimers for surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Thacker, Vivek V.; Herrmann, Lars O.; Sigle, Daniel O.; Zhang, Tao; Liedl, Tim; Baumberg, Jeremy J.; Keyser, Ulrich F.

    2014-03-01

    Plasmonic sensors are extremely promising candidates for label-free single-molecule analysis but require exquisite control over the physical arrangement of metallic nanostructures. Here we employ self-assembly based on the DNA origami technique for accurate positioning of individual gold nanoparticles. Our innovative design leads to strong plasmonic coupling between two 40 nm gold nanoparticles reproducibly held with gaps of 3.3±1 nm. This is confirmed through far field scattering measurements on individual dimers which reveal a significant red shift in the plasmonic resonance peaks, consistent with the high dielectric environment due to the surrounding DNA. We use surface-enhanced Raman scattering (SERS) to demonstrate local field enhancements of several orders of magnitude through detection of a small number of dye molecules as well as short single-stranded DNA oligonucleotides. This demonstrates that DNA origami is a powerful tool for the high-yield creation of SERS-active nanoparticle assemblies with reliable sub-5 nm gap sizes.

  10. Elevated gold ellipse nanoantenna dimers as sensitive and tunable surface enhanced Raman spectroscopy substrates

    SciTech Connect

    Jubb, A. M.; Jiao, Y.; Eres, Gyula; Retterer, Scott T.; Gu, Baohua

    2016-02-15

    Here we demonstrate large area arrays of elevated gold ellipse dimers with precisely controlled gaps for use as sensitive and highly controllable surface enhanced Raman scattering (SERS) substrates. The significantly enhanced Raman signal observed with SERS arises from both localized and long range plasmonic effects. By controlling the geometry of a SERS substrate, in this case the size and aspect ratio of individual ellipses, the plasmon resonance can be tuned in a broad wavelength range, providing a method for designing the response of SERS substrates at different excitation wavelengths. Plasmon effects exhibited by the elevated gold ellipse dimer substrates are also demonstrated and confirmed through finite difference time domain (FDTD) simulations. A plasmon resonance red shift with an increase of the ellipse aspect ratio is observed, allowing systematic control of the resulting SERS signal intensity. Optimized elevated ellipse dimer substrates with 10±2 nm gaps exhibit uniform SERS enhancement factors on the order of 109 for adsorbed p-mercaptoaniline molecules.

  11. Gold nanoparticle incorporated inverse opal photonic crystal capillaries for optofluidic surface enhanced Raman spectroscopy.

    PubMed

    Zhao, Xiangwei; Xue, Jiangyang; Mu, Zhongde; Huang, Yin; Lu, Meng; Gu, Zhongze

    2015-10-15

    Novel transducers are needed for point of care testing (POCT) devices which aim at facile, sensitive and quick acquisition of health related information. Recent advances in optofluidics offer tremendous opportunities for biological/chemical analysis using extremely small sample volumes. This paper demonstrates nanostructured capillary tubes for surface enhanced Raman spectroscopy (SERS) analysis in a flow-through fashion. The capillary tube integrates the SERS sensor and the nanofluidic structure to synergistically offer sample delivery and analysis functions. Inside the capillary tube, inverse opal photonic crystal (IO PhC) was fabricated using the co-assembly approach to form nanoscale liquid pathways. In the nano-voids of the IO PhC, gold nanoparticles were in situ synthesized and functioned as the SERS hotspots. The advantages of the flow-through SERS sensor are multifold. The capillary effect facilities the sample delivery process, the nanofluidic channels boosts the interaction of analyte and gold nanoparticles, and the PhC structure strengthens the optical field near the SERS hotspots and results in enhanced SERS signals from analytes. As an exemplary demonstration, the sensor was used to measure creatinein spiked in artificial urine samples with detection limit of 0.9 mg/dL.

  12. Surface interactions of gold nanorods and polysaccharides: From clusters to individual nanoparticles.

    PubMed

    de Barros, Heloise Ribeiro; Piovan, Leandro; Sassaki, Guilherme L; de Araujo Sabry, Diego; Mattoso, Ney; Nunes, Ábner Magalhães; Meneghetti, Mario R; Riegel-Vidotti, Izabel C

    2016-11-05

    Gold nanorods (AuNRs) are suitable for constructing self-assembled structures for the development of biosensing devices and are usually obtained in the presence of cetyltrimethylammonium bromide (CTAB). Here, a sulfated chitosan (ChiS) and gum arabic (GA) were employed to encapsulate CTAB/AuNRs with the purpose of studying the interactions of the polysaccharides with CTAB, which is cytotoxic and is responsible for the instability of nanoparticles in buffer solutions. The presence of a variety of functional groups such as the sulfate groups in ChiS and the carboxylic groups in GA, led to efficient interactions with CTAB/AuNRs as evidenced through UV-vis and FTIR spectroscopies. Electron microscopies (HR-SEM and TEM) revealed that nanoparticle clusters were formed in the GA-AuNRs sample, whereas individual AuNRs, surrounded by a dense layer of polysaccharides, were observed in the ChiS-AuNRs sample. Therefore, the presented work contributes to the understanding of the driving forces that control the surface interactions of the studied materials, providing useful information in the building-up of gold self-assembled nanostructures.

  13. Time-of-flight-secondary ion mass spectrometry and cyclic voltammetry studies of self-assembly of dodecanethiol on a nanoporous gold surface.

    PubMed

    Hafez, Aly M; Huber, Andreas; Wenclawiak, Bernd W

    2013-03-19

    Preparation of a nanoporous gold surface by dealloying (etching) of a 585 gold plate (58.5% Au, 30% Ag, and 11.5% non-noble metals) was studied by applying acidic and thermal treatment of the gold plate. The gold plate surface was studied before and after the etching process using different analytical techniques like field emission scanning electron microscope (FE-SEM) with an energy dispersive X-ray spectroscopy analyzer (EDX), cyclic voltammetry (CV), and time-of-flight-secondary ion mass spectrometry (TOF-SIMS). CV analysis of the gold surface has shown that overnight etching with warm nitric acid increases the surface area 20 times higher than before etching. FE-SEM analysis has shown that a nanoporous gold surface with pore diameter ≤100 nm was obtained. SIMS depth profile analysis and EDX analysis have shown that the nanoporous gold surface was obtained as a result of removing the silver and copper from the first layers of the plate. The nanoporous gold surface was used as a substrate for self-assembly of dodecanethiol and has shown a higher extraction efficiency than the unetched gold alloy.

  14. Reconnaissance investigations of ancient gold mines in the southern part of the Wadi Bidah District, Jabal Ibrahim and Al Aqiq quadrangles, Kingdom of Saudi Arabia

    USGS Publications Warehouse

    Worl, R.G.; Smith, C.W.

    1982-01-01

    Ancient gold mines in the southern part of the Wadi Bidah district, Kingdom of Saudi Arabia, are located either within lenses of ferruginous chert or in large felsic intrusions of Precambrian age. All are associated with quartz veins, stringers, and stockworks. Samples from both types of deposits have low silver and base-metal contents; samples from deposits within ferruginous chert have anomalous arsenic contents. None of the deposits are large enough to be considered as prime exploration targets at this time. Analytical results from the Bani Sar deposit, which is located within felsic plutonic rocks, are encouraging, but additional surface investigations are needed to define the size and extent of the mineralized zone. Deposits associated with ferruginous chert are also of exploration interest. Anomalous gold contents and other evidence of mineralization were found along a considerable exposure of the metasedimentary unit that contains the chert lenses.

  15. Determination of gold and silver in geological samples by focused infrared digestion: A re-investigation of aqua regia digestion.

    PubMed

    Wang, Yong; Baker, Laura A; Brindle, Ian D

    2016-02-01

    Focused infrared radiation-based digestions, for the determination of gold and silver, can be achieved in a timeframe as short as 10-15 min, making it an attractive candidate technology for the mining industry, where very large numbers of samples are analyzed on a daily basis. An investigation was carried out into gold and silver dissolution chemistry from geological samples using this novel digestion technique. This study investigated in-depth the issue of low recoveries of gold from aqua regia (AR) digestions, reported by a number of researchers. Conventional AR digestions consistently delivered gold recoveries in a range of 69-80% of the certified values for the four certified reference materials (CRM) employed (CCU-1d, SN26, OREAS 62c, and AMiS 0274), while silver recoveries were satisfactory. By gradually shifting the HCl:HNO3 ratio (v/v) from 3:1 to a reversed 1:3 ratio, recoveries of gold and silver exhibited inverse trends. At a HCl:HNO3 ratio of 1:3, complete recovery of gold was achieved with excellent reproducibility in all CRMs. Meanwhile, silver recoveries plunged significantly at this ratio in samples with higher silver concentrations. Silver values were recovered, however, when the silver was re-solubilized by adding a small volume of concentrated HCl to the cooled reverse aqua regia digests. Recoveries of base metals, such as Fe and Cu, were satisfactory throughout and were much less sensitive to changes in the digestion medium. Using four CRMs and five real-world gold/silver containing samples, the utility of the proposed reverse aqua regia was systematically studied. The uncomplicated nature of the digestion methods reported here, that are fast, effective and inexpensive, may be useful to analysts developing/optimizing their methods for the rapid determination of Au and Ag in a variety of mineral phases, particularly where rapid results are desirable, such as in prospecting and mine development.

  16. Gold nanoparticle localization at the core surface by using thermosensitive core-shell particles as a template.

    PubMed

    Suzuki, Daisuke; Kawaguchi, Haruma

    2005-12-06

    We report novel thermosensitive hybrid core-shell particles via in situ gold nanoparticle formation using thermosensitive core-shell particles as a template. This method for the in situ synthesis of gold nanoparticles with microgel interiors offers the advantage of eliminating or significantly reducing particle aggregation. In addition, by using thermosensitive microgel structures in which the shell has thermosensitive and gel properties in water--whereas the core itself is a water-insoluble polymer--we were able to synthesize the gold nanoparticles only at the surface of the core, which had reactive sites to bind metal ions. After the gold nanoparticles were synthesized, electroless gold plating was carried out to control the thickness of the gold nanoshells. The dispersions of the obtained hybrid particles were characterized by dynamic light scattering and UV-vis absorption spectroscopy, and the dried particles were also observed by electron microscopy. Adaptation of the technique shown here will create a number of applications as optical, electronic, and biomedical functional materials.

  17. Silver and gold nanoparticles produced by pulsed laser ablation in liquid to investigate their interaction with Ubiquitin

    NASA Astrophysics Data System (ADS)

    Dell'Aglio, M.; Mangini, V.; Valenza, G.; De Pascale, O.; De Stradis, A.; Natile, G.; Arnesano, F.; De Giacomo, A.

    2016-06-01

    The interaction of nanoparticles (NPs) with proteins is widely investigated since it can be a key issue in addressing the problem of nanotoxicity, particularly in the case of biological and medical applications. In this work, silver and gold nanoparticles (AgNPs and AuNPs) were produced in water by Pulsed Laser Ablation in Liquid (PLAL) and allowed to react with Ubiquitin (Ub) (a small human protein essential for degradative processes in cells). NPs produced by PLAL are completely free of undesired contaminants and do not require the use of stabilizers. We found that the NPs + Ub system behaves differently if the NPs are or are not treated with a stabilizer before performing the interaction with Ub, since the presence of capping agents modifies the surface reactivity of the metal-NPs. The surface plasmon resonance (SPR) absorption spectroscopy was employed to monitor the fast changes occurring in the NP colloidal solutions upon interaction with Ub. The results obtained by SPR were confirmed by TEM analysis. Therefore, when Ub interacts with bare NPs a rapid aggregation occurs and, at the same time, Ub undergoes an amyloid transition. Notably, the aggregation of AuNPs occurs at a much greater rate than that of analogous AgNPs and the Ub fibrils that are formed can be imaged by thioflavin T fluorescence.

  18. [Ocular surface investigations in dry eye].

    PubMed

    Labbé, A; Brignole-Baudouin, F; Baudouin, C

    2007-01-01

    Dry eye is a complex clinicopathological entity involving tear film, lacrimal glands, eyelids, and a wide spectrum of ocular surface cells, including epithelial, inflammatory, immune, and goblet cells. From the tightly regulated lacrimal film functions and structure, a large variety of investigations have been developed, including tear meniscus measurements, fluorophotometry, meibometry, interference pattern analysis, evaporation rate, tear osmolarity, and thermography. Dry eye conditions also interfere with the ocular surface, causing corneal irregularities that may be explored using the techniques of videokeratography and in vivo confocal microscopy, or optical impairment, as confirmed by aberrometry. At the level of ocular surface cells, impression cytology remains a standard for assessing cell alterations. It has greatly benefited from new confocal microscopy, molecular biology, and flow cytometry techniques. Biological assessment of tear proteins or other mediators is also useful. Major limits should be acknowledged, however, such as technical issues in tear film collection, especially in dry eyes, and the lack of standardization of most measurements. Tear osmolarity, electrophoresis, and dosage of normal tear proteins, such as lysozyme or lactoferrin, remain the most useful tests. Finally, some extraocular explorations such as accessory gland biopsy or serum antinuclear antibody dosage may be useful for assessing the diagnosis of Sjögren's syndrome.

  19. Fast nucleotide identification through fingerprinting using gold nanoparticle-based surface-assisted laser desorption/ionisation.

    PubMed

    Larguinho, Miguel; Capelo, José L; Baptista, Pedro V

    2013-02-15

    We report a method centred on gold nanoparticle-based surface-assisted laser desorption/ionisation for analysis of deoxynucleotides and alkylated nucleobases. Gold nanoparticles allow for enhanced analysis capability by eliminating undesired signature peaks; thus more elegant mass spectra can be attained that allow identification by nucleotide mass fingerprint. The resulting fingerprinting patterns on the spectra are compared and associated with the presence of different nucleotides in the sample. This method can be easily extended to modified nucleotides implicated in genome lesions due to exposure to environment chemicals, such as DNA adducts (e.g. guanine adducts). The use of gold nanoparticles for surface-assisted laser desorption/ionisation can be an useful tool to resolve common issues of background noise when analysing nucleic acids samples.

  20. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    NASA Astrophysics Data System (ADS)

    Bertolino, María Candelaria; Granados, Alejandro Manuel

    2016-10-01

    In this work we present a detailed study of classic reactions such as "click reaction" and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV-vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  1. Thermal-driven attachment of gold nanoparticles prepared with ascorbic acid onto indium tin oxide surfaces

    NASA Astrophysics Data System (ADS)

    Aziz, Md. Abdul; Oyama, Munetaka

    2013-05-01

    Thermal-driven attachment of gold nanoparticles (AuNPs), of which size was less than 50 nm, onto the surfaces of indium tin oxide (ITO) is reported as a new phenomenon. This was permitted by preparing AuNPs via the reduction of hydrogen tetrachloroaurate (HAuCl4) with ascorbic acid (AA). While the AuNPs prepared via the AA reduction sparsely attached on the surface of ITO even at room temperature, a heat-up treatment at ca. 75 °C caused denser attachment of AuNPs on ITO surfaces. The attached density and the homogeneity after the thermal treatment were better than those of AuNP/ITO prepared using 3-aminopropyl-trimethoxysilane linker molecules. The denser attachment was observed similarly both by the immersion of ITO samples after the preparations of AuNPs by AA and by the in situ preparation of AuNPs with AA together with ITO samples. Thus, it is considered that the thermal-driven attachment of AuNPs would occur after the formation of AuNPs in the aqueous solutions, not via the growth of AuNPs on ITO surfaces. The preparation of AuNPs with AA would be a key for the thermal-driven attachment because the same attachments were not observed for AuNPs prepared with citrate ions or commercially available tannic acid-capped AuNPs.

  2. Gold nanoparticle biodistribution: Cell, blood, and tissue interactions as a function of nanoparticle surface properties

    NASA Astrophysics Data System (ADS)

    Shah, Neha B.

    Intravenously injected gold nanoparticles (GNPs) hold a great promise for clinical diagnostic and therapeutic applications. A critical issue in their implementation is incomplete mechanistic understanding of their in vivo biodistribution. Two major limitations in optimizing the biodistribution of NPs are: (1) achieving the highest accumulation at the disease site, and (2) avoiding accumulation in healthy organs including liver and spleen. To overcome these limitations, the interactions of GNPs with biological system must be better understood. The research described in this dissertation sought to advance the field of GNP in vivo biodistribution by elucidating the effects of GNP surface properties such as surface charge, ligand, and polyethylene glycol (PEG) coverage. It was shown that the interactions of GNPs with cells and tissues were a function of their surface properties. A Confocal Raman Microscopy based technique was developed to study GNPs interactions with cells in vitro in fast, label-free, and non-invasive way. It was further shown that GNP surface properties strongly influence their blood circulation time in vivo. It was demonstrated that GNPs interact with circulating blood cells including platelets and monocytes, which may play a role in their clearance from blood stream. Most of the injected dose was shown to accumulate in liver and spleen; however, both organs displayed a different mechanism of uptake and distribution of GNPs. Long-term biodistribution studies further suggested that GNPs were still found in liver and spleen after 4 months, but GNPs showed clearance from liver overtime.

  3. Excess thermodynamic properties of thin water films confined between hydrophobized gold surfaces.

    PubMed

    Wang, Jialin; Yoon, Roe-Hoan; Eriksson, Jan Christer

    2011-12-01

    Surface forces between gold surfaces were measured in pure water at temperatures in the range of 10-40 °C using an atomic force microscope (AFM). The surfaces were hydrophobized by self-assembly of alkanethiols (C(n)SH) with n=2 and 16 in ethanol solutions. The data were used to determine the changes in excess free energies (ΔG(f)) of the thin water films per unit area by using the Derjaguin approximation [1]. The free energy data were then used to determine the changes in excess film entropy (ΔS(f)) and the excess film enthalpy (ΔH(f)) per unit area. The results show that both ΔS(f) and ΔH(f) decrease with decreasing film thickness, suggesting that the macroscopic hydrophobic interaction involves building some kind of structures in the intervening thin films of water. It was found that |ΔH(f)|>|TΔS(f)|, which is a necessary condition for an attractive force to appear when the enthalpy and entropy changes are both negative. That macroscopic hydrophobic interaction is enthalpically driven is contrary to the hydrophobic interactions at molecular scale. The results obtained in the present work are used to discuss possible origins for the long-range attractions observed between hydrophobic surfaces.

  4. Highly Sensitive Detection of Target Biomolecules on Cell Surface Using Gold Nanoparticle Conjugated with Aptamer Probe

    NASA Astrophysics Data System (ADS)

    Kim, Hyonchol; Terazono, Hideyuki; Hayashi, Masahito; Takei, Hiroyuki; Yasuda, Kenji

    2012-06-01

    A method of gold nanoparticle (Au NP) labeling with backscattered electron (BE) imaging of field emission scanning electron microscopy (FE-SEM) was applied for specific detection of target biomolecules on a cell surface. A single-stranded DNA aptamer, which specifically binds to the target molecule on a human acute lymphoblastic leukemia cell, was conjugated with a 20 nm Au NP and used as a probe to label its target molecule on the cell. The Au NP probe was incubated with the cell, and the interaction was confirmed using BE imaging of FE-SEM through direct counting of the number of Au NPs attached on the target cell surface. Specific Au NP-aptamer probes were observed on a single cell surface and their spatial distributions including submicron-order localizations were also clearly visualized, whereas the nonspecific aptamer probes were not observed on it. The aptamer probe can be potentially dislodged from the cell surface with treatment of nucleases, indicating that Au NP-conjugated aptamer probes can be used as sensitive and reversible probes to label target biomolecules on cells.

  5. Biocompatible gold nanorods: one-step surface functionalization, highly colloidal stability, and low cytotoxicity.

    PubMed

    Liu, Kang; Zheng, Yuanhui; Lu, Xun; Thai, Thibaut; Lee, Nanju Alice; Bach, Udo; Gooding, J Justin

    2015-05-05

    The conjugation of gold nanorods (AuNRs) with polyethylene glycol (PEG) is one of the most effective ways to reduce their cytotoxicity arising from the cetyltrimethylammonium bromide (CTAB) and silver ions used in their synthesis. However, typical PEGylation occurs only at the tips of the AuNRs, producing partially modified AuNRs. To address this issue, we have developed a novel, facile, one-step surface functionalization method that involves the use of Tween 20 to stabilize AuNRs, bis(p-sulfonatophenyl)phenylphosphine (BSPP) to activate the AuNR surface for the subsequent PEGylation, and NaCl to etch silver from the AuNRs. This method allows for the complete removal of the surface-bound CTAB and the most active surface silver from the AuNRs. The produced AuNRs showed far lower toxicity than other methods to PEGylate AuNRs, with no apparent toxicity when their concentration is lower than 5 μg/mL. Even at a high concentration of 80 μg/mL, their cell viability is still four times higher than that of the tip-modified AuNRs.

  6. Gold Nanoparticles Supported on Carbon Nitride: Influence of Surface Hydroxyls on Low Temperature Carbon Monoxide Oxidation

    SciTech Connect

    Singh, Joseph A; Dudney, Nancy J; Li, Meijun; Overbury, Steven {Steve} H; Veith, Gabriel M

    2012-01-01

    This paper reports the synthesis of 2.5 nm gold clusters on the oxygen free and chemically labile support carbon nitride (C3N4). Despite having small particle sizes and high enough water partial pressure these Au/C3N4 catalysts are inactive for the gas phase and liquid phase oxidation of carbon monoxide. The reason for the lack of activity is attributed to the lack of surface OH groups on the C3N4. These OH groups are argued to be responsible for the activation of CO in the oxidation of CO. The importance of basic OH groups explains the well document dependence of support isoelectric point versus catalytic activity.

  7. Photothermal activation of astrocyte cells using localized surface plasmon resonance of gold nanorods.

    PubMed

    Eom, Kyungsik; Hwang, Seoyoung; Yun, Seunghyeon; Byun, Kyung Min; Jun, Sang Beom; Kim, Sung June

    2017-04-01

    Although it has been revealed that astrocytes, generally known as star-shaped glial cells, play critical roles in the functions of central nervous system, there have been few efforts to directly modulate their activities and responses. In this study, an optical stimulation strategy for producing intracellular Ca(2+) transients of astrocytes is demonstrated using near-infrared (NIR) light and localized surface plasmon resonance. It is presented that NIR stimulation of micro-second duration combined with gold nanorods (GNRs) efficiently produces stronger Ca(2+) transients of astrocytes, which seems to be associated with a local heat generation by photothermal effects of GNRs. Since the proposed scheme can directly activate astrocytes with a high reliability, it is expected that GNR-mediated NIR stimulation could be utilized to facilitate minimally invasive physiological studies on the astrocyte functions. Photos of intracellular Ca(2+) transient of astrocytes with membrane-bound GNRs after optical stimulation at 30 s.

  8. Detection of melamine on fractals of unmodified gold nanoparticles by surface-enhanced Raman scattering.

    PubMed

    Roy, Pradip Kumar; Huang, Yi-Fan; Chattopadhyay, Surojit

    2014-01-01

    A simple way of detecting melamine in raw milk is demonstrated via surface-enhanced Raman spectroscopy (SERS) using fractals of bare and nonfunctionalized ~30 nm gold nanoparticles (AuNP) distributed on a solid support. The technique demonstrates the formation of AuNP fractals, from a random distribution, upon exposure to melamine, that enhance the Raman scattering cross-section to enable detection by SERS. The agglomeration, which is pronounced at higher melamine concentrations, is demonstrated directly through imaging, and the red-shift of the plasmon absorption peak of the AuNP fractal away from 530 nm by finite difference time domain (FDTD) calculations. The agglomeration results in a strong plasmon field, shown by FDTD, over the interparticle sites that enhances the Raman scattering cross-section of melamine and ensures unambiguous detection. Limit of detection of 100 ppb could be achieved reproducibly.

  9. Light-Induced Reversible Self-Assembly of Gold Nanoparticles Surface-Immobilized with Coumarin Ligands.

    PubMed

    He, Huibin; Feng, Miao; Chen, Qidi; Zhang, Xinqi; Zhan, Hongbing

    2016-01-18

    A novel light-induced reversible self-assembly (LIRSA) system is based on the reversible photodimerization and photocleavage of coumarin groups on the surface of gold nanoparticles (AuNPs) in THF solution. Facilitated by coumarin groups, light irradiation at 365 nm triggers the stable assembly of monodisperse AuNPs; the resulting self-assembly system can be disassembled back to the disassembled state by a relatively short exposure to benign UV light. The reversible self-assembly cycle can be repeated 4 times. A specific concentration range of coumarin ligand and the THF solvent were identified to be the two predominant factors that contribute to the LIRSA of AuNPs. This is the first successful application of reversible photodimerization based on a coumarin derivative in the field of AuNP LIRSA. This LIRSA system may provide unique opportunities for the photoregulated synthesis of many adjustable nanostructures and devices.

  10. Many-body theory of the neutralization of strontium ions on gold surfaces

    NASA Astrophysics Data System (ADS)

    Pamperin, M.; Bronold, F. X.; Fehske, H.

    2015-01-01

    Motivated by experimental evidence for mixed-valence correlations affecting the neutralization of strontium ions on gold surfaces, we set up an Anderson-Newns model for the Sr:Au system and calculate the neutralization probability α as a function of temperature. We employ quantum-kinetic equations for the projectile Green functions in the finite -U noncrossing approximation. Our results for α agree reasonably well with the experimental data as far as the overall order of magnitude is concerned, showing in particular the correlation-induced enhancement of α . The experimentally found nonmonotonous temperature dependence, however, could not be reproduced. Instead of an initially increasing and then decreasing α , we find over the whole temperature range only a weak negative temperature dependence. It arises, however, clearly from a mixed-valence resonance in the projectile's spectral density and thus supports qualitatively the interpretation of the experimental data in terms of a mixed-valence scenario.

  11. Induced pH-dependent shift by local surface plasmon resonance in functionalized gold nanorods

    PubMed Central

    2013-01-01

    Localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles is a powerful tool for chemical and biological sensing experiments. In this study, we observed LSPR shifts of 11-mercaptoundecanoic acid modified gold nanorods (GNR-MUA) for the pH range of 6.41 to 8.88. We proposed a mechanism involving changes of the dipole moment after protonation/deprotonation carboxylic groups of 11-mercaptoundecanoic acid (MUA) which plays an important role by modulating LSPR around the functionalized GNR. Such a stable and easily prepared GNR-MUA has potential to become one of the most efficient and promising pH nanosensors to study intra- or extra-cellular pH in a wide range of chemical or biological systems. PMID:23432999

  12. Vapour-phase gold-surface-mediated coupling of aldehydes with methanol.

    PubMed

    Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan; Friend, Cynthia M

    2010-01-01

    Selective coupling of oxygenates is critical to many synthetic processes, including those necessary for the development of alternative fuels. We report a general process for selective coupling of aldehydes and methanol as a route to ester synthesis. All steps are mediated by oxygen-covered metallic gold nanoparticles on Au(111). Remarkably, cross-coupling of methanol with formaldehyde, acetaldehyde, benzaldehyde and benzeneacetaldehyde to methyl esters is promoted by oxygen-covered Au(111) below room temperature with high selectivity. The high selectivity is attributed to the ease of nucleophilic attack of the aldehydes by the methoxy intermediate-formed from methanol on the surface-which yields the methyl esters. The competing combustion occurs via attack of both methanol and the aldehydes by oxygen. The mechanistic model constructed in this study provides insight into factors that control selectivity and clearly elucidates the crucial role of Au nanoparticles as active species in the catalytic oxidation of alcohols, even in solution.

  13. Strong surface enhanced Raman scattering from gold nanoarrays obtained by direct laser writing

    NASA Astrophysics Data System (ADS)

    Ivanov, V. G.; Todorov, N. D.; Petrov, L. S.; Ritacco, T.; Giocondo, M.; Vlakhov, E. S.

    2016-10-01

    We report for surface enhanced Raman scattering (SERS) from arrays of gold nanoparticles produced by 2-photons photo-reduction of the metallic precursor (HAuCl4) hosted in a Poly-Vinyl Alcohol (PVA) matrix, on glass substrates. Samples with the same pattern but featuring different nanoparticles size and density were obtained by varying the writing laser power and scanning speed. The Raman spectra were recorded from samples immersed in a solution of rhodamine-6G (R6G), as well as, after exposure of the samples in xylene. SERS enhancement factors of up to ∼104 were obtained for both analytes. The measurements show that the SERS enhancement is maximized on golden strips produced at higher writing laser power and lower scanning speed, where closer nanoparticles packing is obtained..

  14. Hybrid Structures for Surface-Enhanced Raman Scattering: DNA Origami/Gold Nanoparticle Dimer/Graphene.

    PubMed

    Prinz, Julia; Matković, Aleksandar; Pešić, Jelena; Gajić, Radoš; Bald, Ilko

    2016-10-01

    A combination of three innovative materials within one hybrid structure to explore the synergistic interaction of their individual properties is presented. The unique electronic, mechanical, and thermal properties of graphene are combined with the plasmonic properties of gold nanoparticle (AuNP) dimers, which are assembled using DNA origami nanostructures. This novel hybrid structure is characterized by means of correlated atomic force microscopy and surface-enhanced Raman scattering (SERS). It is demonstrated that strong interactions between graphene and AuNPs result in superior SERS performance of the hybrid structure compared to their individual components. This is particularly evident in efficient fluorescence quenching, reduced background, and a decrease of the photobleaching rate up to one order of magnitude. The versatility of DNA origami structures to serve as interface for complex and precise arrangements of nanoparticles and other functional entities provides the basis to further exploit the potential of the here presented DNA origami-AuNP dimer-graphene hybrid structures.

  15. High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides.

    PubMed

    Costa, Jean Claudio Santos; Ando, Rômulo Augusto; Sant'Ana, Antonio Carlos; Rossi, Liane Marcia; Santos, Paulo Sérgio; Temperini, Márcia Laudelina Arruda; Corio, Paola

    2009-09-14

    The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

  16. Liquid Surface X-ray Studies of Gold Nanoparticle-Phospholipid Films at the Air/Water Interface.

    PubMed

    You, Siheng Sean; Heffern, Charles T R; Dai, Yeling; Meron, Mati; Henderson, J Michael; Bu, Wei; Xie, Wenyi; Lee, Ka Yee C; Lin, Binhua

    2016-09-01

    Amphiphilic phospholipids and nanoparticles functionalized with hydrophobic capping ligands have been extensively investigated for their capacity to self-assemble into Langmuir monolayers at the air/water interface. However, understanding of composite films consisting of both nanoparticles and phospholipids, and by extension, the complex interactions arising between nanomaterials and biological membranes, remains limited. In this work, dodecanethiol-capped gold nanoparticles (Au-NPs) with an average core diameter of 6 nm were incorporated into 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayers with surface densities ranging from 0.1 to 20% area coverage at a surface pressure of 30 mN/m. High resolution liquid surface X-ray scattering studies revealed a phase separation of the DPPC and Au-NP components of the composite film, as confirmed with atomic force microscopy after the film was transferred to a substrate. At low Au-NP content, the structural organization of the phase-separated film is best described as a DPPC film containing isolated islands of Au-NPs. However, increasing the Au-NP content beyond 5% area coverage transforms the structural organization of the composite film to a long-range interconnected network of Au-NP strands surrounding small seas of DPPC, where the density of the Au-NP network increases with increasing Au-NP content. The observed phase separation and structural organization of the phospholipid and nanoparticle components in these Langmuir monolayers are useful for understanding interactions of nanoparticles with biological membranes.

  17. Surface chemistry but not aspect ratio mediates the biological toxicity of gold nanorods in vitro and in vivo

    PubMed Central

    Wan, Jiali; Wang, Jia-Hong; Liu, Ting; Xie, Zhixiong; Yu, Xue-Feng; Li, Wenhua

    2015-01-01

    Gold nanorods are a promising nanoscale material in clinical diagnosis and treatment. The physicochemical properties of GNRs, including size, shape and surface features, are crucial factors affecting their cytotoxicity. In this study, we investigated the effects of different aspect ratios and surface modifications on the cytotoxicity and cellular uptake of GNRs in cultured cells and in mice. The results indicated that the surface chemistry but not the aspect ratio of GNRs mediates their biological toxicity. CTAB-GNRs with various aspect ratios had similar abilities to induce cell apoptosis and autophagy by damaging mitochondria and activating intracellular reactive oxygen species (ROS). However, GNRs coated with CTAB/PSS, CTAB/PAH, CTAB/PSS/PAH or CTAB/PAH/PSS displayed low toxicity and did not induce cell death. CTAB/PAH-coated GNRs caused minimally abnormal cell morphology compared with CTAB/PSS and CTAB/PSS/PAH coated GNRs. Moreover, the intravenous injection of CTAB/PAH GNRs enabled the GNRs to reach tumor tissues through blood circulation in animals and remained stable, with a longer half-life compared to the other GNRs. Therefore, our results demonstrated that further coating can prevent cytotoxicity and cell death upon CTAB-coated GNR administration, similar to changing the GNR aspect ratio and CTAB/PAH coated GNRs show superior biological properties with better biocompatibility and minimal cytotoxicity. PMID:26096816

  18. Detection of cell surface calreticulin as a potential cancer biomarker using near-infrared emitting gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Subramaniyam Ramesh, Bala; Giorgakis, Emmanouil; Lopez-Davila, Victor; Kamali Dashtarzheneha, Ashkan; Loizidou, Marilena

    2016-07-01

    Calreticulin (CRT) is a cytoplasmic calcium-binding protein. The aim of this study was to investigate CRT presence in cancer with the use of fluorescent gold nanoclusters (AuNCs) and to explore AuNC synthesis using mercaptosuccinic acid (MSA) as a coating agent. MSA-coated AuNCs conferred well-dispersed, bio-stable, water-soluble nanoparticles with bioconjugation capacity and 800-850 nm fluorescence after broad-band excitation. Cell-viability assay revealed good AuNC tolerability. A native CRT amino-terminus corresponding peptide sequence was synthesised and used to generate rabbit site-specific antibodies. Target specificity was demonstrated with antibody blocking in colorectal and breast cancer cell models; human umbilical vein endothelial cells served as controls. We demonstrated a novel route of AuNC/MSA manufacture and CRT presence on colonic and breast cancerous cell surface. AuNCs served as fluorescent bio-probes specifically recognising surface-bound CRT. These results are promising in terms of AuNC application in cancer theranostics and CRT use as surface biomarker in human cancer.

  19. A retrospective observational study of the effect of surface treatments and cementing media on the durability of gold palatal veneers.

    PubMed

    Chadwick, R G; Linklater, K I

    2004-01-01

    This paper reports on the results of a retrospective observational study that sought to determine both the longevity and effects of surface treatments of gold palatal veneers used to restore tooth surface loss. Details of all gold palatal veneers fabricated from Mattident 60 were sourced from hospital records spanning 11 years and 9 months. The case notes of each individual were accessed and, for each restoration, a note was made of the date and method of cementation, together with the period of patient follow-up. When patients continued their routine checkups, the records were scrutinized closely for evidence of restoration failure. This yielded a data set of 151 palatal gold veneer cementations for which the surface treatments and/or cementing media were known. Survival analysis by the Kaplan-Meier method of alumina blasted veneers revealed median survival times of 4,663 days when cemented with Panavia 21 and 687 days if cemented with Aquacem. Veneers that were alumina blasted, oxidized and cemented with Panavia 21 had a survival probability of 1.0. A Logrank test revealed highly statistically significant differences between the survival curves (p<0.0001). It was concluded that: (1) Alumina blasting the fit surface of a gold veneer prior to cementation with Panavia 21 resulted in a significantly more durable restoration compared to alumina blasting and cementation with Aquacem and no etching of tooth substance. (2) Due to low MST cementing, gold palatal veneers with a conventional glass polyalkenoate cement are not recommended. (3) Pre-treatment of gold palatal veneers by alumina blasting and oxidation prior to cementing with Panavia 21 appears to improve the chances of obtaining a dependable restoration. A greater number of restorations would be required to statistically test this trend.

  20. Influence of various surface pretreatments on adherence of sputtered molybdenum disulfide to silver, gold, copper, and bronze

    NASA Technical Reports Server (NTRS)

    Spalvins, T.

    1973-01-01

    Solid film lubricants of radio frequency sputtered molybdenum disulfide (MoS2) were applied to silver, gold, copper, and bronze surfaces that had various pretreatments (mechanical polishing, sputter etching, oxidation, and sulfurization). Optical and electron transmission micrographs and electron diffraction patterns were used to interpret the film formation characteristics and to evaluate the sputtering conditions in regard to the film and substrate compatibility. Sputtered MoS2 films flaked and peeled on silver, copper, and bronze surfaces except when the surfaces had been specially oxidized. The flaking and peeling was a result of sulfide compound formation and the corresponding grain growth of the sulfide film. Sputtered MoS2 films showed no peeling and flaking on gold surfaces regardless of surface pretreatment.

  1. Label-Free Detection of Rare Cell in Human Blood Using Gold Nano Slit Surface Plasmon Resonance

    PubMed Central

    Mousavi, Mansoureh Z.; Chen, Huai-Yi; Hou, Hsien-San; Chang, Chou-Yuan-Yuan; Roffler, Steve; Wei, Pei-Kuen; Cheng, Ji-Yen

    2015-01-01

    Label-free detection of rare cells in biological samples is an important and highly demanded task for clinical applications and various fields of research, such as detection of circulating tumor cells for cancer therapy and stem cells studies. Surface Plasmon Resonance (SPR) as a label-free method is a promising technology for detection of rare cells for diagnosis or research applications. Short detection depth of SPR (400 nm) provides a sensitive method with minimum interference of non-targets in the biological samples. In this work, we developed a novel microfluidic chip integrated with gold nanoslit SPR platform for highly efficient immunomagnetic capturing and detection of rare cells in human blood. Our method offers simple yet efficient detection of target cells with high purity. The approach for detection consists of two steps. Target cells are firs captured on functionalized magnetic nanoparticles (MNPs) with specific antibody I. The suspension containing the captured cells (MNPs-cells) is then introduced into a microfluidic chip integrated with a gold nanoslit film. MNPs-cells bind with the second specific antibody immobilized on the surface of the gold nanoslit and are therefore captured on the sensor active area. The cell binding on the gold nanoslit was monitored by the wavelength shift of the SPR spectrum generated by the gold nanoslits. PMID:25806834

  2. Quantitative investigation of physical factors contributing to gold nanoparticle-mediated proton dose enhancement

    NASA Astrophysics Data System (ADS)

    Cho, Jongmin; Gonzalez-Lepera, Carlos; Manohar, Nivedh; Kerr, Matthew; Krishnan, Sunil; Cho, Sang Hyun

    2016-03-01

    Some investigators have shown tumor cell killing enhancement in vitro and tumor regression in mice associated with the loading of gold nanoparticles (GNPs) before proton treatments. Several Monte Carlo (MC) investigations have also demonstrated GNP-mediated proton dose enhancement. However, further studies need to be done to quantify the individual physical factors that contribute to the dose enhancement or cell-kill enhancement (or radiosensitization). Thus, the current study investigated the contributions of particle-induced x-ray emission (PIXE), particle-induced gamma-ray emission (PIGE), Auger and secondary electrons, and activation products towards the total dose enhancement. Specifically, GNP-mediated dose enhancement was measured using strips of radiochromic film that were inserted into vials of cylindrical GNPs, i.e. gold nanorods (GNRs), dispersed in a saline solution (0.3 mg of GNRs/g or 0.03% of GNRs by weight), as well as vials containing water only, before proton irradiation. MC simulations were also performed with the tool for particle simulation code using the film measurement setup. Additionally, a high-purity germanium detector system was used to measure the photon spectrum originating from activation products created from the interaction of protons and spherical GNPs present in a saline solution (20 mg of GNPs/g or 2% of GNPs by weight). The dose enhancement due to PIXE/PIGE recorded on the films in the GNR-loaded saline solution was less than the experimental uncertainty of the film dosimetry (<2%). MC simulations showed highly localized dose enhancement (up to a factor 17) in the immediate vicinity (<100 nm) of GNRs, compared with hypothetical water nanorods (WNRs), mostly due to GNR-originated Auger/secondary electrons; however, the average dose enhancement over the entire GNR-loaded vial was found to be minimal (0.1%). The dose enhancement due to the activation products from GNPs was minimal (<0.1%) as well. In conclusion, under the

  3. Quantitative investigation of physical factors contributing to gold nanoparticle-mediated proton dose enhancement.

    PubMed

    Cho, Jongmin; Gonzalez-Lepera, Carlos; Manohar, Nivedh; Kerr, Matthew; Krishnan, Sunil; Cho, Sang Hyun

    2016-03-21

    Some investigators have shown tumor cell killing enhancement in vitro and tumor regression in mice associated with the loading of gold nanoparticles (GNPs) before proton treatments. Several Monte Carlo (MC) investigations have also demonstrated GNP-mediated proton dose enhancement. However, further studies need to be done to quantify the individual physical factors that contribute to the dose enhancement or cell-kill enhancement (or radiosensitization). Thus, the current study investigated the contributions of particle-induced x-ray emission (PIXE), particle-induced gamma-ray emission (PIGE), Auger and secondary electrons, and activation products towards the total dose enhancement. Specifically, GNP-mediated dose enhancement was measured using strips of radiochromic film that were inserted into vials of cylindrical GNPs, i.e. gold nanorods (GNRs), dispersed in a saline solution (0.3 mg of GNRs/g or 0.03% of GNRs by weight), as well as vials containing water only, before proton irradiation. MC simulations were also performed with the tool for particle simulation code using the film measurement setup. Additionally, a high-purity germanium detector system was used to measure the photon spectrum originating from activation products created from the interaction of protons and spherical GNPs present in a saline solution (20 mg of GNPs/g or 2% of GNPs by weight). The dose enhancement due to PIXE/PIGE recorded on the films in the GNR-loaded saline solution was less than the experimental uncertainty of the film dosimetry (<2%). MC simulations showed highly localized dose enhancement (up to a factor 17) in the immediate vicinity (<100 nm) of GNRs, compared with hypothetical water nanorods (WNRs), mostly due to GNR-originated Auger/secondary electrons; however, the average dose enhancement over the entire GNR-loaded vial was found to be minimal (0.1%). The dose enhancement due to the activation products from GNPs was minimal (<0.1%) as well. In conclusion, under the currently

  4. Investigate electrochemical immunosensor of cortisol based on gold nanoparticles/magnetic functionalized reduced graphene oxide.

    PubMed

    Sun, Bolu; Gou, Yuqiang; Ma, Yuling; Zheng, Xiaoping; Bai, Ruibin; Ahmed Abdelmoaty, Ahmed Attia; Hu, Fangdi

    2017-02-15

    A sensitively competitive electrochemical immunosensor for the detection of cortisol was successfully developed based on gold nanoparticles and magnetic functionalized reduced graphene oxide (AuNPs/MrGO). In order to construct the base of the immunosensor, the MrGO was initially fabricated by chemical cross-linking and used to modify the nafion pretreated glassy carbon electrode. Subsequently, the surface of electrode was modified by AuNPs via electrochemical deposition. A variety of cortisol (Cor) can be firmly loaded in the AuNPs/MrGO with large specific surface area and good bioactivity to construct the basic electrode (Cor/AuNPs/MrGO/Nafion@GCE), which was characterized by the cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. Due to the cortisol on the surface of basic electrode and samples can competitively combine with the cortisol antibody labelled by horseradish peroxidase (HRP-Strept-Biotin-Ab). Finally, the detection signal of electrochemical immunosensor (HRP-Strept-Biotin-Ab-Cor/AuNPs/MrGO/Nafion@GCE) in the test liquid had negative correlations with the concentration of cortisol in samples. The AuNPs/MrGO with excellent electrical conductivity being applied, the electrochemical response of the immunosensor was immensely amplified. The immunosensor displayed excellent analytical performance for the detection of cortisol range from 0.1 to 1000ng/mL with a detection limit of 0.05ng/mL at 3σ. Moreover, compared the developed immunoassay with commercially available enzyme linked immunosorbent assay, the proposed method showed good precision, acceptable stability and reproducibility, indicating the immunosensor could be used for the sensitive, efficient and real-time detection of cortisol in real samples. Therefore, the present strategy provides a novel and convenient method for clinical determination of cortisol.

  5. Surface chemistry manipulation of gold nanorods preserves optical properties for bio-imaging applications

    NASA Astrophysics Data System (ADS)

    Polito, Anthony B.; Maurer-Gardner, Elizabeth I.; Hussain, Saber M.

    2015-12-01

    Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable optical properties within the near-infrared (NIR) region. However, cetyl trimethylammonium bromide-related cytotoxicity, overall poor cellular uptake following surface chemistry modifications, and loss of NIR optical properties due to material intracellular aggregation in combination remain as obstacles for nanobased biomedical GNR applications. In this article, we report that tannic acid-coated 11-mercaptoundecyl trimethylammonium bromide (MTAB) GNRs (MTAB-TA) show no significant decrease in either in vitro cell viability or stress activation after exposures to A549 human alveolar epithelial cells. In addition, MTAB-TA GNRs demonstrate a substantial level of cellular uptake while displaying a unique intracellular clustering pattern. This clustering pattern significantly reduces intracellular aggregation, preserving the GNRs NIR optical properties, vital for biomedical imaging applications. These results demonstrate how surface chemistry modifications enhance biocompatibility, allow for higher rate of internalization with low intracellular aggregation of MTAB-TA GNRs, and identify them as prime candidates for use in nanobased bio-imaging applications.

  6. Altering protein surface charge with chemical modification modulates protein-gold nanoparticle aggregation

    NASA Astrophysics Data System (ADS)

    Jamison, Jennifer A.; Bryant, Erika L.; Kadali, Shyam B.; Wong, Michael S.; Colvin, Vicki L.; Matthews, Kathleen S.; Calabretta, Michelle K.

    2011-02-01

    Gold nanoparticles (AuNP) can interact with a wide range of molecules including proteins. Whereas significant attention has focused on modifying the nanoparticle surface to regulate protein-AuNP assembly or influence the formation of the protein "corona," modification of the protein surface as a mechanism to modulate protein-AuNP interaction has been less explored. Here, we examine this possibility utilizing three small globular proteins—lysozyme with high isoelectric point (pI) and established interactions with AuNP; α-lactalbumin with similar tertiary fold to lysozyme but low pI; and myoglobin with a different globular fold and an intermediate pI. We first chemically modified these proteins to alter their charged surface functionalities, and thereby shift protein pI, and then applied multiple methods to assess protein-AuNP assembly. At pH values lower than the anticipated pI of the modified protein, AuNP exposure elicits changes in the optical absorbance of the protein-NP solutions and other properties due to aggregate formation. Above the expected pI, however, protein-AuNP interaction is minimal, and both components remain isolated, presumably because both species are negatively charged. These data demonstrate that protein modification provides a powerful tool for modulating whether nanoparticle-protein interactions result in material aggregation. The results also underscore that naturally occurring protein modifications found in vivo may be critical in defining nanoparticle-protein corona compositions.

  7. Thiol-reactive amphiphilic block copolymer for coating gold nanoparticles with neutral and functionable surfaces.

    PubMed

    Chen, Hongwei; Zou, Hao; Paholak, Hayley J; Ito, Masayuki; Qian, Wei; Che, Yong; Sun, Duxin

    2014-04-21

    Nanoparticles designed for biomedical applications are often coated with polymers containing reactive functional groups, such as -COOH and -NH2, to conjugate targeting ligands or drugs. However, introducing highly charged surfaces promotes binding of the nanoparticles to biomolecules in biological systems through ionic interactions, causing the nanoparticles to aggregate in biological environments and consequently undergo strong non-specific binding to off-target cells and tissues. Developing a unique polymer with neutral surfaces that can be further functionalized directly would be critical to develop suitable nanomaterials for nanomedicine. Here, we report a thiol-reactive amphiphilic block copolymer poly(ethylene oxide)-block-poly(pyridyldisulfide ethylmeth acrylate) (PEO-b-PPDSM) for coating gold nanoparticles (AuNPs). The resultant polymer-coated AuNPs have almost neutral surfaces with slightly negative zeta potentials from -10 to 0 mV over a wide pH range from 2 to 12. Although the zeta potential is close to zero we show that the PEO-b-PPDSM copolymer-coated AuNPs have both good stability in various physiological conditions and reduced non-specific adsorption of proteins/biomolecules. Because of the multiple pyridyldisulfide groups on the PPDSM block, these individually dispersed nanocomplexes with an overall hydrodynamic size around 43.8 nm can be directly functionalized via disulfide-thiol exchange chemistry.

  8. Energetic stabilities of thiolated pyrimidines on gold nanoparticles investigated by Raman spectroscopy and density functional theory calculations.

    PubMed

    Ganbold, Erdene-Ochir; Yoon, Jinha; Cho, Kwang-Hwi; Joo, Sang-Woo

    2015-01-01

    The adsorption structures of 2-thiocytosine (2TC) on gold surfaces were examined by means of vibrational Raman spectroscopy and quantum mechanical density functional theory calculations. The 1H-thione-amino form was calculated to be most stable among the six examined tautomers. The three plausible binding geometries of sulfur, pyrimidine nitrogen, and amino group binding modes were calculated to estimate the binding energies of the 1H-thione-amino form with six gold cluster atoms. Thiouracils including 2-thiouracil (2TU), 4-thiouracil (4TU), and 6-methyl-2-thiouracil (6M2TU) were also studied to compare their relative binding energies on gold atoms. The intracellular localization of a DNA base analog of 2TC on gold nanoparticles (AuNPs) in HeLa cells was identified by means of surface-enhanced Raman scattering. AuNPs were modified with 2TC by self-assembly. Our dark-field microscopy and z-depth-dependent confocal Raman spectroscopy indicated that 2TC-assembled AuNPs could be found inside cancer cells. On the other hand, we did not observe noticeably strong Raman peaks in the cases of thiouracils including 2TU, 4TU, and 6M2TU. This may be due to the additional amino group of 2TC, which can lead to a stronger binding of adsorbates on AuNPs.

  9. 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

  10. Investigation of the ion beryllium surface interaction

    SciTech Connect

    Guseva, M.I.; Birukov, A.Yu.; Gureev, V.M.

    1995-09-01

    The self -sputtering yield of the Be was measured. The energy dependence of the Be self-sputtering yield agrees well with that calculated by W. Eckstein et. al. Below 770 K the self-sputtering yield is temperature independent; at T{sub irr}.> 870 K it increases sharply. Hot-pressed samples at 370 K were implanted with monoenergetic 5 keV hydrogen ions and with a stationary plasma (flux power {approximately} 5 MW/m{sup 2}). The investigation of hydrogen behavior in beryllium shows that at low doses hydrogen is solved, but at doses {ge} 5x10{sup 22} m{sup -2} the bubbles and channels are formed. It results in hydrogen profile shift to the surface and decrease of its concentration. The sputtering results in further concentration decrease at doses > 10{sup 25}m{sup -2}.

  11. Theoretical investigation of gas-surface interactions

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1994-01-01

    The goal of this project was to develop computational tools for the calculation of the electronic structure of molecules containing heavy atoms, and to use these tools in the study of catalytic processes, with the overall objective of gaining an understanding of the catalytic process which could be used to design more efficient catalysts. The main catalytic system of interest was the combustion of hydrogen on platinum surfaces. Under this project, a flexible Dirac-Hartree-Fock (DHF) program has been developed, a code to calculate DHF correlation energies at the second-order Moeller-Plesset perturbation (PP2) level is almost complete, and code to include correlation at the MCSCF and MCSCF/MP2 level is planned. The tools so far developed have been validated and used to calibrate some more approximate methods, and applied to investigate the importance of relativistic effects in the bonding of hydrogen to platinum.

  12. Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

    PubMed

    Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

    2016-01-26

    Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle

  13. In situ surface-enhanced Raman spectroelectrochemical analysis system with a hemin modified nanostructured gold surface.

    PubMed

    Yuan, Tao; Le Thi Ngoc, Loan; van Nieuwkasteele, Jan; Odijk, Mathieu; van den Berg, Albert; Permentier, Hjalmar; Bischoff, Rainer; Carlen, Edwin T

    2015-03-03

    An integrated surface-enhanced Raman scattering (SERS) spectroelectrochemical (SEC) analysis system is presented that combines a small volume microfluidic sample chamber (<100 μL) with a compact three-electrode configuration for in situ surface-enhanced Raman spectroelectrochemistry. The SEC system includes a nanostructured Au surface that serves dual roles as the electrochemical working electrode (WE) and SERS substrate, a microfabricated Pt counter electrode (CE), and an external Ag/AgCl reference electrode (RE). The nanostructured Au WE enables highly sensitive in situ SERS spectroscopy through large and reproducible SERS enhancements, which eliminates the need for resonant wavelength matching of the laser excitation source with the electronic absorption of the target molecule. The new SEC analysis system has the merits of wide applicability to target molecules, small sample volume, and a low detection limit. We demonstrate in situ SERS spectroelectrochemistry measurements of the metalloporphyrin hemin showing shifts of the iron oxidation marker band ν4 with the nanostructured Au working electrode under precise potential control.

  14. Spectroscopic investigations, antimicrobial, and cytotoxic activity of green synthesized gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Lokina, S.; Suresh, R.; Giribabu, K.; Stephen, A.; Lakshmi Sundaram, R.; Narayanan, V.

    2014-08-01

    The gold nanoparticles (AuNPs) were synthesized by using naturally available Punica Granatum fruit extract as reducing and stabilizing agent. The biosynthesized AuNPs was characterized by using UV-Vis, fluorescence, high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric (TGA) analysis. The surface plasmon resonance (SPR) band at 585 nm confirmed the reduction of auric chloride to AuNPs. The crystalline nature of the biosynthesized AuNPs was confirmed from the HRTEM images, XRD and selected area electron diffraction (SAED) pattern. The HRTEM images showed the mixture of triangular and spherical-like AuNPs having size between 5 and 20 nm. The weight loss of the AuNPs was measured by TGA as a function of temperature under a controlled atmosphere. The biomolecules are responsible for the reduction of AuCl4- ions and the formation of stable AuNPs which was confirmed by FTIR measurement. The synthesized AuNPs showed an excellent antibacterial activity against Candida albicans (ATCC 90028), Aspergillus flavus (ATCC 10124), Staphylococcus aureus (ATCC 25175), Salmonella typhi (ATCC 14028) and Vibrio cholerae (ATCC 14033). The minimum inhibitory concentration (MIC) of AuNPs was recorded against various microorganisms. Further, the synthesized AuNPs shows an excellent cytotoxic result against HeLa cancer cell lines at different concentrations.

  15. Spectroscopic investigations, antimicrobial, and cytotoxic activity of green synthesized gold nanoparticles.

    PubMed

    Lokina, S; Suresh, R; Giribabu, K; Stephen, A; Lakshmi Sundaram, R; Narayanan, V

    2014-08-14

    The gold nanoparticles (AuNPs) were synthesized by using naturally available Punica Granatum fruit extract as reducing and stabilizing agent. The biosynthesized AuNPs was characterized by using UV-Vis, fluorescence, high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric (TGA) analysis. The surface plasmon resonance (SPR) band at 585nm confirmed the reduction of auric chloride to AuNPs. The crystalline nature of the biosynthesized AuNPs was confirmed from the HRTEM images, XRD and selected area electron diffraction (SAED) pattern. The HRTEM images showed the mixture of triangular and spherical-like AuNPs having size between 5 and 20nm. The weight loss of the AuNPs was measured by TGA as a function of temperature under a controlled atmosphere. The biomolecules are responsible for the reduction of AuCl4(-) ions and the formation of stable AuNPs which was confirmed by FTIR measurement. The synthesized AuNPs showed an excellent antibacterial activity against Candida albicans (ATCC 90028), Aspergillus flavus (ATCC 10124), Staphylococcus aureus (ATCC 25175), Salmonella typhi (ATCC 14028) and Vibrio cholerae (ATCC 14033). The minimum inhibitory concentration (MIC) of AuNPs was recorded against various microorganisms. Further, the synthesized AuNPs shows an excellent cytotoxic result against HeLa cancer cell lines at different concentrations.

  16. Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species.

    PubMed

    Mullen, Gregory M; Zhang, Liang; Evans, Edward J; Yan, Ting; Henkelman, Graeme; Mullins, C Buddie

    2015-02-14

    Gold catalysts display high activity and good selectivity for partial oxidation of a number of alcohol species. In this work, we discuss the effects of oxygen adatoms and surface hydroxyls on the selectivity for oxidation of allylic alcohols (allyl alcohol and crotyl alcohol) on gold surfaces. Utilizing temperature programmed desorption (TPD), reactive molecular beam scattering (RMBS), and density functional theory (DFT) techniques, we provide evidence to suggest that the selectivity displayed towards partial oxidation versus combustion pathways is dependent on the type of oxidant species present on the gold surface. TPD and RMBS results suggest that surface hydroxyls promote partial oxidation of allylic alcohols to their corresponding aldehydes with very high selectivity, while oxygen adatoms promote both partial oxidation and combustion pathways. DFT calculations indicate that oxygen adatoms can react with acrolein to promote the formation of a bidentate surface intermediate, similar to structures that have been shown to decompose to generate combustion products over other transition metal surfaces. Surface hydroxyls do not readily promote such a process. Our results help explain phenomena observed in previous studies and may prove useful in the design of future catalysts for partial oxidation of alcohols.

  17. Synthesis of gold nanoparticles by laser ablation in toluene: quenching and recovery of the surface plasmon absorption.

    PubMed

    Amendola, Vincenzo; Rizzi, Gian Andrea; Polizzi, Stefano; Meneghetti, Moreno

    2005-12-15

    Gold nanoparticles are synthesized by laser ablation of a gold plate in toluene. The nanoparticles do not show their characteristic surface plasmon absorption (SPA) and are found to be included in a graphitic matrix. The absence of this absorption is found to derive from the presence of the matrix which prevents the growth of large nanoparticles and covers them, suppressing the SPA according to the Mie model for core@shell particles. It is possible to recover the nanoparticle SPA by oxidizing the carbon matrix, obtaining, therefore, some control on the activity of this absorption.

  18. Electrochemical control of creep in nanoporous gold

    SciTech Connect

    Ye, Xing-Long; Jin, Hai-Jun

    2013-11-11

    We have investigated the mechanical stability of nanoporous gold (npg) in an electrochemical environment, using in situ dilatometry and compression experiments. It is demonstrated that the gold nano-ligaments creep under the action of surface stress which leads to spontaneous volume contractions in macroscopic npg samples. The creep of npg, under or without external forces, can be controlled electrochemically. The creep rate increases with increasing potential in double-layer potential region, and deceases to almost zero when the gold surface is adsorbed with oxygen. Surprisingly, we also noticed a correlation between creep and surface diffusivity, which links the deformation of nanocrystals to mobility of surface atoms.

  19. Extremely sensitive sandwich assay of kanamycin using surface-enhanced Raman scattering of 2-mercaptobenzothiazole labeled gold@silver nanoparticles.

    PubMed

    Zengin, Adem; Tamer, Ugur; Caykara, Tuncer

    2014-03-19

    Herein, we report the development of extremely sensitive sandwich assay of kanamycin using a combination of anti-kanamycin functionalized hybrid magnetic (Fe3O4) nanoparticles (MNPs) and 2-mercaptobenzothiazole labeled Au-core@Ag-shell nanoparticles as the recognition and surface-enhanced Raman scattering (SERS) substrate, respectively. The hybrid MNPs were first prepared via surface-mediated RAFT polymerization of N-acryloyl-L-glutamic acid in the presence of 2-(butylsulfanylcarbonylthiolsulfanyl) propionic acid-modified MNPs as a RAFT agent and then biofunctionalized with anti-kanamycin, which are both specific for kanamycin and can be collected via a simple magnet. After separating kanamycin from the sample matrix, they were sandwiched with the SERS substrate. According to our experimental results, the limit of detection (LOD) was determined to be 2pg mL(-1), this value being about 3-7 times more than sensitive than the LOD of previously reported results, which can be explained by the higher SERS activity of silver coated gold nanoparticles. The analysis time took less than 10min, including washing and optical detection steps. Furthermore, the sandwich assay was evaluated for investigating the kanamycin specificity on neomycin, gentamycin and streptomycin and detecting kanamycin in artificially contaminated milk.

  20. High-sensitive surface plasmon resonance microRNA biosensor based on streptavidin functionalized gold nanorods-assisted signal amplification.

    PubMed

    Hao, Kaihong; He, Yu; Lu, Huiting; Pu, Shaotao; Zhang, Yingnan; Dong, Haifeng; Zhang, Xueji

    2017-02-15

    Herein, a facile and sensitive microRNA (miRNA) biosensor was designed by using interfacial biotinylated thiolated DNA molecular beacon (MB) as probe and streptavidin functionalized gold nanorods (Stre-GNRs) as tag for the enhanced surface plasmon resonance (SPR) signal. The MB probe with two terminals labeled with biotin and thiol groups, respectively, was modified on the gold film via thiol-gold interaction. Upon hybridization with the target, the biotinylated group became accessible to the Stre-GNRs. The introduction of the Stre-GNRs tag to the gold film produced strong SPR signal for detection. Our work has illustrated that the plasmonic field extension generated from the gold film to GNRs and the mass increase due to the GNRs have led to drastic sensitivity enhancement. Under optimal conditions, this proposed approach allowed detection of miRNA with the limit of detection (LOD) down to 0.045 pM. The results have shown that the MB probe functionalized sensing film, together with streptavidin-conjugated GNRs, was readily served as a plasmonic coupling partner that can be used as a powerful ultrasensitive sandwich assay for miRNA detection, and GNRs were readily served as promising amplification labels in SPR sensing technology.

  1. Specific interactions of functionalised gold surfaces with ammonium perchlorate or starch; towards a chemical cartography of their mixture

    NASA Astrophysics Data System (ADS)

    Mercier, D.; Mercader, C.; Quere, S.; Hairault, L.; Méthivier, C.; Pradier, C. M.

    2012-10-01

    By functionalising gold samples, planar wafers or AFM tips, with an acid- or an amino acid-terminated thiols, mercaptoundecanoic acid (MUA) and homocystein (H-Cyst) respectively, we were able to differentiate the interactions with ammonium perchlorate (AP) and starch (S), two components of a nanocomposition mixture. To do so, the interaction between gold functionalized surfaces and the two targeted compounds have been characterized and quantified by several complementary techniques. Polarisation modulation-infrared spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS), providing chemical analyses of gold surfaces after contacting S or AP, proved that both compounds were retained on MUA or H-Cyst-modified surfaces, but to various extents. Quartz crystal microbalance on-line measurements enabled to monitor the kinetics of interaction and showed distinct differences in the behaviour of MUA and H-Cyst-surfaces towards the two compounds. Having observed that only H-Cyst-modified surfaces enables to get a contrast on the chemical force microscopy (CFM) images, this new result could be well explained by examining the data obtained by combining the above-mentioned surface characterisation techniques.

  2. Synthesis and characterization of surface-enhanced Raman-scattered gold nanoparticles

    PubMed Central

    Kalmodia, Sushma; Harjwani, Jaidev; Rajeswari, Raguraman; Yang, Wenrong; Barrow, Colin J; Ramaprabhu, Sundara; Krishnakumar, Subramanian; Elchuri, Sailaja V

    2013-01-01

    In this paper, we report a simple, rapid, and robust method to synthesize surface-enhanced Raman-scattered gold nanoparticles (GNPs) based on green chemistry. Vitis vinifera L. extract was used to synthesize noncytotoxic Raman-active GNPs. These GNPs were characterized by ultraviolet-visible spectroscopy, dynamic light-scattering, Fourier-transform infrared (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The characteristic surface plasmon-resonance band at ~ 528 nm is indicative of spherical particles, and this was confirmed by TEM. The N–H and C–O stretches in FTIR spectroscopy indicated the presence of protein molecules. The predominant XRD plane at (111) and (200) indicated the crystalline nature and purity of GNPs. GNPs were stable in the buffers used for biological studies, and exhibited no cytotoxicity in noncancerous MIO-M1 (Müller glial) and MDA-MB-453 (breast cancer) cell lines. The GNPs exhibited Raman spectral peaks at 570, 788, and 1,102 cm−1. These new GNPs have potential applications in cancer diagnosis, therapy, and ultrasensitive biomarker detection. PMID:24235830

  3. Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Cai, Qiran; Li, Lu Hua; Yu, Yuanlie; Liu, Yun; Huang, Shaoming; Chen, Ying; Watanabe, Kenji; Taniguchi, Takashi

    Atomically thin boron nitride (BN) nanosheets have been found an excellent substrate for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets by a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depends on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrate as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of analyte. The Au/BN substrates can be reused by heating in air to remove adsorbed analyte without loss of SERS enhancement.

  4. Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy.

    PubMed

    Cai, Qiran; Li, Lu Hua; Yu, Yuanlie; Liu, Yun; Huang, Shaoming; Chen, Ying; Watanabe, Kenji; Taniguchi, Takashi

    2015-03-28

    Atomically thin boron nitride (BN) nanosheets have been found to be excellent substrates for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets using a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depend on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrates as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of the analyte. The Au/BN substrates can be reused by heating in air to remove the adsorbed analyte without loss of SERS enhancement.

  5. Multifunctional surface modification of gold-stabilized nanoparticles by bioorthogonal reactions.

    PubMed

    Li, Xiuru; Guo, Jun; Asong, Jinkeng; Wolfert, Margreet A; Boons, Geert-Jan

    2011-07-27

    Nanocarriers that combine multiple properties in an all-in-one system hold great promise for drug delivery. The absence of technology to assemble highly functionalized devices has, however, hindered progress in nanomedicine. To address this deficiency, we have chemically synthesized poly(ethylene oxide)-β-poly(ε-caprolactone) (PEO-b-PCL) block polymers modified at the apolar PCL terminus with thioctic acid and at the polar PEO terminus with an acylhydrazide, amine, or azide moiety. The resulting block polymers were employed to prepare nanoparticles that have a gold core, an apolar polyester layer for drug loading, a polar PEO corona to provide biocompatibility, and three different types of surface reactive groups for surface functionalization. The acylhydrazide, amine, or azide moieties of the resulting nanoparticles could be reacted with high efficiencies with modules having a ketone, isocyanate, or active ester and alkyne function, respectively. To demonstrate proof of principle of the potential of multisurface functionalization, we prepared nanoparticles that have various combinations of an oligo-arginine peptide to facilitate cellular uptake, a histidine-rich peptide to escape from lysosomes, and an Alexa Fluor 488 tag for imaging purposes. It has been shown that uptake and subcellular localization of the nanoparticles can be controlled by multisurface modification. It is to be expected that the modular synthetic methodology provides unique opportunities to establish optimal configurations of nanocarriers for disease-specific drug delivery.

  6. In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

    PubMed

    Chen, Daqun; Hu, Weihua

    2017-03-28

    Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of homogeneous polymerization and heterogeneous system (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by self-assembled monolayer of ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information on eSI-ATRP, and offers a powerful platform for in situ investigation of such complicated processes.

  7. Preparation and investigation of the formation mechanism of submicron-sized spherical particles of gold using laser ablation and laser irradiation in liquids.

    PubMed

    Tsuji, Takeshi; Yahata, Tatsuya; Yasutomo, Masato; Igawa, Kazunobu; Tsuji, Masaharu; Ishikawa, Yoshie; Koshizaki, Naoto

    2013-03-07

    Results of very recent studies have shown that laser irradiation (LI) of colloidal nanoparticles (NPs) using a non-focused laser beam at moderate fluence transforms the NPs to submicron-sized spherical particles (SMPs). For this study, we applied this technique to prepare gold SMPs from source gold NPs prepared by laser ablation of a gold plate in an aqueous solution. Results show that SMPs were obtained from NPs in pure water, but a considerably large amount of the source NPs were sedimented without LI. On the other hand, SMPs were not obtained from NPs stabilized by 1 mM citrate. These findings indicate that the agglomeration of the source NPs prior to the laser-induced melting is important to obtain SMPs, although the sedimentation of the source NPs caused by considerable agglomeration should be reduced to obtain SMPs efficiently. A proper condition of the agglomeration tendency of the source NPs to prepare SMPs reducing the sedimentation of the source NPs was obtainable by simply adjusting the citrate solution concentration. Moreover, investigation of the temporal dynamics of the formation process of SMPs suggested that the agglomeration of the source NPs not only is controlled by citrate but also is induced by LI. LI brings about the decomposition and removal of citrate molecules on the surface of the source NPs, and cause the agglomeration of the source NPs dynamically; then it brings about the fusion of the agglomerated NPs.

  8. Mechanism of adsorption of single and double stranded DNA on gold and silver nanoparticles: Investigating some important parameters in bio-sensing applications.

    PubMed

    Farkhari, Nahid; Abbasian, Sara; Moshaii, Ahmad; Nikkhah, Maryam

    2016-12-01

    The mechanism of adsorption of single and double stranded DNAs on colloidal gold and silver nanoparticles has been studied by measuring the resistance of the nanoparticles, surrounded by various oligonucleotides, against salt induced aggregation. It is shown that both single and double stranded DNAs can be adsorbed on the metal nanoparticles and the adsorption strength is determined by the interaction between various bases of DNA and the nanoparticles. By changing the salt concentration, the difference between adsorption of various DNA strands on the nanoparticles can be specified. The results indicate that a key parameter in success of a sensing assay of DNA hybridization is the salt concentration which should be greater than a minimum threshold depending on the nanoparticles characteristics. We have also investigated the interaction mechanism between various DNA bases with the metal nanoparticles. For both gold and silver nanoparticles, adenine has the highest and thymine has the lowest attachment to the nanoparticles. From surface enhanced Raman spectroscopy (SERS) data of various bases in the presence of gold nanoparticles, the probable interaction points in the bases with the nanoparticles have been determined, which are mainly the nitrogen sites of these oligonucleotides.

  9. Investigation of Biophysical Mechanisms in Gold Nanoparticle Mediated Laser Manipulation of Cells Using a Multimodal Holographic and Fluorescence Imaging Setup

    PubMed Central

    Rakoski, Mirko S.; Heinemann, Dag; Schomaker, Markus; Ripken, Tammo; Meyer, Heiko

    2015-01-01

    Laser based cell manipulation has proven to be a versatile tool in biomedical applications. In this context, combining weakly focused laser pulses and nanostructures, e.g. gold nanoparticles, promises to be useful for high throughput cell manipulation, such as transfection and photothermal therapy. Interactions between laser pulses and gold nanoparticles are well understood. However, it is still necessary to study cell behavior in gold nanoparticle mediated laser manipulation. While parameters like cell viability or perforation efficiency are commonly addressed, the influence of the manipulation process on other essential cell parameters is not sufficiently investigated yet. Thus, we set out to study four relevant cell properties: cell volume and area, ion exchange and cytoskeleton structure after gold nanoparticle based laser manipulation. For this, we designed a multimodal imaging and manipulation setup. 200 nm gold nanoparticles were attached unspecifically to canine cells and irradiated by weakly focused 850 ps laser pulses. Volume and area change in the first minute post laser manipulation was monitored using digital holography. Calcium imaging and cells expressing a marker for filamentous actin (F-actin) served to analyze the ion exchange and the cytoskeleton, respectively. High radiant exposures led to cells exhibiting a tendency to shrink in volume and area, possibly due to outflow of cytoplasm. An intracellular raise in calcium was observed and accompanied by an intercellular calcium wave. This multimodal approach enabled for the first time a comprehensive analysis of the cell behavior in gold nanoparticle mediated cell manipulation. Additionally, this work can pave the way for a better understanding and the evaluation of new applications in the context of cell transfection or photothermal therapy. PMID:25909631

  10. Investigation of biophysical mechanisms in gold nanoparticle mediated laser manipulation of cells using a multimodal holographic and fluorescence imaging setup.

    PubMed

    Kalies, Stefan; Antonopoulos, Georgios C; Rakoski, Mirko S; Heinemann, Dag; Schomaker, Markus; Ripken, Tammo; Meyer, Heiko

    2015-01-01

    Laser based cell manipulation has proven to be a versatile tool in biomedical applications. In this context, combining weakly focused laser pulses and nanostructures, e.g. gold nanoparticles, promises to be useful for high throughput cell manipulation, such as transfection and photothermal therapy. Interactions between laser pulses and gold nanoparticles are well understood. However, it is still necessary to study cell behavior in gold nanoparticle mediated laser manipulation. While parameters like cell viability or perforation efficiency are commonly addressed, the influence of the manipulation process on other essential cell parameters is not sufficiently investigated yet. Thus, we set out to study four relevant cell properties: cell volume and area, ion exchange and cytoskeleton structure after gold nanoparticle based laser manipulation. For this, we designed a multimodal imaging and manipulation setup. 200 nm gold nanoparticles were attached unspecifically to canine cells and irradiated by weakly focused 850 ps laser pulses. Volume and area change in the first minute post laser manipulation was monitored using digital holography. Calcium imaging and cells expressing a marker for filamentous actin (F-actin) served to analyze the ion exchange and the cytoskeleton, respectively. High radiant exposures led to cells exhibiting a tendency to shrink in volume and area, possibly due to outflow of cytoplasm. An intracellular raise in calcium was observed and accompanied by an intercellular calcium wave. This multimodal approach enabled for the first time a comprehensive analysis of the cell behavior in gold nanoparticle mediated cell manipulation. Additionally, this work can pave the way for a better understanding and the evaluation of new applications in the context of cell transfection or photothermal therapy.

  11. Optical properties of Yeast Cytochrome c monolayer on gold: an in situ spectroscopic ellipsometry investigation.

    PubMed

    Toccafondi, Chiara; Prato, Mirko; Maidecchi, Giulia; Penco, Amanda; Bisio, Francesco; Cavalleri, Ornella; Canepa, Maurizio

    2011-12-01

    The adsorption of Yeast Cytochrome c (YCC) on well defined, flat gold substrates has been studied by Spectroscopic Ellipsometry (SE) in the 245-1000 nm wavelength range. The investigation has been performed in aqueous ambient at room temperature, focusing on monolayer-thick films. In situ δΨ and δΔ difference spectra have shown reproducibly well-defined features related to molecular optical absorptions typical of the so-called heme group. The data have been reproduced quantitatively by a simple isotropic optical model, accounting for the molecular absorption spectrum and film-substrate interface effects. The simulations allowed a reliable estimate of the film thickness and the determination of the position and the shape of the so-called Soret absorption peak that, within the experimental uncertainty, is the same found for molecules in liquid. These findings suggest that YCC preserves its native structure upon adsorption. The same optical model was able to reproduce also ex situ results on rinsed and dried samples, dominated by the spectral features associated to the polypeptide chain that tend to overwhelm the heme absorption features.

  12. Optical investigation of gold shell enhanced 25 nm diameter upconverted fluorescence emission

    NASA Astrophysics Data System (ADS)

    Green, Kory; Wirth, Janina; Lim, Shuang Fang

    2016-04-01

    We enhance the efficiency of upconverting nanoparticles by investigating the plasmonic coupling of 25 nm diameter NaYF4:Yb, Er nanoparticles with a gold-shell coating, and study the physical mechanism of enhancement by single-particle, time-resolved spectroscopy. A three-fold overall increase in emission intensity, and five-fold increase of green emission for these plasmonically enhanced particles have been achieved. Using a combination of structural and fluorescent imaging, we demonstrate that fluorescence enhancement is based on the photonic properties of single, isolated particles. Time-resolved spectroscopy shows that the increase in fluorescence is coincident with decreased rise time, which we attribute to an enhanced absorption of infrared light and energy transfer from Yb3+ to Er3+ atoms. Time-resolved spectroscopy also shows that fluorescence life-times are decreased to different extents for red and green emission. This indicates that the rate of photon emission is not suppressed, as would be expected for a metallic cavity, but rather enhanced because the metal shell acts as an optical antenna, with differing efficiency at different wavelengths.

  13. Optical investigation of gold shell enhanced 25 nm diameter upconverted fluorescence emission.

    PubMed

    Green, Kory; Wirth, Janina; Lim, Shuang Fang

    2016-04-01

    We enhance the efficiency of upconverting nanoparticles by investigating the plasmonic coupling of 25 nm diameter NaYF4:Yb, Er nanoparticles with a gold-shell coating, and study the physical mechanism of enhancement by single-particle, time-resolved spectroscopy. A three-fold overall increase in emission intensity, and five-fold increase of green emission for these plasmonically enhanced particles have been achieved. Using a combination of structural and fluorescent imaging, we demonstrate that fluorescence enhancement is based on the photonic properties of single, isolated particles. Time-resolved spectroscopy shows that the increase in fluorescence is coincident with decreased rise time, which we attribute to an enhanced absorption of infrared light and energy transfer from Yb(3+) to Er(3+) atoms. Time-resolved spectroscopy also shows that fluorescence life-times are decreased to different extents for red and green emission. This indicates that the rate of photon emission is not suppressed, as would be expected for a metallic cavity, but rather enhanced because the metal shell acts as an optical antenna, with differing efficiency at different wavelengths.

  14. Electrochemical investigation of methyl parathion at gold-sodium dodecylbenzene sulfonate nanoparticles modified glassy carbon electrode.

    PubMed

    Li, Chunya; Wang, Zhengguo; Zhan, Guoqin

    2011-01-01

    A gold/sodium dodecylbenzene sulfonate nanoparticles modified glassy carbon electrode (nano-Au/SDBS/GCE) was electrochemically fabricated with a constant potential at -0.4V. The obtained nano-Au/SDBS/GCE was characterized with scanning electronic microscopy, X-ray photoelectron spectroscopy and electrochemical techniques. Electrochemical behaviors of methyl parathion at the nano-Au/SDBS/GCE were thoroughly investigated. Compared to the unmodified electrode, the peak current obviously increased and the oxidation peak potential negatively shifted. These changes indicated that the composite nanoparticles possess good electrocatalytic performance on the electrochemical reaction of methyl parathion. Experimental parameters such as deposition time, pH value and accumulation conditions were optimized. Under optimum conditions, the peak current corresponding to the oxidation of the hydroxylamine group was found in a good linear relationship with the methyl parathion concentration. In addition, a calibration curve with excellent linearity was obtained in the concentration range from 5.0×10(-7)molL(-1) to 1.0×10(-4)molL(-1) with an estimated detection limit of 8.6×10(-8)molL(-1) (S/N=3). The successful determination of methyl parathion in real samples demonstrated the usefulness and potential applications of this method.

  15. Radiation defects induced by helium implantation in gold-based alloys investigated by positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Thome, T.; Grynszpan, R. I.

    2006-06-01

    The formation of gas bubbles in metallic materials may result in drastic degradation of in-service properties. In order to investigate this effect in high density and medium-low melting temperature ( T-M ) alloys, positron annihilation spectroscopy measurements were performed on helium-implanted gold-silver solid solutions after isochronal annealing treatments. Three recovery stages are observed, attributed to the migration and elimination of defects not stabilized by helium atoms, helium bubble nucleation and bubble growth. Similarities with other metals are found for the recovery stages involving bubble nucleation and growth processes. Lifetime measurements indicate that He implantation leads to the formation of small and over-pressurized bubbles that generate internal stresses in the material. A comprehensive picture is drawn for possible mechanisms of helium bubble evolution. Two values of activation energy (0.26 and 0.53 eV) are determined below and above 0.7 T-M , respectively, from the variation of the helium bubble radius during the bubble growth stage. The migration and coalescence mechanism, which accounts for these very low activation energies, controls the helium bubble growth.

  16. Electron beam/γ-ray irradiation synthesis of gold nanoparticles and investigation of antioxidant activity

    NASA Astrophysics Data System (ADS)

    Duy Nguyen, Ngoc; Phu Dang, Van; Le, Anh Quoc; Hien Nguyen, Quoc

    2014-12-01

    Colloidal solutions of 1 mM gold nanoparticles (AuNPs) were synthesized by γ-ray Co-60 and electron beam irradiation using 1% water soluble chitosan (WSC) with different molecular weight (Mw) as stabilizer. The AuNPs size measured from TEM images was of 7.1 and 15.1 nm for electron beam and γ-ray Co-60, respectively. The AuNPs sizes of 9.8, 15.1 and 22.4 nm stabilized by different WSC Mw of 155 × 103, 78 × 103 and 29 × 103 g mol-1, respectively, were also synthesized by γ-ray Co-60 irradiation. Antioxidant activity of AuNPs with different size from 7.1 to 20.0 nm was investigated using free radical 2,2‧-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS•+). Results indicated that the smaller size of AuNPs exhibited higher antioxidant activity. In particular, the antioxidant efficiency was of nearly 100, 75, 65, 52 and 30% for 7.1, 9.8, 15.1, 20.0 nm AuNPs and WSC 0.1%, respectively, at the same reaction time of 270 min. Thus, due to the compatibility of WSC and the unique property of AuNPs, the pure colloidal AuNPs/WSC solutions synthesized by irradiation method can be potentially applied in biomedicine, cosmetics and in other fields as well.

  17. Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

    PubMed Central

    Lee, Chi-Ying; Gong, Ping; Harbers, Gregory M.; Grainger, David W.; Castner, David G.; Gamble, Lara J.

    2006-01-01

    Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s → π* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in complex

  18. Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

    SciTech Connect

    Lee,C.; Gong, P.; Harbers, G.; Grainger, D.; Castner, D.; Gamble, L.

    2006-01-01

    Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s{yields}{pi}* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in

  19. Investigation of argon ion sputtering on the secondary electron emission from gold samples

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Cui, Wanzhao; Li, Yun; Xie, Guibai; Zhang, Na; Wang, Rui; Hu, Tiancun; Zhang, Hongtai

    2016-09-01

    Secondary electron (SE) yield, δ, is a very sensitive surface property. The values of δ often are not consistent for even identical materials. The influence of surface changes on the SE yield was investigated experimentally in this article. Argon ion sputtering was used to remove the contamination from the surface. Surface composition was monitored by X-ray photoelectron spectroscopy (XPS) and surface topography was scanned by scanning electron microscope (SEM) and atomic force microscope (AFM) before and after every sputtering. It was found that argon sputtering can remove contamination and roughen the surface. An "equivalent work function" is presented in this thesis to establish the relationship between SE yield and surface properties. Argon ion sputtering of 1.5keV leads to a significant increase of so called "work function" (from 3.7 eV to 6.0 eV), and a decrease of SE yield (from 2.01 to 1.54). These results provided a new insight into the influence of surface changes on the SE emission.

  20. Increase in the β-Sheet Character of an Amyloidogenic Peptide upon Adsorption onto Gold and Silver Surfaces.

    PubMed

    Soltani, Nima; Gholami, Mohammad Reza

    2017-03-03

    Fibrillation of amyloid beta (Aβ) peptide is the hallmark of Alzheimer's disease. Given that interactions at the bio-nano interface affect the fibrillation tendency of this peptide, an understanding of the interactions at Aβ peptide-inorganic surfaces on the microscopic level can help to determine the possible neurotoxicity of nanoparticles. Here, the interactions between a fibril-forming peptide, Aβ25-35 , and (111) and (100) facets of gold and silver surfaces have been studied by conducting atomistic molecular dynamics simulations. The obtained results indicate that the adsorption onto gold and silver surfaces force the peptide into the β-sheet-rich conformations, which is prone to aggregation, suggesting a new mechanism for the acceleration of fibril formation upon interaction with nanoparticles. To quantify the β-sheet content for a single peptide, a new metrics based on the Ramachandran probability distribution is introduced.

  1. A novel electrode surface fabricated by directly attaching gold nanoparticles onto NH2+ ions implanted-indium tin oxide substrate

    NASA Astrophysics Data System (ADS)

    Liu, Chenyao; Jiao, Jiao; Chen, Qunxia; Xia, Ji; Li, Shuoqi; Hu, Jingbo; Li, Qilong

    2010-12-01

    A new type of gold nanoparticle attached to a NH2+ ion implanted-indium tin oxide surface was fabricated without using peculiar binder molecules, such as 3-(aminopropyl)-trimethoxysilane. A NH 2/indium tin oxide film was obtained by implantation at an energy of 80 keV with a fluence of 5 × 10 15 ions/cm 2. The gold nanoparticle-modified film was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy and electrochemical techniques and compared with a modified bare indium tin oxide surface and 3-(aminopropyl)-trimethoxysilane linked surface, which exhibited a relatively low electron transfer resistance and high electrocatalytic activity. The results demonstrate that NH2+ ion implanted-indium tin oxide films can provide an important route to immobilize nanoparticles, which is attractive in developing new biomaterials.

  2. Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering

    PubMed Central

    Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

    2016-01-01

    Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3′-diethylthiatricarbocyanine iodide] and DTDC [3,3′-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist. PMID:26730189

  3. Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering.

    PubMed

    Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

    2016-01-01

    Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3'-diethylthiatricarbocyanine iodide] and DTDC [3,3'-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist.

  4. Investigation of Enhanced Surface Spray Cooling

    NASA Technical Reports Server (NTRS)

    Silk, Eric A.; Kim, Jungho; Kiger, Ken

    2004-01-01

    Experiments were conducted to study the effects of enhanced surfaces on heat transfer during spray cooling. The surface enhancements consisted of cubic pin fins, pyramids, and straight fins (uniform cross sectional straight fins) machined on the top surface of copper heater blocks. Each had a cross-sectional area of 2.0 square cm. Measurements were also obtained on a heater block with a flat surface for baseline comparison purposes. A 2x2 nozzle array was used with PF-5060 as the working fluid. Thermal performance data was obtained under nominally degassed (chamber pressure of 41.4 kPa ) and gassy conditions (chamber with N2 gas at 101 kPa). The results show that the straight fins had the largest enhancement in heat flow. Critical heat flux (CHF) for this surface showed an increase of 55% in comparison to the flat surface for the nominally degassed condition. The cubic pin finned and pyramid surfaces provided slightly more than half the heat flux enhancement (30% - 40% greater than the flat surface) of the straight fins. The gassy case showed that the straight fins again provided the largest enhancement (48%) in CHF relative to the flat surface. This was followed by the cubic pin fins, and pyramids which had increases of 31% and 18% respectively. No significant effect was observed in the surface temperature at which CHF occurs for either portion of the study.

  5. Surface Modification of Gold Nanoparticles with Small Molecules for Biochemical Analysis.

    PubMed

    Chen, Yiping; Xianyu, Yunlei; Jiang, Xingyu

    2017-02-21

    As one of the major tools for and by chemical science, biochemical analysis is becoming increasingly important in fields like clinical diagnosis, food safety, environmental monitoring, and the development of chemistry and biochemistry. The advancement of nanotechnology boosts the development of analytical chemistry, particularly the nanoparticle (NP)-based approaches for biochemical assays. Functional NPs can greatly improve the performance of biochemical analysis because they can accelerate signal transduction, enhance the signal intensity, and enable convenient signal readout due to their unique physical and chemical properties. Surface chemistry is a widely used tool to functionalize NPs, and the strategy for surface modification is of great significance to the application of NP-mediated biochemical assays. Surface chemistry not only affects the quality of NPs (stability, monodispersity, and biocompatibility) but also provides functional groups (-COO(-), -NH3(+), -CHO, and so on) or charges that can be exploited for bioconjugation or ligand exchange. Surface chemistry also dictates the sensitivity and specificity of the NP-mediated biochemical assays, since it is vital to the orientation, accessibility, and bioactivity of the functionalized ligands on the NPs. In this Account, we will focus on surface chemistry for functionalization of gold nanoparticles (AuNPs) with small organic molecules for biochemical analysis. Compared to other NPs, AuNPs have many merits including controllable synthesis, easy surface modification and high molar absorption coefficient, making them ideal probes for biochemical assays. Small-molecule functionalized AuNPs are widely employed to develop sensors for biochemical analysis, considering that small molecules, such as amino acids and sulfhydryl compounds, are more easily and controllably bioconjugated to the surface of AuNPs than biomacromolecules due to their less complex structure and steric hindrance. The orientation and

  6. Thermal/plasma-driven reversible wettability switching of a bare gold film on a poly(dimethylsiloxane) surface by electroless plating.

    PubMed

    Wu, Jian; Bai, Hai-Jing; Zhang, Xian-Bo; Xu, Jing-Juan; Chen, Hong-Yuan

    2010-01-19

    We report an approach for fabricating a tunable wettability surface by electroless gold plating on poly(dimethylsiloxane) (PDMS). A two-layer structured gold film with a tight layer and a loose layer can be obtained on the surface of a PDMS chip when the PDMS chip is immersed in a gold plating solution at 30 degrees C for 4 h. Its wettability can be rapidly switched between superhydrophilicity and superhydrophobicity by plasma and heat treatments without any self-assembled monolayer, and the superhydrophobicity can be even changed from the gecko-foot-hair-like character to the lotus-leaf-like character. Benefiting from the various wettabilities of the prepared gold/PDMS composites, protein patterning is successfully achieved on a patterned superhydrophobic/superhydrophilic gold/PDMS composite; a superhydrophobic needle for transferring supersmall water droplets (1 microL) to a superhydrophobic surface is successfully fabricated.

  7. Use of surface plasmon resonance to investigate lateral wall deposition kinetics and properties of polydopamine films.

    PubMed

    Li, Hui; Cui, Dafu; Cai, Haoyuan; Zhang, Lulu; Chen, Xing; Sun, Jianhai; Chao, Yapeng

    2013-03-15

    Dopamine (DA) is a particularly important neurotransmitter. Polydopamine (pDA) films have been demonstrated to be important materials for the immobilization of biomolecules onto almost any type of solid substrate. In this study, a surface plasmon resonance (SPR)-based sensor system with the sensor chip surface parallel to the direction of gravity was used to investigate the lateral wall deposition kinetics and properties of pDA films. The deposition kinetics of pDA Films are limited by the oxidation process. The pDA film could not be removed from the sensor chip completely by a strongly alkaline solution, indicating that the pDA film was heterogeneous in the direction of deposition. The pDA film formed near the interior of the solution was less stable than the film formed near the gold-solution interface. Adsorption of proteins on pDA film was studied compared with that on bare gold and dextran sensor chip. The reduction of Au(111) cations by the pDA film, forming a layer of gold particles, was monitored using SPR.

  8. Measurement and scaling of air-surface mercury exchange from substrates in the vicinity of two Nevada gold mines.

    PubMed

    Miller, Matthieu B; Gustin, Mae S; Eckley, Chris S

    2011-09-01

    The state of Nevada has extensive mineral resources, and is the largest producer of gold in the USA as well as fourth in world gold production. Mercury (Hg) is often present in the hydrothermal systems that produce gold deposits, and can be found in elevated concentrations in gold ore. As a result, mining of gold ore in Nevada has been shown to release Hg to the atmosphere from point and non-point sources. This project focused on measurement of air-soil Hg exchange associated with undisturbed soils and bedrock outcrops in the vicinity of two large gold mines. Field and laboratory data collected were used to identify the important variables controlling Hg flux from these surfaces, and to estimate a net flux from the areas adjacent to the active mines as well as that occurring from the mined area pre-disturbance. Mean daily flux by substrate type ranged from 9 ng m(-2) day(-1) to 140 ng m(-2) day(-1). Periods of net deposition of elemental Hg were observed when air masses originating from a mine site moved over sampling locations. Based on these observations and measured soil Hg concentrations we suggest that emissions from point and non-point sources at the mines are a source of Hg to the surrounding substrates with the amount deposited not being of an environmental concern but of interest mainly with respect to the cycling of atmospheric elemental Hg. Observations indicate that while some component of the deposited Hg is sequestered in the soil, this Hg is gradually released back to the atmosphere over time. Estimated pre-disturbance emissions from the current mine footprints based on field data were 0.1 and 1.7 kg yr(-1), compared to that estimated for the current non-point mining sources of 19 and 109 kg yr(-1), respectively.

  9. Synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent and the catalytic oxidation of α-naphthylamine

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Song, Y.; Cheng, Z. P.; Zhou, J. F.; Wei, C.

    2013-01-01

    Electrochemical synthesis of gold nanoparticles on the surface of pyrolytic graphite using penicillin as a stabilizing reagent was proposed. The gold nanoparticles were characterized by scanning electron microscopy, cyclic voltammetry, IR spectra, UV spectra, and powder X-ray diffraction spectra. The electro-chemical catalysis of penicillin for α-naphthylamine was demonstrated.

  10. Self-assembly of large gold nanoparticles for surface-enhanced Raman spectroscopy

    DOE PAGES

    Yang, Guang; Nanda, Jagjit; Wang, Boya; ...

    2017-04-05

    Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode–electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm.more » The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. Lastly, the EFs for the best performing Au NP monolayer are between 106 and 108 and give quantitative signal response when analyte concentration is changed.« less

  11. Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy.

    PubMed

    Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T

    2017-04-05

    Performance of portable technologies from mobile phones to electric vehicles is currently limited by the energy density and lifetime of lithium batteries. Expanding the limits of battery technology requires in situ detection of trace components at electrode-electrolyte interphases. Surface-enhance Raman spectroscopy could satisfy this need if a robust and reproducible substrate were available. Gold nanoparticles (Au NPs) larger than 20 nm diameter are expected to greatly enhance Raman intensity if they can be assembled into ordered monolayers. A three-phase self-assembly method is presented that successfully results in ordered Au NP monolayers for particle diameters ranging from 13 to 90 nm. The monolayer structure and Raman enhancement factors (EFs) are reported for a model analyte, rhodamine, as well as the best performing polymer electrolyte salt, lithium bis(trifluoromethane)sulfonimide. Experimental EFs for the most part correlate with predictions based on monolayer geometry and with numerical simulations that identify local electromagnetic field enhancements. The EFs for the best performing Au NP monolayer are between 10(6) and 10(8) and give quantitative signal response when analyte concentration is changed.

  12. Silver nanoparticles decorated nanoporous gold for surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Yang, Min; Zhang, Ling; Chen, Bin; Wang, Zheng; Chen, Chao; Zeng, Heping

    2017-02-01

    Raman spectra are considered as signatures of matter and have been widely used to identify several classes of materials. The development of mobile spectrometers further extends applications of Raman spectroscopy, and both indoor/outdoor and in vivo/in vitro measurements have been evaluated on site. However, the finite detection level restricts its application in high density matters. Here we report a facile silver nanoparticle decorated nanoporous gold (NanoAg@NPG) substrate, which can provide high enhancement of the Raman signal from nearby molecules by 785 nm photoexcitation. This enhancement is attributed to the abundant Raman-active nanogaps constructed by adjacent nanoparticles and also by the NPG ligaments and adhered nanoparticles. This NanoAg@NPG substrate shows great potential as a reproducible and quantifiable near infrared surface-enhanced Raman scattering probe for various targets, since it performs well in the so-called biological window which can avoid autofluorescence and absorption either from targets or surroundings in the visible optical region.

  13. A novel electrochemical sensor surface for the detection of hydrogen peroxide using cyclic bisureas/gold nanoparticle composite.

    PubMed

    Mathew, Manjusha; Sandhyarani, N

    2011-10-15

    A novel electrochemical sensor surface with enhanced sensitivity for the detection of hydrogen peroxide has been developed based on the layer-by-layer assembly of mercapto propionic acid (MPA), cystine-based polymethylene-bridged cyclic bisureas (CBU)/gold nanoparticle (AuNP) and horseradish peroxidase (HRP) on gold electrode. Possibility of a large number of hydrogen bonds, allowed by the chemical and sterical structure of the CBU ensures the proper immobilization of the enzyme in favorable orientation and retention of enzymatic activity. Efficient electron tunneling property of AuNP together with its electrocatalytic activity leads to higher sensitivity in the detection of H(2)O(2). In cyclic voltammetry measurements a cathodic current due to direct electron transfer of HRP is observed which, indicates excellent electrocatalytic activity of the sensor surface. The biosensor surface modified with gold nanoparticle and CBU showed a lower detection limit of 50 nM for hydrogen peroxide. Chronoamperometry is performed at -0.3 V and Michaelis-Menten constant K(M)(app) value is estimated to be 4.5 μM. The newly developed sensor surface showed very high stability, reproducibility and high sensitivity.

  14. Microwave-Accelerated Surface Modification of Plasmonic Gold Thin Films with Self-Assembled Monolayers of Alkanethiols

    PubMed Central

    Grell, Tsehai A.J.; Alabanza, Anginelle M.; Gaskell, Karen; Aslan, Kadir

    2013-01-01

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in less than 10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in 1) a semi-continuous and 2) a continuous fashion and at room temperature (24 hours, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET were confirmed by contact angle measurements, Fourier–transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 hours) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structure of SAMs prepared using both microwave heating and at room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process was carried out using both microwave heating and at room temperature. PMID:24083414

  15. Microwave-accelerated surface modification of plasmonic gold thin films with self-assembled monolayers of alkanethiols.

    PubMed

    Grell, Tsehai A J; Alabanza, Anginelle M; Gaskell, Karen; Aslan, Kadir

    2013-10-29

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in <10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in (1) a semicontinuous fashion and (2) a continuous fashion at room temperature (24 h, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET was confirmed by contact angle measurements, Fourier transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 h) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structures of SAMs prepared using both microwave heating and room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process had been conducted using both microwave heating and room temperature.

  16. Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO 2 (110)

    SciTech Connect

    Goldman, Nir; Browning, Nigel D.

    2011-06-16

    Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

  17. Biopolymer coated gold nanocrystals prepared using the green chemistry approach and their shape-dependent catalytic and surface-enhanced Raman scattering properties.

    PubMed

    Chou, Chih-Wei; Hsieh, Hui-Hsuan; Hseu, You-Cheng; Chen, Ko-Shao; Wang, Gou-Jen; Chang, Hsien-Chang; Pan, Yong-Li; Wei, Yi-Syuan; Chang, Ko Hsin; Harn, Yeu-Wei

    2013-07-21

    This study deals with the preparation of multi-shaped nanoscale gold crystals under synthetically simple, green, and efficient conditions using a seed-mediated growth approach in the presence of hyaluronic acid (HA). These highly biocompatible multi-shaped gold nanocrystals were examined to evaluate their catalytic and surface enhanced Raman scattering (SERS) properties. The results show that the size and shape of the nanocrystals are mainly correlated to the amount of seed, seed size, HA concentration, and reaction temperature. Gold seeds accelerate the reduction of the gold precursor to form gold nanocrystals using HA. The HA serves as a reducing agent and a growth template for the reduction of Au(III) and nanocrystal stabilization. The multi-shaped gold nanocrystals showed superior catalytic properties and higher SERS performance. The simple, green approach efficiently controls the nanocrystals and creates many opportunities for future applications.

  18. Diffuse reflectivity of gold plating with high power laser irradiation

    NASA Astrophysics Data System (ADS)

    Wu, Yong; Zhang, Lei; Yang, Pengling; Wang, Zhenbao; Tao, Mengmeng; Liu, Fuhua; Feng, Guobin

    2015-05-01

    The discoloration and optical characteristics of the gold plating film under long-time high power laser irradiation are investigated. The fabrication process of gold plating on nickel underplate on rough surface of copper and aluminum alloy substrates is introduced. The measurement results of the diffuse reflectivity for the samples with different surface roughness indicate that roughness of the gold layer surface should be 4μm to obtain the maximum value of diffuse reflectivity. The discoloration and variation of diffuse reflectivity are experimentally studied under 2000W irradiation. The research results show that the discoloration and degrading of reflectivity are caused by the diffusion of Ni to the gold plating surface and forming NiO thin film due to the porosity of the gold film and high temperature treatment. A change of diffuse reflectivity related mechanism is described. Several plating solution recipes are used to eliminate the discoloration and mitigate the degrading of the reflectivity on gold surface.

  19. Dissimilar kinetic behavior of electrically manipulated single- and double-stranded DNA tethered to a gold surface.

    PubMed

    Rant, Ulrich; Arinaga, Kenji; Tornow, Marc; Kim, Yong Woon; Netz, Roland R; Fujita, Shozo; Yokoyama, Naoki; Abstreiter, Gerhard

    2006-05-15

    We report on the electrical manipulation of single- and double-stranded oligodeoxynucleotides that are end tethered to gold surfaces in electrolyte solution. The response to alternating repulsive and attractive electric surface fields is studied by time-resolved fluorescence measurements, revealing markedly distinct dynamics for the flexible single-stranded and stiff double-stranded DNA, respectively. Hydrodynamic simulations rationalize this finding and disclose two different kinetic mechanisms: stiff polymers undergo rotation around the anchoring pivot point; flexible polymers, on the other hand, are pulled onto the attracting surface segment by segment.

  20. Investigating the Surface Roughness of Mercury

    NASA Astrophysics Data System (ADS)

    Susorney, H. C. M.; Barnouin, O. S.; Ernst, C. M.

    2014-12-01

    The Mercury Laser Altimeter (MLA) on the MErcury, Surface, Space ENviorment, GEochemistry, and Ranging (MESSENGER) spacecraft has acquired high-resolution topographic measurements of Mercury's northern hemisphere. These measurements permit the quantification of surface roughness on Mercury over baselines between 500 m and 200 km. In contrast to previous studies of Mercury's surface roughness, which have employed median differential surface slope, we calculate surface roughness as the root mean square (RMS) deviation of the difference in height. If the topography is self-affine or fractal, a power law can be fit to the RMS deviation as a function of baseline length. The exponent of this fit is called the Hurst exponent. This Hurst exponent describes whether or not a surface is self-affine, which occurs when processes produce a surface roughness that is inherently random. The surface roughness of Mercury's northern hemisphere reflects the observed bimodal nature of Mercury: the northern smooth plains have lower roughness values than the rougher heavily cratered terrain and intercrater plains. The relationship between RMS height and baseline length on Mercury shows two fractal sections, one between lengths of 500 m and 1 km, and another between lengths of 1 km and 20 km. We also find that the northern rise is indistinguishable from the surrounding smooth plains across all measured baselines, implying that the rise did not alter its surface topography at the baselines used in this study. Craters that host radar-bright deposits have similar roughness values to craters that do not host such deposits. Finally, fresh crater ejecta within the smooth plains have similar roughness values (particularly at the 1 km baseline) to the intercrater plains, supporting the interpretation that the intercrater plains may result from the modification of volcanic plains via cratering.

  1. PM IRRAS investigation of thin silica films deposited on gold. Part 1. Theory and proof of concept.

    PubMed

    Zawisza, Izabella; Wittstock, Gunther; Boukherroub, Rabah; Szunerits, Sabine

    2007-08-28

    Polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) was successfully used for the first time to characterize an optically transparent thin oxide film. SiO2 layers of 7 nm thickness were synthesized by plasma enhanced chemical vapor deposition (PECVD) on 200 nm thick gold covered glass slides. Despite the fact that silica is transparent and absorptive to IR radiation when deposited in the form of thin films on a gold surface, it preserves the high metallic reflectivity for the IR light. At grazing angles of incidence of the IR beam, the enhancement of the normal component of the electric field at the interface is comparable to that of Au alone. In addition, the analysis of the structure of a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid monolayer deposited using the Langmuir-Blodgett technique is demonstrated.

  2. Investigation of Surfaces after Non Conventional Machining

    NASA Astrophysics Data System (ADS)

    Micietova, Anna; Neslusan, Miroslav; Cillikova, Maria

    2016-12-01

    This paper deals with analysis of surface integrity of steel after electro discharge machining (EDM), water jet machining, (WJM) laser beam machining (LBM) and plasma beam machining (PBM). The paper discusses surface integrity expressed in surface roughness, sample precision expressed in perpendicularity deviation as well as stress state. This study also demonstrates influence of the various non-conventional methods on structure transformations and reports about sensitivity of the different non-conventional methods of machining with regard to variable thickness of machined samples.

  3. SU-E-T-518: Investigation of Gold Nanoparticle Radiosensitization for Carbon Ion Therapy

    SciTech Connect

    Lin, Y; Held, K; Paganetti, H; Schuemann, J; McMahon, S

    2015-06-15

    Purpose The aim of this work is to investigate the radiosensitization effect of gold nanoparticles (GNP) in carbon ion irradiation. Nano-scale dosimetric characteristics of GNP interaction with carbon ions as well as the secondary particles generated as a carbon beam traverses the water phantom were studied. Methods Monte Carlo simulations were carried out using TOPAS (Tool for Particle Simulation). First, a water phantom was irradiated by the carbon ion beam and the particle shower spectrum at several depths was recorded in phase spaces. We analyzed the number and energy spectrum of each particle type. Then, the phase spaces obtained from Step 1 were modified to nanometer scale to irradiate a single 50 nm GNP. The secondary electrons that escaped from the GNPs following interactions with each particle type were recorded as phase spaces. The number and energy spectrum of the secondary electrons were studied. The same simulations were repeated replacing the GNPs with water nanoparticles (WNPs) with the same size. The energy absorbed in either GNP or WNP was scored. Results There is a large amount of secondary particles generated through carbon ion beam interaction with the water phantom. Analysis of the secondary electrons generated by the primary particles which escape from the nanoparticle revealed that majority (above 80%) of these electrons were generated by the GNP interaction with Carbon beam itself, making it the biggest contributor to the enhancement. The ratio of the energy absorbed by GNP and WNP is about 8–10 for charged particles and above 3000 for gammas. Conclusion We showed in the study the GNPs may potentially be used to enhance carbon ion therapy, and the main mechanism of enhancement is the interaction with Carbon ion particles itself.

  4. Tight and uniform layer of covalently bound aminoethylophenyl groups perpendicular to gold surface for attachment of biomolecules.

    PubMed

    Fau, Michal; Kowalczyk, Agata; Olejnik, Piotr; Nowicka, Anna M

    2011-12-15

    Strongly adhered layers of the compound with the primary amino group directed toward the solution were obtained at the gold surface by chronoamperometric electroreduction of 4-aminoethylobenzenodiazonium salt (AEBD) in acetonitrile solution at appropriately selected potential. The used techniques (EQCM, AFM, EIS, PM, IRRAS) showed that the nature and thickness of formed aminoethylophenyl layer strongly depend on the potential applied to the electrode. Electroreduction of AEBD salt at a potential more negative than -0.6 V (vs Ag/AgCl) leads to about monolayer on the gold surface. Additionally, such a layer was very tight and uniform. The electrochemical measurements indicate that the efficient and precise attachment of biomolecules to the aminoethylophenyl layer is only possible when this layer is formed at appropriate potential. This was shown for ss- and dsDNA.

  5. Gold-plating of Mylar lift films to capitalize on surface enhanced Raman spectroscopy for chemical extraction of drug residues.

    PubMed

    Fox, James D; Waverka, Kristin N; Verbeck, Guido F

    2012-03-10

    The method of residue extraction through electrostatic lifting provides a distinctive mode of performing ultra-trace analysis. These lifts provide a medium for analyte extraction via nanomanipulation-coupled to nanospray ionization-mass spectrometry (NSI-MS). This method of extraction can be coupled to Raman spectroscopy for supplemental verification of analytes using surface enhanced Raman scattering (SERS). The gold surface used for SERS provides an enhanced effect on peak signal intensity allowing ultra-trace amounts to be detected more effectively. The aim of this research is to utilize gold-coated films with electrostatic lifting in order to collect latent materials and analyze chemicals of interest contained in them via SERS.

  6. Propagation length of mid-infrared surface plasmon polaritons on gold: Impact of morphology change by thermal annealing

    NASA Astrophysics Data System (ADS)

    Hiramatsu, Nobuyoshi; Kusa, Fumiya; Imasaka, Kotaro; Morichika, Ikki; Takegami, Akinobu; Ashihara, Satoshi

    2016-11-01

    We studied the propagation length of surface plasmon polaritons (SPPs) at the gold/air interface in the mid-infrared range. We showed that SPPs propagate for a distance of about or above 10 mm at a wavelength of 10.6 μm, in good agreement with the value predicted from the dielectric constant of polycrystalline gold. We also demonstrated that a simple treatment of thermal annealing led to noticeable elongation of SPP propagation length, accompanied by increased grain size and decreased surface roughness. Quantitative evaluation of SPP propagation length, in correlation with material's morphology, is important in designing plasmonic devices and beneficial for understanding the mechanisms of SPP's losses that underlie electric-field enhancement.

  7. Ultra-sensitive immunosensor for detection of hepatitis B surface antigen using multi-functionalized gold nanoparticles.

    PubMed

    Shourian, M; Ghourchian, H; Boutorabi, M

    2015-10-01

    The signal amplification for analytical purposes has considerable potential in detecting trace levels of analytes for clinical, security or environmental applications. In the present report a strategy based on a sandwich type immunoassay system was designed for the detection of hepatitis B surface antigen which exploits the specific affinity interaction between streptavidin and biotin recognition systems. The method involves the specific coupling of multi-functionalized gold nanoparticles (bearing biotin and luminol molecules) to the streptavidin modified by secondary antibody. The chemiluminescent signal is produced by the gold nanoparticles in the presence of HAuCl4 as catalyst and hydrogen peroxide as oxidant. The immunosensor was able to detect hepatitis B surface antigen in the linear concentration range from 1.7 to 1920 pg mL(-1) and the detection limit of 0.358 pg mL(-1), at signal/noise = 3.

  8. Rapid Detection and Identification of Overdose Drugs in Saliva by Surface-Enhanced Raman Scattering Using Fused Gold Colloids

    PubMed Central

    Farquharson, Stuart; Shende, Chetan; Sengupta, Atanu; Huang, Hermes; Inscore, Frank

    2011-01-01

    The number of drug-related emergency room visits in the United States doubled from 2004 to 2009 to 4.6 million. Consequently there is a critical need to rapidly identify the offending drug(s), so that the appropriate medical care can be administered. In an effort to meet this need we have been investigating the ability of surface-enhanced Raman spectroscopy (SERS) to detect and identify numerous drugs in saliva at ng/mL concentrations within 10 minutes. Identification is provided by matching measured spectra to a SERS library comprised of over 150 different drugs, each of which possess a unique spectrum. Trace detection is provided by fused gold colloids trapped within a porous glass matrix that generate SERS. Speed is provided by a syringe-driven sample system that uses a solid-phase extraction capillary combined with a SERS-active capillary in series. Spectral collection is provided by a portable Raman analyzer. Here we describe successful measurement of representative illicit, prescribed, and over-the-counter drugs by SERS, and 50 ng/mL cocaine in saliva as part of a focused study. PMID:24310588

  9. The Impact of Surface Ligands and Synthesis Method on the Toxicity of Glutathione-Coated Gold Nanoparticles.

    PubMed

    Harper, Bryan; Sinche, Federico; Wu, Rosina Ho; Gowrishankar, Meenambika; Marquart, Grant; Mackiewicz, Marilyn; Harper, Stacey L

    2014-06-01

    Gold nanoparticles (AuNPs) are increasingly used in biomedical applications, hence understanding the processes that affect their biocompatibility and stability are of significant interest. In this study, we assessed the stability of peptide-capped AuNPs and used the embryonic zebrafish (Danio rerio) as a vertebrate system to investigate the impact of synthesis method and purity on their biocompatibility. Using glutathione (GSH) as a stabilizer, Au-GSH nanoparticles with identical core sizes were terminally modified with Tryptophan (Trp), Histidine (His) or Methionine (Met) amino acids and purified by either dialysis or ultracentrifugation. Au-GSH-(Trp)2 purified by dialysis elicited significant morbidity and mortality at 200 μg/mL, Au-GSH-(His)2 induced morbidity and mortality after purification by either method at 20 and 200 μg/mL, and Au-GSH-(Met)2 caused only sublethal responses at 200 μg/mL. Overall, toxicity was significantly reduced and ligand structure was improved by implementing ultracentrifugation purifications at several stages during the multi-step synthesis and surface modification of Au-GSH nanoparticles. When carefully synthesized at high purity, peptide-functionalized AuNPs showed high biocompatibility in biological systems.

  10. The Impact of Surface Ligands and Synthesis Method on the Toxicity of Glutathione-Coated Gold Nanoparticles

    PubMed Central

    Harper, Bryan; Sinche, Federico; Ho Wu, Rosina; Gowrishankar, Meenambika; Marquart, Grant; Mackiewicz, Marilyn; Harper, Stacey L.

    2014-01-01

    Gold nanoparticles (AuNPs) are increasingly used in biomedical applications, hence understanding the processes that affect their biocompatibility and stability are of significant interest. In this study, we assessed the stability of peptide-capped AuNPs and used the embryonic zebrafish (Danio rerio) as a vertebrate system to investigate the impact of synthesis method and purity on their biocompatibility. Using glutathione (GSH) as a stabilizer, Au-GSH nanoparticles with identical core sizes were terminally modified with Tryptophan (Trp), Histidine (His) or Methionine (Met) amino acids and purified by either dialysis or ultracentrifugation. Au-GSH-(Trp)2 purified by dialysis elicited significant morbidity and mortality at 200 µg/mL, Au-GSH-(His)2 induced morbidity and mortality after purification by either method at 20 and 200 µg/mL, and Au-GSH-(Met)2 caused only sublethal responses at 200 µg/mL. Overall, toxicity was significantly reduced and ligand structure was improved by implementing ultracentrifugation purifications at several stages during the multi-step synthesis and surface modification of Au-GSH nanoparticles. When carefully synthesized at high purity, peptide-functionalized AuNPs showed high biocompatibility in biological systems. PMID:26213631

  11. Geologic and isotopic investigation of the South Willow creek gold prospect, Madison County, Montana

    SciTech Connect

    Saunders, M.M.; Ripley, E.M.

    1985-01-01

    The South Willow Creek gold prospect is located in the southwestern part of the Potosi tungsten district, southwest Montana. Gold-quartz veins occur in the Bismark shear zone within granodiorite host rocks of the late Cretaceous-early Tertiary Tobacco Root batholith. Four well developed zones of progressive alteration are found adjacent to faults and veins in the area. Gold occurs in solid solution with silver as inclusion in pyrite and alone with quartz. The highest gold assay values occur closest to the Bismark shear zone. Sulfur isotope values for pyrite, galena, and molybdenum range from -6.5 to +1.7 per thousands. Pyrite-galena and pyrite-molybdenum ..delta.. values indicate sulfide deposition temperatures ranging from 220 to 265/sup 0/C. Isotopic values suggest that deposition occurred from a fluid with a delta/sup 34/S value of near 0 per thousand, at redox conditions near those of the ..sigma..sulfate/..sigma..sulfide boundary. Mineral assemblages and delta/sup 34/S values are consistent with gold transport as a chloride complex under acid oxidizing conditions. Increases in pH and decreases in temperature accompanying wallrock alteration are the likely causes of gold deposition. Sericite deltaD values are variable, ranging from -69 to -136 per thousand. Computed delta/sup 18/O/sub H/sub 2/O/ and deltaD/sub H/sub 2/O/ values are most easily interpreted as indicating a predominantly magmatic fluid source, with locally variable contributions of meteoric water. However, non-equilibrium delta/sup 18/O values of coexisting quartz and sericite, and the deltaD values of sericite, both suggest that isotopic exchange rates were variable, and limit the unambiguous determination of fluid source.

  12. Wettability Control of Gold Surfaces Modified with Benzenethiol Derivatives: Water Contact Angle and Thermal Stability.

    PubMed

    Tatara, Shingo; Kuzumoto, Yasutaka; Kitamura, Masatoshi

    2016-04-01

    The water wettability of Au surfaces has been controlled using various benzenethiol derivatives including 4-methylbenzenethiol, pentafluorobenzenethiol, 4-flubrobenzenethiol, 4-methoxy-benzenethiol, 4-nitrobenzenethiol, and 4-hydroxybenzenethiol. The water contact angle of the Au surface modified with the benzenethiol derivative was found to vary in the wide range of 30.9° to 88.3°. The contact angle of the modified Au films annealed was also measured in order to investigate their thermal stability. The change in the contact angle indicated that the modified surface is stable at temperatures below about 400 K. Meanwhile, the activation energy of desorption from the modified surface was estimated from the change in the contact angle. The modified Au surface was also examined using X-ray photoelectron spectroscopy.

  13. Polydopamine-enabled surface functionalization of gold nanorods for cancer cell-targeted imaging and photothermal therapy

    PubMed Central

    Black, Kvar CL; Yi, Ji; Rivera, José G; Zelasko-Leon, Daria C; Messersmith, Phillip B

    2012-01-01

    Aim A novel biomimetic strategy was employed for presenting antibodies on gold nanorods (NRs) to target growth factor receptors on cancer cells for use in photothermal therapy. Materials & methods Polydopamine (PD) was polymerized onto gold NRs, and EGF receptor antibodies (anti-EGFR) were immobilized onto the layer. Cell-binding affinity and light-activated cell death of cancer cells incubated with anti-EGFR-PD-NRs were quantified by optical imaging. Results PD was deposited onto gold NRs, and antibodies were bound to PD-coated NRs. Anti-EGFR-PD-NRs were stable in media, and were specifically bound to EGFR-overexpressing cells. Illumination of cells targeted with anti-EGFR-PD-NRs enhanced cell death compared with nonirradiated controls and cells treated with antibody-free NRs. Conclusion PD facilitates the surface functionalization of gold NRs with biomolecules, allowing cell targeting and photothermal killing of cancer cells. PD can potentially coat a large variety of nanoparticles with targeting ligands as a strategy for biofunctionalization of diagnostic and therapeutic nanoparticles. PMID:22891865

  14. Bimetallic nanostructures as active Raman markers: gold-nanoparticle assembly on 1D and 2D silver nanostructure surfaces.

    PubMed

    Gunawidjaja, Ray; Kharlampieva, Eugenia; Choi, Ikjun; Tsukruk, Vladimir V

    2009-11-01

    It is demonstrated that bimetallic silver-gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with well-defined geometries by means of electrostatic interactions. One-dimensional (1D) silver nanowires, two-dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom-up assembly. The gold nanoparticles are electrostatically bound onto the 1D silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle-to-particle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best-performing silver-gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir-Blodgett technique. An optimized design of a single-nanostructure substrate for surface-enhanced Raman spectroscopy (SERS), based on a wet-assembly technique proposed here, can serve as a compact and low-cost alternative to fabricated nanoparticle arrays.

  15. Surface plasmon enhanced energy transfer between gold nanorods and fluorophores: application to endocytosis study and RNA detection.

    PubMed

    Zhang, Yinan; Wei, Guoke; Yu, Jun; Birch, David J S; Chen, Yu

    2015-01-01

    Previously we have demonstrated surface plasmon enhanced energy transfer between fluorophores and gold nanorods under two-photon excitation using fluorescence lifetime imaging microscopy (FLIM) in both solution and intracellular phases. These studies demonstrated that gold nanoparticle-dye energy transfer combinations are appealing, not only in Förster resonance energy transfer (FRET) imaging, but also energy transfer-based fluorescence lifetime sensing of bio-analytes. Here, we apply this approach to study the internalization of gold nanorods (GNRs) in HeLa cells using the early endosome labeling marker GFP. The observed energy transfer between GFP and the GNRs indicates the involvement of endocytosis in GNR uptake. Moreover, a novel nanoprobe based on oligonucleotide functionalized gold nanorods for nucleic acid sensing via dye-GNRs energy transfer is demonstrated, potentially opening up new possibilities in cancer diagnosis and prognosis. The influence of oligonucleotide design on such nanoprobe performance was studied for the first time using time-resolved fluorescence spectroscopy, bringing new insights to the optimization of the nanoprobe.

  16. Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-11-29

    The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2. Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state

  17. Study of Molecular Trapping by Gold Nanofinger Arrays on Surface-Enhanced Raman Substrates

    DTIC Science & Technology

    2011-01-21

    finger, nanoimprint lighography Abstract: The binding of trans-1,2-bis(4-pyridyl)-ethylene ( BPE ) molecules on substrates arrayed with gold...XPS results, BPE molecules are found to interact with the gold nanofingers through the lone pair electrons of pyridyl nitrogens, not through...delocalized π electrons. Furthermore, by comparing the AR-XPS spectra of finger arrays pre-closed before exposure to BPE with the spectra of arrays that

  18. RGD-conjugated silica-coated gold nanorods on the surface of carbon nanotubes for targeted photoacoustic imaging of gastric cancer

    NASA Astrophysics Data System (ADS)

    Wang, Can; Bao, Chenchen; Liang, Shujing; Fu, Hualin; Wang, Kan; Deng, Min; Liao, Qiande; Cui, Daxiang

    2014-05-01

    Herein, we reported for the first time that RGD-conjugated silica-coated gold nanorods on the surface of multiwalled carbon nanotubes were successfully used for targeted photoacoustic imaging of in vivo gastric cancer cells. A simple strategy was used to attach covalently silica-coated gold nanorods (sGNRs) onto the surface of multiwalled carbon nanotubes (MWNTs) to fabricate a hybrid nanostructure. The cross-linked reaction occurred through the combination of carboxyl groups on the MWNTs and the amino group on the surface of sGNRs modified with a silane coupling agent. RGD peptides were conjugated with the sGNR/MWNT nanostructure; resultant RGD-conjugated sGNR/MWNT probes were investigated for their influences on viability of MGC803 and GES-1 cells. The nude mice models loaded with gastric cancer cells were prepared, the RGD-conjugated sGNR/MWNT probes were injected into gastric cancer-bearing nude mice models via the tail vein, and the nude mice were observed by an optoacoustic imaging system. Results showed that RGD-conjugated sGNR/MWNT probes showed good water solubility and low cellular toxicity, could target in vivo gastric cancer cells, and obtained strong photoacoustic imaging in the nude model. RGD-conjugated sGNR/MWNT probes will own great potential in applications such as targeted photoacoustic imaging and photothermal therapy in the near future.

  19. RGD-conjugated silica-coated gold nanorods on the surface of carbon nanotubes for targeted photoacoustic imaging of gastric cancer.

    PubMed

    Wang, Can; Bao, Chenchen; Liang, Shujing; Fu, Hualin; Wang, Kan; Deng, Min; Liao, Qiande; Cui, Daxiang

    2014-01-01

    Herein, we reported for the first time that RGD-conjugated silica-coated gold nanorods on the surface of multiwalled carbon nanotubes were successfully used for targeted photoacoustic imaging of in vivo gastric cancer cells. A simple strategy was used to attach covalently silica-coated gold nanorods (sGNRs) onto the surface of multiwalled carbon nanotubes (MWNTs) to fabricate a hybrid nanostructure. The cross-linked reaction occurred through the combination of carboxyl groups on the MWNTs and the amino group on the surface of sGNRs modified with a silane coupling agent. RGD peptides were conjugated with the sGNR/MWNT nanostructure; resultant RGD-conjugated sGNR/MWNT probes were investigated for their influences on viability of MGC803 and GES-1 cells. The nude mice models loaded with gastric cancer cells were prepared, the RGD-conjugated sGNR/MWNT probes were injected into gastric cancer-bearing nude mice models via the tail vein, and the nude mice were observed by an optoacoustic imaging system. Results showed that RGD-conjugated sGNR/MWNT probes showed good water solubility and low cellular toxicity, could target in vivo gastric cancer cells, and obtained strong photoacoustic imaging in the nude model. RGD-conjugated sGNR/MWNT probes will own great potential in applications such as targeted photoacoustic imaging and photothermal therapy in the near future.

  20. Gold nanoparticles as a substrate in bio-analytical near-infrared surface-enhanced Raman spectroscopy.

    PubMed

    Butler, Holly J; Fogarty, Simon W; Kerns, Jemma G; Martin-Hirsch, Pierre L; Fullwood, Nigel J; Martin, Francis L

    2015-05-07

    As biospectroscopy techniques continue to be developed for screening or diagnosis within a point-of-care setting, an important development for this field will be high-throughput optimization. For many of these techniques, it is therefore necessary to adapt and develop parameters to generate a robust yet simple approach delivering high-quality spectra from biological samples. Specifically, this is important for surface-enhanced Raman spectroscopy (SERS) wherein there are multiple variables that can be optimised to achieve an enhancement of the Raman signal from a sample. One hypothesis is that "large" diameter (>100 nm) gold nanoparticles provide a greater enhancement at near-infrared (NIR) and infrared (IR) wavelengths than those <100 nm in diameter. Herein, we examine this notion using examples in which SERS spectra were acquired from MCF-7 breast cancer cells incubated with 150 nm gold nanoparticles. It was found that 150 nm gold nanoparticles are an excellent material for NIR/IR SERS. Larger gold nanoparticles may better satisfy the theoretical restraints for SERS enhancement at NIR/IR wavelengths compared to smaller nanoparticles. Also, larger nanoparticles or their aggregates are more readily observed via optical microscopy (and especially electron microscopy) compared to smaller ones. This allows rapid and straightforward identification of target areas containing a high concentration of nanoparticles and facilitating SERS spectral acquisition. To some extent, these observations appear to extend to biofluids such as blood plasma or (especially) serum; SERS spectra of such biological samples often exhibit a low signal-to-noise ratio in the absence of nanoparticles. With protein-rich biofluids such as serum, a dramatic SERS effect can be observed; although this might facilitate improved spectral biomarker identification in the future, it may not always improve classification between control vs. cancer. Thus, use of "large" gold nanoparticles are a good starting

  1. A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters.

    PubMed

    Marocico, Cristian A; Zhang, Xia; Bradley, A Louise

    2016-01-14

    We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green's tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r(-6) regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and acceptor

  2. A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters

    NASA Astrophysics Data System (ADS)

    Marocico, Cristian A.; Zhang, Xia; Bradley, A. Louise

    2016-01-01

    We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green's tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r-6 regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and acceptor

  3. A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters

    SciTech Connect

    Marocico, Cristian A.; Zhang, Xia; Bradley, A. Louise

    2016-01-14

    We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green’s tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r{sup −6} regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and

  4. In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS (Extended X-Ray Absorption Fine Structure).

    DTIC Science & Technology

    1988-01-28

    D-Al 263 INN-PLANE STRUCTURE OF UNDERPOTENTIALLY DEPOSITED COPPER /. ON GOLD (Iii) DET (U) PUERTO RICO UNIV RIO PIEDRAS DEPT OF PHVS I CS 0 R...051-0776 TECHNICAL REPORT #33 In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS by O.R. Melroy*, M.G...Strueture of Underpotentially Deposited Copper on Gold ( 11) determincd hv Surface EXAFS 0. R. Melroy*, N1. G. Samant, G. L. Borges. and J. G. Gordon

  5. IR investigations of surfaces and adsorbates

    SciTech Connect

    Gwyn Williams

    2001-12-10

    Synchrotron infrared reflection-absorption measurements on single crystal metal surfaces with adsorbates have led to the determination of many key parameters related to the bonding vibrational modes and the dynamics of adsorbates. In particular, energy couplings between electrons and adsorbate motion have been shown to be a dominant mechanism on metal surfaces. Excellent agreement has been obtained with calculations for many of the observations, and the synergy between theory and experiment has led to a deeper understanding of the roles of electrons and phonons in determining the properties of interfaces and their roles in phenomena as diverse as friction, lubrication, catalysis and adhesion. Nonetheless, as the experiments are pushed harder, to describe such effects as co-adsorbed systems, disagreements continue to challenge the theory and our comprehension also is still evolving.

  6. Green synthesis of biocompatible gold nanocrystals with tunable surface plasmon resonance using garlic phytochemicals.

    PubMed

    Menon, Deepthy; Basanth, Amritha; Retnakumari, Archana; Manzoor, K; Nair, Shantikumar V

    2012-12-01

    Synthesis of biocompatible gold nanoparticles having tunable optical absorbance finds immense use in biomedical applications such as cancer diagnosis and photothermal therapy. Hence, it is imperative to develop environment and bio-friendly green chemical processes that aid in preparing gold nanoparticles with tunable optical properties. In the present work, phytochemicals present in the medicinal herb, viz., garlic, were used to provide the dual effects of reduction of gold salts to gold nanoparticles as well as stabilization, in a single step process. The optical tunability of nanogold with respect to concentration of precursor and volume of garlic extract, processing conditions of garlic, its differing molecular weight fractions, reaction time and temperature has been demonstrated. The presence of a range of anisotropic nanogold including nanotriangles, nanorods and nanospheres as evident from TEM endows the colloid with a tunable optical absorption, specifically into the near infrared region. In vitro stability studies of the colloidal suspension in various media including saline, BSA, histidine and PBS showed that gold nanoparticles did not aggregate with time or differing pH conditions. The role of the garlic phytochemicals in providing stability against agglomeration was also substantiated by FTIR studies. Cytotoxicity studies performed using spherical and anisotropic gold nanoparticles on MCF-7 and L929 cell lines proved the biocompatibility of the material up to high doses of 500 microg/ml. The present work highlights the role of garlic phytochemicals in preparing biocompatible metallic gold nanoparticles with tunable optical properties and good in vitro stability, suggesting its potential use for molecular imaging or therapeutic nanomedicines.

  7. Fabrication and manipulation of solid-state SiO2 nano-gears on a gold surface.

    PubMed

    Deng, J; Troadec, C; Ample, F; Joachim, C

    2011-07-08

    A process is presented to fabricate solid-state nano-gears down to a 60 nm outer diameter with six teeth, where the 350 nm diameter ones already have 24 teeth. The small gears are free to move on a polycrystalline gold surface. The gears can be manipulated one by one, using an atomic force microscope (AFM) tip, to construct a train of gears where mechanical motion can be transmitted from one gear to another by mastering the surface friction. This is a first step on the way to bridge the fabrication gap between microfabricated and molecule gears.

  8. Fabrication and manipulation of solid-state SiO2 nano-gears on a gold surface

    NASA Astrophysics Data System (ADS)

    Deng, J.; Troadec, C.; Ample, F.; Joachim, C.

    2011-07-01

    A process is presented to fabricate solid-state nano-gears down to a 60 nm outer diameter with six teeth, where the 350 nm diameter ones already have 24 teeth. The small gears are free to move on a polycrystalline gold surface. The gears can be manipulated one by one, using an atomic force microscope (AFM) tip, to construct a train of gears where mechanical motion can be transmitted from one gear to another by mastering the surface friction. This is a first step on the way to bridge the fabrication gap between microfabricated and molecule gears.

  9. Tuning gold nanoparticles interfaces by specific peptide interaction for surface enhanced Raman spectroscopy (SERS) and separation applications.

    PubMed

    Manikas, Anastasios C; Causa, Filippo; Della Moglie, Raffaella; Netti, Paolo A

    2013-08-28

    Surface functionalization and control over nanostructured interfaces represents a key aspect in nanoscience and nanobiotechnology. Nanoplasmonic structures for analyte detection typically require sophisticated nanofabrication techniques, as well as bioactivated nanostructures that need multistep conjugations for chemical ligation. An alternative to such complex processes is to rely on specific biomolecules adsorption for decoration or self-assembly of nanoparticles at solid/liquid interface. In principle, small biomolecules with specific binding properties to nanostructures could control the assembly without modifying the nanoparticle chemistry, pH of the solution or salt concentration. Importantly, such an approach could be direct, robust, and reversible. In this work, we report about the use of a specific peptide for direct and reversible adsorption on gold nanoparticles with tuned interfacial properties just by simply adjusting the ratio between the numbers of peptide molecules to the number of gold nanoparticles. This easy, direct and reversible assembly of gold nanoparticles mediated by the specific peptide makes this platform ideal for small-volume samples and low concentrations detection using surface enhanced Raman Spectroscopy, as well as for the capture or separation of biomolecules in complex mix.

  10. Replacement of CTAB with peptidic ligands at the surface of gold nanorods and their self-assembling properties.

    PubMed

    Hamon, C; Bizien, T; Artzner, F; Even-Hernandez, P; Marchi, V

    2014-06-15

    Herein, we describe the self-assembling of gold nanorods (GNRs) induced during the ligand exchange at their surface. An exchange reaction between tricysteine PEGylated peptidic ligands and cetyltrimethylammonium bromide (CTAB)-protected gold nanorods is conducted. We demonstrated that the terminal group charge (positively or negatively charged) and the hydrophobicity of the peptidic ligands (bearing or not an undecanoyl chain) strongly affects the self-organization of the GNRs occurring in solution. Adjusting the amount of short PEGylated peptides causes a self-organization of the gold nanorods in solution, resulting in a red- or blue-shift of the plasmon bands. The decrease of their surface charge and the self-assembling in solution were first shown by zetametry, by Dynamic Light Scattering and UV-spectroscopy. Thanks to Small Angle X-ray Scattering experiments and Transmission Electron Microscopy images, the self-organization of the nanorods in solution was clearly demonstrated and correlated to the spectroscopic change in absorbance. Conversely, in the case of longer PEGylated peptidic ligands including an undecanoyl chain, the GNRs are particularly stable against aggregation for several days after purification. By controlled drying on a substrate, we showed their ability to self-organize into well-defined ordered structures making them very attractive as building blocks to design optical materials.

  11. Phthalocyaninato complexes with peripheral alkylthio chains: disk-like adsorbate species for the vertical anchoring of ligands on gold surfaces

    PubMed Central

    Siemeling, Ulrich; Schirrmacher, Christian; Glebe, Ulrich; Bruhn, Clemens; Baio, Joe E.; Árnadóttir, Líney; Castner, David G.; Weidner, Tobias

    2011-01-01

    Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, β-positioned, alkylthio substituents SR (1a: R = n-C8H17, 1b: R = n-C12H25), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether–gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to MnII. PMID:21857743

  12. In situ SEM and ToF-SIMS analysis of IgG conjugated gold nanoparticles at aqueous surfaces

    SciTech Connect

    Yang, Li; Zhu, Zihua; Yu, Xiao-Ying; Rodek, Gene; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Cowin, James P.

    2014-04-01

    In this study, we report new results of in situ study of 5 nm goat anti-mouse IgG gold nanoparticles in a novel portable vacuum compatible microfluidic device using scanning electron microscope (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The unique feature of the liquid flow cell is that the detection window is open to the vacuum allowing direct probing of the liquid surface. The flow cell is composed of a silicon nitride (SiN) membrane and polydimethylsiloxane (PDMS), and it is fully compatible with vacuum operations for surface analysis. The aperture can be drilled through the 100 nm SiN membrane using a focused ion beam. Characteristic signals of the conjugated gold nanoparticles were successfully observed through the aperture by both energy-dispersive X-ray spectroscopy (EDX) in SEM and ToF-SIMS. Comparison was also made among wet samples, dry samples, and liquid sample in the flow cell using SEM/EDX. Stronger gold signal can be observed in our novel portable device by SEM/EDX compared with the wet or dry samples, respectively. Our results indicate that analyses of the nanoparticle components are better made in their native liquid environment. This is made possible using our unique microfluidic flow cell.

  13. High surface area Au-SBA-15 and Au-MCM-41 materials synthesis: tryptophan amino acid mediated confinement of gold nanostructures within the mesoporous silica pore walls.

    PubMed

    Selvakannan, Pr; Mantri, Kshudiram; Tardio, James; Bhargava, Suresh K

    2013-03-15

    Advantages of confining the gold nanostructures formation within the mesoporous silica pore walls during its silica condensation and consequent improvement in the textural properties such as specific surface area, pore volume, pore diameter have been demonstrated, while retaining gold nanostructures within the silica walls. This has been achieved by tryptophan mediated confinement of gold nanoparticles formation within the condensing silica framework, to obtain Au-SBA-15 (SSA 1247 m(2)/g, V(t)~1.37 cm(3)/g) and Au-MCM-41 (SSA 1287 m(2)/g, V(t)~1.1 cm(3)/g), mesoporous silica materials having the combination of very high surface area from the porous support as well as gold nanoparticles infiltrated silica walls. Choice of tryptophan for this purpose is that it has an indole group, which was known to reduce gold ions to form gold nanoparticles and its amine and carboxylic acid groups, catalyze the hydrolysis of silica precursors in a wide range of pH. These properties have been utilized in restricting the gold nanostructures formation inside the condensing silica phase without affecting the self assembly between the silica precursors and the triblock copolymer (for SBA-15) or cetyltrimethylammonium bromide template (for MCM-41). The polytryptophan and the gold nanostructures, which were encapsulated within the silica framework and upon removal of the template by calcination resulting in the formation mesoporous materials wherein the silica walls become microporous due to the removal of occluded polytryptophan and the resulting microchannels contain very small gold nanostructures. Hence, the resulting materials have very high surface area, high pore volume and narrow pore size distribution as compared to their parent SBA-15, MCM-41 and SBA-15, MCM-41 post functionalized with gold nanoparticles inside the pores.

  14. Inkjet-printed gold nanoparticulate patterns for surface finish in electronic package

    NASA Astrophysics Data System (ADS)

    Jang, Seonhee; Cho, Hyejin; Kang, Seongkoo; Oh, Sungil; Kim, Donghoon

    2011-11-01

    Gold (Au) pads for surface finish in electronic package were developed by the inkjet printing method. The Au ink for printing was prepared by Au nanoparticles (NPs) coated with capping molecules of dodecylamine (C12H25NH2). The microstructures of the inkjet-printed Au films were characterized after sintering in various gas flows. The film sintered in air showed that bonding between NPs was not enough for further grain growth due to the incomplete decomposition of the capping layer. The film sintered under nitrogen (N2) had NPs existing on the surface and the bottom which did not participate in sintering. When the film was sintered under N2-bubbled through formic acid (FA/N2), a large portion of the pores were observed to make a holey pancake-like structure of the film. The microstructures of the inkjet-printed Au film became denser with grain growth when Au NPs were sintered under mixed gas flows of FA/N2 and N2. The resistivity of film was 4.79 μΩ cm, about twice the bulk value. Organic analysis showed that about 0.43% of residual organics was left in the film. Therefore, this Au film was chosen for solder ball shear test because the microstructure was denser compared to the films sintered under other gasses such as N2 or FA/N2 and less organic residue was found from organic analyses. Even though the film sintered under N2 showed the best electrical property (4.35 μΩ cm), it was not adopted in the shear test because NPs remaining on the bottom of the film could lead to the poor adhesion between the film and substrate and show low shear strength. The shear force was 8.04 newton (N) on average and the strength was 64 MPa. This shear strength is good enough to substitute the inkjet-printed Au nanoparticulate film for electroplating in electronic package.

  15. Development of gold induced surface plasmon enhanced CIGS absorption layer on polyimide substrate

    NASA Astrophysics Data System (ADS)

    Park, Seong-Un; Sharma, Rahul; Sim, Jae-Kwan; Baek, Byung Joon; Ahn, Haeng-Kwun; Kim, Jin Soo; Lee, Cheul-Ro

    2013-09-01

    Localized surface plasmon resonance (LSPR) with metal nanoparticles is the promising phenomenon to increase light absorption by trapping light in thin film solar cells. In this study we demonstrate a successful LSPR effect with gold (Au) nanoparticles onto the Cu(In,Ga)Se2 (CIGS) absorption layer. First, the CIGS absorber layers is fabricated onto the Mo coated polyimide (PI) substrate by using two stage process as DC sputtering of CIG thin film followed by the selenization at 400 °C. Finally, the Au nanoparticles are deposited onto the CIGS layer with increasing particles size from 4-15 nm by using sputter coater for 10-120 s. The X-ray diffraction (XRD) patterns confirm the formation of CIGS/Au nanocomposite structure with prominent peak shift of CIGS reflections and increasing intensity for Au phase. The CIGS/Au nanocomposite morphologies with Au particle size distribution uniformity and surface coverage is examined under ultra-high resolution field effect scanning electron microscope (UHR-FESEM). A peak at 176 cm-1 in Raman spectra, associated with the “A1” mode of lattice vibration for the attributed to the pure chalcopyrite structure. The secondary ion mass spectroscopy (SIMS) showed ∼200 nm depth converge of Au nanoparticles into the CIGS absorption layer. The optical properties as transmittance, reflectance and absorbance of CIGS/Au layers were found to expand in the infrared region and the LSPR effect is the most prominent for Au particles (5-7 nm) deposited for 60 s. The absorption coefficient and band gap measurement also confirms that the LSPR effect for 5-7 nm Au particles with band gap improvement from 1.31 to 1.52 eV for CIGS/Au layer as the defect density decreases due to the deposition of Au nanoparticles onto the CIGS layer. Such LSPR effect in CIGS/Au nanocomposite absorption layer will be a key parameter to further improve performance of the solar cell.

  16. Designing Morphology in Epitaxial Silicon Nanowires: The Role of Gold, Surface Chemistry, and Phosphorus Doping.

    PubMed

    Kim, Seokhyoung; Hill, David J; Pinion, Christopher W; Christesen, Joseph D; McBride, James R; Cahoon, James F

    2017-03-28

    Vertically aligned semiconductor nanowires (NWs) have many potential applications for NW-based technologies, ranging from solar cells to intracellular sensors. Aligned NWs can be fabricated by top-down etching of planar wafers or synthesized from the bottom up using the vapor-liquid-solid (VLS) mechanism to induce epitaxial growth on lattice-matched substrates. The VLS process permits the modulation of dopants along the NW growth axis, which if combined with dopant-dependent wet-chemical etching, can be used to encode precise morphology. However, the synthesis of vertical and linear NWs with complex morphology is nontrivial, requiring control over multiple interdependent aspects of the VLS process. Here, we demonstrate sub-10 nm morphology in ⟨111⟩ epitaxial silicon (Si) NWs grown by the VLS mechanism on (111) Si substrates with gold (Au) catalysts. Using silane (SiH4), phosphine (PH3), and hydrochloric acid (HCl) precursor gases at 480 °C, precise morphology is encoded through abrupt phosphorus (P) dopant transitions, which are found to be less than 5 nm in width. The results highlight three mechanistic attributes of the process. First, NW growth in the ⟨111⟩ direction is found to be unstable at high SiH4 partial pressures and growth rates unless using HCl, which stabilizes NW growth through chlorination of the NW sidewall. Second, aggregated Au deposited on the NW surface by the VLS catalyst is found to be immobile on the chlorinated surface and to impede selective wet-chemical etching by potassium hydroxide (KOH) solution, preventing the design of precise morphology. Third, the aggregation of Au is found to be strongly dependent on the SiH4 partial pressure and NW growth rate, and values exceeding ∼100 mTorr and ∼150 nm/min, respectively, are required to minimize Au and thereby enable selective wet-chemical etching. Under optimized growth conditions, we find that abrupt, complex, and arbitrary dopant profiles and morphologies can be encoded in

  17. Simple control of surface topography of gold nanoshells by a surfactant-less seeded-growth method.

    PubMed

    Topete, Antonio; Alatorre-Meda, Manuel; Villar-Álvarez, Eva M; Cambón, Adriana; Barbosa, Silvia; Taboada, Pablo; Mosquera, Víctor

    2014-07-23

    We report the synthesis of branched gold nanoshells (BGNS) through a seeded-growth surfactant-less method. This was achieved by decorating chitosan-Pluronic F127 stabilized poly(lactic-co-gycolic) acid nanoparticles (NPs) with Au seeds (NP-seed), using chitosan as an electrostatic self-assembling agent. Branched shells with different degrees of anisotropy and optical response were obtained by modulating the ratios of HAuCl4/K2CO3 growth solution, ascorbic acid (AA) and NP-seed precursor. Chitosan and AA were crucial in determining the BGNS size and structure, acting both as coreductants and structure directing growth agents. Preliminary cytotoxicity experiments point to the biocompatibility of the obtained BGNS, allowing their potential use in biomedical applications. In particular, these nanostructures with "hybrid" compositions, which combine the features of gold nanoshells and nanostars showed a better performance as surface enhanced Raman spectroscopy probes in detecting intracellular cell components than classical smoother nanoshells.

  18. An original electrochemical method for assembling multilayers of terpyridine-based metallic complexes on a gold surface.

    PubMed

    Liatard, Sébastien; Chauvin, Jérôme; Balestro, Franck; Jouvenot, Damien; Loiseau, Frédérique; Deronzier, Alain

    2012-07-24

    A new method based on the electrochemical oxidation of thiols was used to easily generate multilayer assemblies of coordination complexes on a gold surface. For this purpose, two complexes bearing two anchoring groups for surface attachment have been prepared: [Ru(tpySH)(2)](2+) (1) and [Fe(tpySH)(2)](2+) (2) (tpySH = 4'-(2-(p-phenoxy)ethanethiol)-2,2':6',2″-terpyridine). Cyclic voltammetry of 1 in CH(3)CN exhibits two successive oxidation processes. The first is irreversible and attributed to the oxidation of the thiol substituents, whereas the second is reversible and corresponds to the 1 e(-) metal-centered oxidation. In the case of 2 both processes are superimposed. Monolayers of 1 or 2 have been formed on gold electrodes by spontaneous adsorption from micromolar solutions of the complexes in CH(3)CN. SAMs (self-assembled monolayers) exhibit redox behavior similar to the complexes in solution. The high surface coverage value obtained (Γ = 6 × 10(-10) and 4 × 10(-10) mol cm(-2) for 1 and 2, respectively) is consistent with a vertical orientation for the complexes; thus, one thiol is bound to the gold electrode, with the second unreacted thiol moiety exposed to the outer surface. Successive cyclic voltammetry induced a layer-by-layer nanostructural growth at the surface of the SAMs, and this is presumably due to the electrochemical formation of disulfide bonds, where the thiol moieties play a double role of both an anchoring group and an electroactive coupling agent. The conditions of the deposition are studied in detail. Modified electrodes containing both 1 and 2 alternatively can be easily prepared following this new approach. The film proved to be stable, displaying a similar current/voltage response for more than 10 repeating cycles in oxidation up to 0.97 V vs Ag/AgNO(3) (10(-2) M).

  19. Investigations of redox-labeled silica and gold nanoparticles in solution and as films on electrodes

    NASA Astrophysics Data System (ADS)

    Beasley, Christopher A.

    Chapter One serves as a background for Au nanoparticles (AuNP) and silica nanoparticles (SiNP). A brief history of the synthesis and characterization of AuNPs will be followed by a discussion on the recent application of the particles in sensing and energy-related applications. The second portion of the chapter will be a discussion on the functionalization of SiNPs and their application in a variety of sensing systems. Chapter Two discusses the irreversible adsorption onto electrode surfaces of highly ionic, mixed-monolayer AuNPs containing an N,N,N-triethylammonium terminated thiol and an 6-(ferrocenylhexane) thiol. The AuNP films are entropically stabilized due to the multidentate nature of the particles and can be transferred to NP-free electrolyte solutions for further investigation. The most interesting aspect of the film is the ability to monitor ion and accompanying solvent transfer between the film and electrolyte solution despite the films being one to two monolayers thick. Comparisons will be drawn to ion transfer between two immiscible electrolyte solutions. Chapter Three will discuss the controlled growth of films of highly ionic, mixed monolayer AuNPs containing deprotonated mercaptoundecanoic acid and 6-(ferrocenylhexane) thiol. The controlled deposition of films of AuNPs without the addition of a metal ion to facilitate binding between particles provides a new route to controlling film thicknesses for applications in Surface Enhanced Raman Spectroscopy and energy storage. Electrochemical quartz crystal microbalance studies, impedance spectroscopy and theoretical modeling show that the large peak-to-peak separation for the ferrocene/ferrocenium couple in cyclic voltammograms arises solely from uncompensated resistance effects within the film, i.e., the rates of ion permeation. Chapter Four examines ferrocenated SiNPs as charge storage devices. Focus is initially on the surface functionalization. Spectroscopic characterizations are used to estimate the

  20. Growth of Gold Nanosheets and Nanopolyhedra in Pyrrolidinium-Based Ionic Liquids: Investigation of the Cation Effect on the Resulting Morphologies

    SciTech Connect

    Bouvy, Claire; Baker, Gary A; Yin, Hongfeng; Dai, Sheng

    2010-01-01

    Large gold nanosheets and small gold polyhedra have been successfully synthesized in room-temperature ionic liquids (ILs) by an ionothermal reduction of HAuCl{sub 4} under N{sub 2} atmosphere, without using any additives. The effect of the organic cation on the final morphologies of the gold particles has been studied, and a series of pyrrolidinium-, imidazolium-, and quaternary amine-based ionic liquids have been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements. Our results show that these ILs favor the anisotropic growth of gold by acting as template agents and that only gold microspheres can be obtained with the IL containing a reductive functionality.

  1. Gold Cluster Formation on C60 Surfaces: Au-Cluster Beads and Self-Organized Structures

    NASA Astrophysics Data System (ADS)

    Reinke, Petra; Liu, Hui

    2007-03-01

    Petra Reinke, Hui Liu, Department of Materials Science and Engineering, University of Virginia The investigation of C60-Au interaction is central to the advancement of solar cell and nanotechnology applications of C60. C60 grows in a quasi-layer-by-layer mode on a pristine graphite surface and form a special surface structure (coexistence of round and fractal islands). The deposition of Au leads to the formation of a complex array of different surface structures, while the basic island structure of the C60 is preserved. The Au-clusters nucleate preferentially at the graphite-first fullerene layer islands edge forming beadlike structures. A roughness analysis of the fullerene surface indicates the presence of Au atoms embedded in the fullerene surface, situated in the troughs in between the large molecules. The analysis of the spatial and size distributions of Au clusters provides the basis for the development of a qualitative model which describes the relevant surface processes in the Au-fullerene system. The simultaneous deposition of Au and C60 leads to the formation of organized structures, in which Au clusters are embedded in a ring of fullerene molecules with a constant width.

  2. Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

    SciTech Connect

    Techane, Sirnegeda D.; Baer, Donald R.; Castner, David G.

    2011-09-01

    Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) and x-ray photoelectron spectroscopy (XPS). XPS measurements of C16 COOH SAMs on flat gold surfaces were made at 9 different photoelectron take-off angles (5o to 85o in 5o increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. Based on the glancing angle results, it was found that inclusion of a hydrocarbon contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1Å/CH2 group, an RSA of 1.05 and a 1.5Å CH2-contamination overlayer (total film thickness = 21.5Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs were determined to be 0.9Å/CH2 group and 1.06 RSA with a 1.5Å CH2-contamination overlayer (total film thickness = 18.5Å). The three angstrom difference in SAM thickness between the flat Au and AuNP surfaces suggests the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

  3. Simulation and modeling of self-assembled monolayers of carboxylic acid thiols on flat and nanoparticle gold surfaces.

    PubMed

    Techane, Sirnegeda; Baer, Donald R; Castner, David G

    2011-09-01

    Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) software and X-ray photoelectron spectroscopy (XPS) experimental measurements. XPS measurements of C16 COOH-SAMs on flat gold surfaces were made at nine different photoelectron emission angles (5-85° in 10° increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. On the basis of the glancing-angle results, it was found that inclusion of a hydrocarbon-contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1 Å/CH(2) group, an RSA of 1.05, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 21.5 Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat-surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs indicated a slightly thinner overlayer with parameters of 0.9 Å/CH(2) group in the SAM, an RSA of 1.06 RSA, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 18.5 Å). The 3 Å difference in SAM thickness between the flat Au and AuNP surfaces suggests that the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

  4. Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

    SciTech Connect

    Lin, Yuyuan; Wu, Zili; Wen, Jianguo; Poeppelmeier, Kenneth R; Marks, Laurence D

    2015-01-01

    Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.

  5. Investigating asteroid surface thermal inertias with NEOWISE

    NASA Astrophysics Data System (ADS)

    Nugent, C.; Mainzer, A.; Masiero, J.; Lysek, M.; Grav, T.; Bauer, J.; Cutri, R.; Wright, E.

    2014-07-01

    NEOWISE, the asteroid-hunting mission that employs the Wide-field Infrared Survey Explorer (WISE) spacecraft, has observed over 150,000 minor planets over four infrared wavelength bands (Mainzer et al. 2011). Several of these asteroids have also been observed by radar, and have associated shapes and spin states (e.g., Busch et al. 2011, see current list maintained by L. Benner at http://echo.jpl.nasa.gov/˜lance/shapes/ asteroid_shapes.html). We combine these datasets via thermophysical modeling, a technique that combines 3-D asteroid shapes, a model of heat transport, and infrared observations to determine the thermal inertia of an asteroid (e.g., Leyrat et al. 2011). Thermal inertia measurements can constrain regolith composition and density, which can be linked to collisional history and dynamical evolution. Measurements of thermal conductivity and heat capacity (components of thermal inertia), can refine predictions of the Yarkovsky drift, a non-gravitational force that can change asteroid orbits (Bottke et al. 2006). We present thermal inertia measurements derived from the NEOWISE dataset, such as surface thermal inertia measurements of 2008 EV5 (see figure).

  6. Raman and surface enhanced Raman scattering study of the orientation of cruciform 9,10-anthracene thiophene and furan derivatives deposited on a gold colloidal surface

    NASA Astrophysics Data System (ADS)

    Muñoz-Pérez, J.; Leyton, P.; Paipa, C.; Soto, J. P.; Brunet, J.; Gómez-Jeria, J. S.; Campos-Vallette, M. M.

    2016-10-01

    The 9,10-di(thiophen-2-yl)anthracene (TAT), 9,10-di(furan-2-yl)anthracene (FAF) and 2-[(10-(thiophen-2-yl)anthracen-9-yl)]furan (TAF) cruciform molecular systems were synthesized using one-step coupling reactions and structurally characterized via Raman, infrared, 1H NMR, 13C NMR and mass spectroscopies. The orientation of the analytes on a gold colloidal surface was inferred from a surface-enhanced Raman scattering (SERS) study. The metal surface interaction was driven by the S and O atoms of the thiophene and furan α-substituents, and the plane of the anthracene fragment remained parallel to the surface. Theoretical calculations based on a simplified molecular model for the analyte-surface interaction provide a good representation of the experimental data.

  7. Inhibition of Electrochemical Reactions at Gold Surfaces by Grafted, Highly Fluorinated, Hyperbranched Polymer Films

    DTIC Science & Technology

    1996-10-01

    50 atom% F; These films are very hydrophobic (water contact angle of 114 deg) and block electrochemical reactions on gold electrodes. Cyclic ... voltammetry in basic solution shows that while an electrode covered with a 3-layer PAA (3-PAA) film mimics an assembly of microelectrodes, a fluorinated 3

  8. Plasmonically Enhanced Photocatalytic Hydrogen Production from Water: The Critical Role of Tunable Surface Plasmon Resonance from Gold-Silver Nanoshells.

    PubMed

    Li, Chien-Hung; Li, Min-Chih; Liu, Si-Ping; Jamison, Andrew C; Lee, Dahye; Lee, T Randall; Lee, Tai-Chou

    2016-04-13

    Gold-silver nanoshells (GS-NSs) having a tunable surface plasmon resonance (SPR) were employed to facilitate charge separation of photoexcited carriers in the photocalytic production of hydrogen from water. Zinc indium sulfide (ZnIn2S4; ZIS), a visible-light-active photocatalyst, where the band gap varies with the [Zn]/[In] ratio, was used as a model ZIS system (E(g) = 2.25 eV) to investigate the mechanisms of plasmonic enhancement associated with the nanoshells. Three types of GS-NS cores with intense absorptions centered roughly at 500, 700, and 900 nm were used as seeds for preparing GS-NS@ZIS core-shell structures via a microwave-assisted hydrothermal reaction, yielding core-shell particles with composite diameters of ∼200 nm. Notably, an interlayer of dielectric silica (SiO2) between the GS-NSs and the ZIS photocatalyst provided another parameter to enhance the production of hydrogen and to distinguish the charge-transfer mechanisms. In particular, the direct transfer of hot electrons from the GS-NSs to the ZIS photocatalyst was blocked by this layer. Of the 10 particle samples examined in this study, the greatest hydrogen gas evolution rate was observed for GS-NSs having a SiO2 interlayer thickness of ∼17 nm and an SPR absorption centered at ∼700 nm, yielding a rate 2.6 times higher than that of the ZIS without GS-NSs. The apparent quantum efficiencies for these core-shell particles were recorded and compared to the absorption spectra. Analyses of the charge-transfer mechanisms were evaluated and are discussed based on the experimental findings.

  9. Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified glass slide: a strategy for SPR substrates.

    PubMed

    Jin, Y; Kang, X; Song, Y; Zhang, B; Cheng, G; Dong, S

    2001-07-01

    The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

  10. Quantitative kinetic investigation of triazole-gold(I) complex catalyzed [3,3]-rearrangement of propargyl ester.

    PubMed

    Xi, Yumeng; Wang, Qiaoyi; Su, Yijin; Li, Minyong; Shi, Xiaodong

    2014-02-28

    The triazole-gold(I) complex catalyzed [3,3]-rearrangement of propargyl ester has been quantitatively investigated through in situ IR. First order dependence of the initial rates on [Au] and [propargyl ester] suggested that the turnover-limiting step is the associative ligand substitution. The activation enthalpy was also determined to be 7.8 kcal mol(-1). TA-Au catalysts with different triazole derivatives were also tested, giving a linear free energy relationship with a ρ value of 0.74.

  11. Theoretical investigation of gas-surface interactions

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1992-01-01

    The investigation into the appearance of intruder states from the negative continuum when some of the two-electron integrals were omitted was completed. The work shows that, provided all integrals involving core contracted functions in an atomic general contraction are included, or that the core functions are radially localized, meaningful results are obtained and intruder states do not appear. In the area of program development, the Dirac-Hartree-Fock (DHF) program for closed-shell polyatomic molecules was extended to permit Kramers-restricted open-shell DHF calculations with one electron in an open shell or one hole in a closed shell, or state-averaged DHF calculations over several particle or hole doublet states. One application of the open-shell code was to the KO molecule. Another major area of program development is the transformation of integrals from the scalar basis in which they are generated to the 2-spinor basis employed in parts of the DHF program, and hence to supermatrix form. Particularly concerning the omission of small component integrals, and with increase in availability of disk space, it is now possible to consider transforming the integrals. The use of ordered integrals, either in the scalar basis or in the 2-spinor basis, would considerably speed up the construction of the Fock matrix, and even more so if supermatrices were constructed. A considerable amount of effort was spent on analyzing the integral ordering and tranformation for the DHF program. The work of assessing the reliability of the relativistic effective core potentials (RECPs) was continued with calculation of the group IV monoxides. The perturbation of the metal atom provided by oxygen is expected to be larger than that provided by hydrogen and thus provide a better test of the qualification of the RECPs. Calculations on some platinum hydrides were carried out at nonrelativistic (NR), perturbation theory (PT) and DHF levels. Reprints of four papers describing this work are

  12. Two-photon excited surface plasmon enhanced energy transfer between DAPI and gold nanoparticles: Opportunities in intra-cellular imaging and sensing

    NASA Astrophysics Data System (ADS)

    Zhang, Yinan; Birch, David J. S.; Chen, Yu

    2011-09-01

    We have demonstrated energy transfer between 4'-6-Diamidino-2-phenylindole (DAPI), a commonly used DNA label, and gold nanoparticles under two-photon excitation in solution using fluorescence lifetime imaging microscopy (FLIM). With comparable size and concentration, gold nanorods (GNRs) are shown to provide more efficient energy transfer than gold nanospheres (GNSs). We attribute this transfer enhancement effect to the longitudinal surface plasmon mode of GNRs overlapping with the excitation wavelength. Energy transfer under two-photon excitation between GNRs and DAPI has also been observed in cell culture and found to be in accord with the solution phase results.

  13. High spatial resolution mapping of surface plasmon resonance modes in single and aggregated gold nanoparticles assembled on DNA strands

    PubMed Central

    2013-01-01

    Abstract We present the mapping of the full plasmonic mode spectrum for single and aggregated gold nanoparticles linked through DNA strands to a silicon nitride substrate. A comprehensive analysis of the electron energy loss spectroscopy images maps was performed on nanoparticles standing alone, dimers, and clusters of nanoparticles. The experimental results were confirmed by numerical calculations using the Mie theory and Gans-Mie theory for solving Maxwell's equations. Both bright and dark surface plasmon modes have been unveiled. PACS 78.67.Bf; 61.46.Df; 87.64.Ee PMID:23890222

  14. Electrical detection of surface plasmon resonance phenomena by a photoelectronic device integrated with gold nanoparticle plasmon antenna

    NASA Astrophysics Data System (ADS)

    Hashimoto, Tatsuya; Fukunishi, Yurie; Zheng, Bin; Uraoka, Yukiharu; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

    2013-02-01

    We have proposed a concept of a photoelectronic hybrid device utilizing gold nanoparticles (GNPs), which are supposed to function not only as the plasmon antenna but also as the sensing part. The photocurrent in the fabricated device, consisting of a transparent Nb-doped TiO2 channel and Au electrodes, was enhanced more than eight times at a specific wavelength with GNP arrays located between the electrodes, indicating that surface plasmon resonance was electrically detected with the hybrid device. This result will open new doors for ultra-small biosensor chips integrated with multi-functional solid-state devices.

  15. Real-Time Label-Free Surface Plasmon Resonance Biosensing with Gold Nanohole Arrays Fabricated by Nanoimprint Lithography

    PubMed Central

    Martinez-Perdiguero, Josu; Retolaza, Aritz; Otaduy, Deitze; Juarros, Aritz; Merino, Santos

    2013-01-01

    In this work we present a surface plasmon resonance sensor based on enhanced optical transmission through sub-wavelength nanohole arrays. This technique is extremely sensitive to changes in the refractive index of the surrounding medium which result in a modulation of the transmitted light. The periodic gold nanohole array sensors were fabricated by high-throughput thermal nanoimprint lithography. Square periodic arrays with sub-wavelength hole diameters were obtained and characterized. Using solutions with known refractive index, the array sensitivities were obtained. Finally, protein absorption was monitored in real-time demonstrating the label-free biosensing capabilities of the fabricated devices. PMID:24135989

  16. pH-responsive one-dimensional periodic relief grating of polymer brush-gold nanoassemblies on silicon surface.

    PubMed

    Chen, Jem-Kun; Pai, Ping-Chun; Chang, Jia-Yaw; Fan, Shih-Kang

    2012-04-01

    In this work, we focus on the fabrication of the nanoassemblies consisting of the poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) brushes and gold nanoparticles (AuNPs). The employed process involves grafting of the PDMAEMA chains on an underlying substrate in a brush conformation followed by the immobilization of surface functionalized AuNPs by means of physical interaction (electrostatic attraction, entanglement, and hydrogen bonding). Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and UV-vis spectroscopy have been employed to characterize the prepared PDMAEMA-AuNP nanoassemblies. Polymer brushes possessing various thicknesses have been found to suppress the nanoparticles' aggregation and, hence, facilitate the surface coverage. Furthermore, we patterned the PDMAEMA-AuNP nanoassemblies as an one-dimensional periodic relief grating (OPRG). The subwavelength structure of OPRG has the optical features including artificial refractive index, form birefringence and resonance and band gap effects. A mean refractive index of the PDMAEMA-AuNP nanoassemblies can be controlled by the filling factors of the OPRG structure, so that a desired distribution of refractive index of the polymer brushes-gold OPRG under various stimuli can be realized. The employed approach is simple and highly versatile for the modification of surfaces with a wide range of NPs.

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

    PubMed

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

    2016-03-15

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

  18. Investigation of mechanical properties of twin gold crystal nanowires under uniaxial load by molecular dynamics method

    NASA Astrophysics Data System (ADS)

    Zhang, Guo-Wei; Yang, Zai-Lin; Luo, Gang

    2016-08-01

    Twin gold crystal nanowires, whose loading direction is parallel to the twin boundary orientation, are simulated. We calculate the nanowires under tensile or compressive loads, different length nanowires, and different twin boundary nanowires respectively. The Young modulus of nanowires under compressive load is about twice that under tensile load. The compressive properties of twin gold nanowires are superior to their tensile properties. For different length nanowires, there is a critical value of length with respect to the mechanical properties. When the length of nanowire is greater than the critical value, its mechanical properties are sensitive to length. The twin boundary spacing hardly affects the mechanical properties. Project supported by the National Science and Technology Pillar Program, China (Grant No. 2015BAK17B06), the Earthquake Industry Special Science Research Foundation Project, China (Grant No. 201508026-02), the Natural Science Foundation of Heilongjiang Province, China (Grant No. A201310), and the Scientific Research Starting Foundation for Post Doctorate of Heilongjiang Province, China (Grant No. LBHQ13040).

  19. Comparative sessile drop and dip pen nanolithography investigation for various hydrophilic ink/surface systems.

    PubMed

    Yadav, Pradeep K; Lemoine, Patrick

    2012-01-01

    We present a dip pen nanolithography study of various hydrophilic ink/surface systems with application in the field of biosensors and novel nano-materials. The inking process was investigated by studying a number of inks, such as Deoxyribonucleic acid (DNA), Bovine serum albumin (BSA), Streptavidin, 16-mercaptohexadecanoic acid (MHA) and a 20 nm nanosphere (NS) polystyrene solution onto a range of substrates, namely glass, silicon, gold and tetrahedral amorphous carbon (taC). In the majority of cases, this resulted in patterns with sub-100 nm line widths and dot diameters. Importantly, contact angle measurements in the microl range showed a decrease of contact angle with drop volume, interpreted as a line tension effect. The significance of this to the nanoscale wetting behaviour is discussed. The effect of dwell time and writing speed indicates that the inking process is not solely defined by surface diffusion but also influenced by the ink dissolution rate from the tip.

  20. Friction and transfer of copper, silver, and gold to iron in the presence of various adsorbed surface films

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with the noble metals copper, silver, and gold and two binary alloys of these metals contacting iron in the presence of various adsorbates including, oxygen, methyl mercaptan, and methyl chloride. A pin on disk specimen configuration was used with a load of 100 grams, sliding velocity of 60 mm/min; at 25 C with the surfaces saturated with the adsorbates. Auger emission spectroscopy was used to monitor surface films. Results of the experiments indicate that friction and transfer characteristics are highly specific with respect to both the noble metal and surface film present. With all three metals and films transfer of the noble metal to iron occurred very rapidly. With all metals and films transfer of the noble metal to iron continuously increased with repeated passes except for silver and copper sliding on iron sulfide.

  1. Delivery and efficacy of a cancer drug as a function of the bond to the gold nanoparticle surface.

    PubMed

    Cheng, Yu; Samia, Anna C; Li, Jun; Kenney, Malcolm E; Resnick, Andrew; Burda, Clemens

    2010-02-16

    In this feature article, gold nanoparticle conjugates loaded with phthalocyanine-based PDT drugs are prepared and tested for delivery efficiency and PDT efficacy on HeLa cancer cells. It could be shown that the delivery and PDT outcome are strongly affected by the bond that links the drug load to the nanoparticle surface. Whereas labile amino adsorption to the Au nanoparticle surface allows for efficient drug release into the cancer cells and for efficient PDT, a covalent thiol bond to the Au nanoparticle leads to the delivery of the drug into cell vesicles, and no PDT effect is observed. This work highlights the importance of carefully choosing the interaction between drug molecules and the nanoparticle surface.

  2. Negative ionization of the secondary ions of silver and gold sputtered from their elemental surfaces

    NASA Astrophysics Data System (ADS)

    Sindona, A.; Riccardi, P.; Maletta, S.; Rudi, S. A.; Falcone, G.

    2007-03-01

    Calculations of the ionization probabilities of Ag- and Au- particles, ejected during sputtering of clean Ag(1 0 0) and Au(1 0 0) surfaces, respectively, are reported. An effective one-electron theory is used to describe: the plane metal surface, with a projected band gap, the secondary emitted atom, whose charge state is investigated, and its nearest-neighbor substrate atom, put in motion by the collision cascade generated by the primary ion beam. Suitable rectilinear trajectories are selected to describe the motion of these two atoms outside the solid. A good agreement is found with van Der Heide's experiments (P.A.W. van Der Heide, Nucl. Instr. and Meth. B 157 (1999) 126).

  3. Controlled surface plasmon enhanced fluorescence from 1D gold gratings via azimuth rotations

    NASA Astrophysics Data System (ADS)

    Byrne, Daragh; Duggan, Paul; McDonagh, Colette

    2017-03-01

    We demonstrate a method to maximise the fluorescence enhancement from a dye using gold coated diffraction gratings. Rotations about the azimuth provides a convenient approach to maximise the coupling between the grating and excitation source while achieving enhancements comparable to traditional optical configurations where the grating and in plane light vectors are parallel. This approach yields a 30 fold enhancement in the fluorescence signal over metal free substrates, while opening up the range of possible orientations and configurations suitable for fluorescence enhancement applications.

  4. Omega-Terminated Alkanethiolate Monolayers on Surfaces of Copper, Silver and Gold Have Similar Wettabilities

    DTIC Science & Technology

    1991-12-01

    metal cxides and form oriented, oleophobic monolayers,25 0-hydroxy- and W-amino-alkanoic acids adsorb and form poorly organized films that are not wet...gold. Experinental Materials . 1l-Bromo-undecyl t-butyldimethylsilyl ether and most alkanethiols were available from pcrevious studies;6, 2 1, 4 8 ctn...er materials were obtained from Aldrich and used as received unless Specified. Octadecanethiol was distilled under reduced pressure prior to use

  5. Controlled surface plasmon enhanced fluorescence from 1D gold gratings via azimuth rotations.

    PubMed

    Byrne, Daragh; Duggan, Paul; McDonagh, Colette

    2017-03-01

    We demonstrate a method to maximise the fluorescence enhancement from a dye using gold coated diffraction gratings. Rotations about the azimuth provides a convenient approach to maximise the coupling between the grating and excitation source while achieving enhancements comparable to traditional optical configurations where the grating and in plane light vectors are parallel. This approach yields a 30 fold enhancement in the fluorescence signal over metal free substrates, while opening up the range of possible orientations and configurations suitable for fluorescence enhancement applications.

  6. Formation of patina on a copper surface in polyacrylate gels with gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, E. T.; Abdulmenova, E. V.; Lyamina; Godymchuk, A. Yu

    2015-11-01

    The experimental research demonstrates the effective use of patination of the copper and copper alloys in containing gold nanoparticles in order to increase their protective properties. The copper samples were examined by cyclic voltammetry method, optical microscopy, and X-ray analysis. It has been shown that patinas obtained in the polymer gel solution have a better corrosion resistance in comparison with the patinas obtained with chemical methods.

  7. Enhancing laser thermal-therapy using ultrasound-microbubbles and gold nanorods: In vitro investigation

    NASA Astrophysics Data System (ADS)

    Tarapacki, Christine; Kumaradas, Carl; Karshafian, Raffi

    2012-11-01

    Gold nanorods (GNR) in laser-induced thermal therapy can significantly increase light absorption, leading to a local temperature increase and causing irreversible cell damage. One of the key challenges in using GNR as a thermal therapy agent is to deliver a concentration of GNR to generate sufficient heat and cause cell death. In this study, ultrasound and microbubble induced sonoporation is used to enhance intracellular uptake of GNR and improve the therapeutic outcome of laserinduced thermal therapy. Acute myeloid leukemia (AML) cells in suspension (0.6 mL) were treated with ultrasound and microbubbles (USMB) at 1 MHz frequency, 16 microseconds pulse duration, 1 kHz pulse repetition frequency, 1 minute insonation time, varying acoustic pressures (0, 1.26 and 1.73 MPa) and 10 μL Definity microbubble agent with and without GNR (12 nm × 48 nm) at varying concentration (1.0×1010 to 2.5×1011 GNR/mL). The GNR were manufactured through wet chemical synthesis process and measured using Transmission Electron Microscopy (TEM) and Atomic Absorption Spectroscopy (AAS) for size and concentration respectively. Following ultrasound and microbubble treatment, cells were centrifuged to remove excess gold nanorods and treated in suspension with an 810 nm laser (Diomed 60 NIR) at 4 W for 5 minutes. A thermal camera (FLIR Thermovision A40) was positioned to monitor the sample temperature throughout laser treatment and cell viability was assessed using flow cytometry with propidium iodide. Cell viability of 18±2% was achieved with GNR+USMB (1.26 MPa) compared to 72±3% with GNR alone (12 hour incubation) and 99±0.2% with USMB (1.26 MPa) alone. With increasing GNR concentration during ultrasound and microbubble treatment, laser induced sample temperature increased and consequently cell viability decreased. Cell viability decreased from 92±1% at 1.0×1011 GNR/mL to 29±5% at 1.5×1011 GNR/mL concentration with corresponding maximum temperatures of 50°C and 54°C, respectively

  8. Controlled growth of hexagonal gold nanostructures during thermally induced self-assembling on Ge(001) surface

    NASA Astrophysics Data System (ADS)

    Jany, B. R.; Gauquelin, N.; Willhammar, T.; Nikiel, M.; van den Bos, K. H. W.; Janas, A.; Szajna, K.; Verbeeck, J.; van Aert, S.; van Tendeloo, G.; Krok, F.

    2017-02-01

    Nano-sized gold has become an important material in various fields of science and technology, where control over the size and crystallography is desired to tailor the functionality. Gold crystallizes in the face-centered cubic (fcc) phase, and its hexagonal closed packed (hcp) structure is a very unusual and rare phase. Stable Au hcp phase has been reported to form in nanoparticles at the tips of some Ge nanowires. It has also recently been synthesized in the form of thin graphene-supported sheets which are unstable under electron beam irradiation. Here, we show that stable hcp Au 3D nanostructures with well-defined crystallographic orientation and size can be systematically created in a process of thermally induced self-assembly of thin Au layer on Ge(001) monocrystal. The Au hcp crystallite is present in each Au nanostructure and has been characterized by different electron microscopy techniques. We report that a careful heat treatment above the eutectic melting temperature and a controlled cooling is required to form the hcp phase of Au on a Ge single crystal. This new method gives scientific prospects to obtain stable Au hcp phase for future applications in a rather simple manner as well as redefine the phase diagram of Gold with Germanium.

  9. Electrocatalytic behaviour and application of manganese porphyrin/gold nanoparticle- surface modified glassy carbon electrodes

    NASA Astrophysics Data System (ADS)

    Sebarchievici, I.; Tăranu, B. O.; Birdeanu, M.; Rus, S. F.; Fagadar-Cosma, E.

    2016-12-01

    The main purpose of this research was to obtain manganese porphyrin/gold nanoparticle-modified glassy carbon electrodes and to use them for the detection of H2O2. Two sets of modified electrodes were prepared by drop-cast deposition of 5,10,15,20-tetra(4-methyl-phenyl)porphyrinato manganese(III) chloride alone and of the same Mn-porphyrin and gold-colloid solution and comparatively characterized by Raman, UV-vis, ellipsometry, AFM and TEM microscopy, XPS and cyclic voltammetry. XPS spectrum recorded for GC_MnP_nAu modified electrode displayed the characteristic signals of gold nanoparticles. The optical parameters have greater values for GC_MnP_nAu in comparison with GC_MnP, due to increasing charge transfer efficiency. The MnP_nAu film mediates the electron transfer between H2O2 and GC, evidenced by an increase in the current intensity of the anodic peak, and facilitates the electrochemical regeneration of oxidized H2O2 at cathodic potentials. From the cyclic voltammetry experiments a linear relationship between H2O2 concentration vs oxidation and reduction currents was observed. The linear dependence between density of current and the square root of the scan rate indicates that the oxidation and reduction processes of H2O2 are diffusion controlled. The GC_MnP_nAu modified electrode shows great potential as electrochemical sensor for determination of hydrogen peroxide.

  10. Controlled growth of hexagonal gold nanostructures during thermally induced self-assembling on Ge(001) surface

    PubMed Central

    Jany, B. R.; Gauquelin, N.; Willhammar, T.; Nikiel, M.; van den Bos, K. H. W.; Janas, A.; Szajna, K.; Verbeeck, J.; Van Aert, S.; Van Tendeloo, G.; Krok, F.

    2017-01-01

    Nano-sized gold has become an important material in various fields of science and technology, where control over the size and crystallography is desired to tailor the functionality. Gold crystallizes in the face-centered cubic (fcc) phase, and its hexagonal closed packed (hcp) structure is a very unusual and rare phase. Stable Au hcp phase has been reported to form in nanoparticles at the tips of some Ge nanowires. It has also recently been synthesized in the form of thin graphene-supported sheets which are unstable under electron beam irradiation. Here, we show that stable hcp Au 3D nanostructures with well-defined crystallographic orientation and size can be systematically created in a process of thermally induced self-assembly of thin Au layer on Ge(001) monocrystal. The Au hcp crystallite is present in each Au nanostructure and has been characterized by different electron microscopy techniques. We report that a careful heat treatment above the eutectic melting temperature and a controlled cooling is required to form the hcp phase of Au on a Ge single crystal. This new method gives scientific prospects to obtain stable Au hcp phase for future applications in a rather simple manner as well as redefine the phase diagram of Gold with Germanium. PMID:28195226

  11. Investigating the Synthesis, Structure, and Catalytic Properties of Versatile Gold-Based Nanocatalvsts

    NASA Astrophysics Data System (ADS)

    Pretzer, Lori A.

    Transition metal nanomaterials are used to catalyze many chemical reactions, including those key to environmental, medicinal, and petrochemical fields. Improving their catalytic properties and lifetime would have significant economic and environmental rewards. Potentially expedient options to make such advancements are to alter the shape, size, or composition of transition metal nanocatalysts. This work investigates the relationships between structure and catalytic properties of synthesized Au, Pd-on-Au, and Au-enzyme model transition metal nanocatalysts. Au and Pd-on-Au nanomaterials were studied due to their wide-spread application and structure-dependent electronic and geometric properties. The goal of this thesis is to contribute design procedures and synthesis methods that enable the preparation of more efficient transition metal nanocatalysts. The influence of the size and composition of Pd-on-Au nanoparticles (NPs) was systematically investigated and each was found to affect the catalyst's surface structure and catalytic properties. The catalytic hydrodechlorination of trichloroethene and reduction of 4-nitrophenol by Pd-on-Au nanoparticles were investigated as these reactions are useful for environmental and pharmaceutical synthesis applications, respectively. Structural characterization revealed that the dispersion and oxidation state of surface Pd atoms are controlled by the Au particle size and concentration of Pd. These structural changes are correlated with observed Pd-on-Au NP activities for both probe reactions, providing new insight into the structure-activity relationships of bimetallic nanocatalysts. Using the structure-dependent electronic properties of Au NPs, a new type of light-triggered biocatalyst was prepared and used to remotely control a model biochemical reaction. This biocatalyst consists of a model thermophilic glucokinase enzyme covalently attached to the surface of Au nanorods. The rod-like shape of the Au nanoparticles made the

  12. Molecular-level insights of early-stage prion protein aggregation on mica and gold surface determined by AFM imaging and molecular simulation.

    PubMed

    Lou, Zhichao; Wang, Bin; Guo, Cunlan; Wang, Kun; Zhang, Haiqian; Xu, Bingqian

    2015-11-01

    By in situ time-lapse AFM, we investigated early-stage aggregates of PrP formed at low concentration (100 ng/mL) on mica and Au(111) surfaces in acetate buffer (pH 4.5). Remarkably different PrP assemblies were observed. Oligomeric structures of PrP aggregates were observed on mica surface, which was in sharp contrast to the multi-layer PrP aggregates yielding parallel linear patterns observed Au(111) surface. Combining molecular dynamics and docking simulations, PrP monomers, dimers and trimers were revealed as the basic units of the observed aggregates. Besides, the mechanisms of the observed PrP aggregations and the corresponding molecular-substrate and intermolecular interactions were suggested. These interactions involved gold-sulfur interaction, electrostatic interaction, hydrophobic interaction, and hydrogen binding interaction. In contrast, the PrP aggregates observed in pH 7.2 PBS buffer demonstrated similar large ball-like structures on both mica and Au(111) surfaces. The results indicate that the pH of a solution and the surface of the system can have strong effects on supramolecular assemblies of prion proteins. This study provides in-depth understanding on the structural and mechanistic nature of PrP aggregation, and can be used to study the aggregation mechanisms of other proteins with similar misfolding properties.

  13. A combined QCM and XPS investigation of asphaltene adsorption on metal surfaces.

    PubMed

    Rudrake, Amit; Karan, Kunal; Horton, J Hugh

    2009-04-01

    To investigate asphaltene-metal interactions, a combined quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS) study of asphaltene adsorption on a gold surface was conducted. Adsorption experiments were conducted at 25 degrees C with solutions of asphaltenes in toluene at concentrations ranging from 50 to 1500 ppm. QCM measurements yielded information on the kinetics of adsorption and further assessment of the data allowed the estimation of equilibrium adsorption levels. XPS analysis of adsorbed and bulk asphaltene demonstrated the presence of carboxylic, thiophenic, sulfide, pyridinic and pyrrolic type functional groups. The intensity of the main carbon (C-H) peak was related to surface coverage of adsorbed asphaltene as a function of asphaltene concentration by a simple mathematical model. The mass adsorption data from the QCM experiments also allowed estimation of the surface coverage, which was compared to those from XPS analyses. Surface coverage estimates as a function of asphaltene concentration could be described by a Langmuir (type-I) isotherm. The free energy of asphaltene adsorption was estimated to be -26.8+/-0.1 and -27.3+/-0.1 kJ/mol from QCM and XPS data, respectively assuming asphaltene molar mass of 750 g/gmol. QCM and XPS data was also analyzed to estimate adsorbed layer thickness after accounting for surface coverage. The thickness of the adsorbed asphaltene estimated from both XPS and QCM data analyses ranged from 6-8 nm over the entire range of adsorption concentrations investigated.

  14. Kinetic investigation of sulfidizing annealing of scorodite in processing of refractory oxidized gold-containing ores

    NASA Astrophysics Data System (ADS)

    Boboev, I. R.; Strizhko, L. S.; Bobozoda, Sh.; Gorbunov, E. P.

    2016-03-01

    The results of kinetic studies on the removal of arsenic from scorodite using sulfidizing annealing are presented. The reaction order with respect to the reactant and the activation energy are established from the experimental data. The rate-determining step of the sulfidizing annealing process is determined. The main reactions that occur during the sulfidizing of arsenic in scorodite are proposed on the basis of the obtained results and confirmed by thermodynamic calculations and chemical analyses. The major results of testing this technology, as applied to the refractory oxidized ores in which arsenic is mainly concentrated in scorodite, are presented. Arsenic removal from this ore is confirmed by chemical and quantitative X-ray diffraction analyses and by qualitative phase analysis. Industrial use of this technology provides safe and efficient processing of refractory gold-containing ores, where arsenic is mainly concentrated in scorodite.

  15. Tuning the EDTA-induced self-assembly and plasmonic spectral properties of gold nanorods: application in surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Li, Jian-jun; Zhang, Ning; Wang, Jingyuan; Yang, Chun-yu; Zhu, Jian; Zhao, Jun-wu

    2016-02-01

    Self-assembly of cetyl trimethyl ammonium bromide-protected colloidal gold nanorods with different aspect ratios has been studied by adding the ethylene diamine tetraacetic acid (EDTA). Both the assembly strength and assembly configuration fashion of the gold nanorods could be tuned by changing the aspect ratio. For gold nanorods with small aspect ratio, side-by-side assembly takes the major role in the aggregation. In this case, the blue shift of the longitudinal absorption and the increase of the transverse absorption lead to the great uplift of the middle spectrum dip as the EDTA is increased. For gold nanorods with large aspect ratio, end-to-end assembly takes the major role in the aggregation. In this case, the longitudinal absorption peak fades down rapidly and a tailing absorption peak at longer wavelength uplifts greatly as the EDTA is increased. The surface-enhanced Raman scattering (SERS) activity of the assembled gold nanorods has been studied using alpha-fetoprotein (AFP) as the Raman active probe. It has been found that both the side-by-side assembly and end-to-end assembly of the gold nanorods could effectively improve the Raman signal of the AFP. And the gold nanorod substrate with side-by-side assembly has higher SERS activity.

  16. Light harvesting, energy transfer and electron cycling of a native photosynthetic membrane adsorbed onto a gold surface.

    PubMed

    Magis, Gerhard J; den Hollander, Mart-Jan; Onderwaater, Willem G; Olsen, John D; Hunter, C Neil; Aartsma, Thijs J; Frese, Raoul N

    2010-03-01

    Photosynthetic membranes comprise a network of light harvesting and reaction center pigment-protein complexes responsible for the primary photoconversion reactions: light absorption, energy transfer and electron cycling. The structural organization of membranes of the purple bacterial species Rb. sphaeroides has been elucidated in most detail by means of polarized light spectroscopy and atomic force microscopy. Here we report a functional characterization of native and untreated membranes of the same species adsorbed onto a gold surface. Employing fluorescence confocal spectroscopy and light-induced electrochemistry we show that adsorbed membranes maintain their energy and electron transferring functionality. Gold-adsorbed membranes are shown to generate a steady high photocurrent of 10 microA/cm(2) for several minutes and to maintain activity for up to three days while continuously illuminated. The surface-adsorbed membranes exhibit a remarkable functionality under aerobic conditions, even when exposed to light intensities well above that of direct solar irradiation. The component at the interface of light harvesting and electron cycling, the LH1 complex, displays exceptional stability, likely contributing to the robustness of the membranes. Peripheral light harvesting LH2 complexes show a light intensity dependent decoupling from photoconversion. LH2 can act as a reversible switch at low-light, an increased emitter at medium light and photobleaches at high light.

  17. Polymer nanopillar-gold arrays as surface-enhanced Raman spectroscopy substrate for the simultaneous detection of multiple genes.

    PubMed

    Picciolini, Silvia; Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Bedoni, Marzia; Pellacani, Paola; Marchesini, Gerardo; Valsesia, Andrea; Prosperi, Davide; Tresoldi, Cristina; Ciceri, Fabio; Gramatica, Furio

    2014-10-28

    In our study, 2D nanopillar arrays with plasmonic crystal properties are optimized for surface-enhanced Raman spectroscopy (SERS) application and tested in a biochemical assay for the simultaneous detection of multiple genetic leukemia biomarkers. The special fabrication process combining soft lithography and plasma deposition techniques allows tailoring of the structural and chemical parameters of the crystal surfaces. In this way, it has been possible to tune the plasmonic resonance spectral position close to the excitation wavelength of the monochromatic laser light source in order to maximize the enhancing properties of the substrate. Samples are characterized by scanning electron microscopy and reflectance measurements and tested for SERS activity using malachite green. Besides, as the developed substrate had been prepared on a simple glass slide, SERS detection from the support side is also demonstrated. The optimized substrate is functionalized with thiol-modified capture oligonucleotides, and concentration-dependent signal of the target nucleotide is detected in a sandwich assay with labeled gold nanoparticles. Gold nanoparticles functionalized with different DNA and various Raman reporters are applied in a microarray-based assay recognizing a disease biomarker (Wilms tumor gene) and housekeeping gene expressions in the same time on spatially separated microspots. The multiplexing performance of the SERS-based bioassay is illustrated by distinguishing Raman dyes based on their complex spectral fingerprints.

  18. Three-dimensional donut-like gold nanorings with multiple hot spots for surface-enhanced raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zheng, Mengjie; Zhu, Xupeng; Chen, Yiqin; Xiang, Quan; Duan, Huigao

    2017-01-01

    Seeking for the best possible substrates for surface-enhanced Raman spectroscopy (SERS) is of great interest for single-molecule-level detection applications. Lithographic plasmonic nanostructures are supposed to enable uniform enhancement and thus have attracted extensive interest in the past decade. In this work, we propose and demonstrate a lithographic three-dimensional (3D) donut-like gold nanoring array as a SERS substrate with an enhancement factor (EF) up to 3.84 × 107. This 3D nanoring array could be directly fabricated using electron-beam-lithography-defined templates without any additional lift-off process and thus promises ultraclean metallic surfaces. Meanwhile, the 3D configuration allows multiple hot spots for improving SERS performance compared to planar counterparts with comparable plasmon resonance position. Systematic experiments and simulations were conducted to gain understanding of the origin of the improved SERS performance. The results imply that the 3D donut-like gold nanorings with multiple hot spots can serve as a promising configuration for SERS applications.

  19. Effect of Size and Surface Charge of Gold Nanoparticles on their Skin Permeability: A Molecular Dynamics Study

    PubMed Central

    Gupta, Rakesh; Rai, Beena

    2017-01-01

    Molecular level understanding of permeation of nanoparticles through human skin establishes the basis for development of novel transdermal drug delivery systems and design and formulation of cosmetics. Recent experiments suggest that surface coated nano-sized gold nanoparticles (AuNPs) can penetrate the rat and human skin. However, the mechanisms by which these AuNPs penetrate are not well understood. In this study, we have carried out coarse grained molecular dynamics simulations to explore the permeation of dodecanethiol coated neutral hydrophobic AuNPs of different sizes (2–5 nm) and surface charges (cationic and anionic) through the model skin lipid membrane. The results indicate that the neutral hydrophobic AuNPs disrupted the bilayer and entered in it with in ~200 ns, while charged AuNPs were adsorbed on the bilayer headgroup. The permeation free energy calculation revealed that at the head group of the bilayer, a very small barrier existed for neutral hydrophobic AuNP while a free energy minimum was observed for charged AuNPs. The permeability was maximum for neutral 2 nm gold nanoparticle (AuNP) and minimum for 3 nm cationic AuNP. The obtained results are aligned with recent experimental findings. This study would be helpful in designing customized nanoparticles for cosmetic and transdermal drug delivery application. PMID:28349970

  20. Surface topology investigation for ancient coinage assessment using optical interferometry

    NASA Astrophysics Data System (ADS)

    Grynszpan, R. I.; Pastol, J. L.; Lesko, S.; Paris, E.; Raepsaet, C.

    In order to demonstrate the capabilities of white-light interferometry depth profiling (WLI-DP) for ancient coinage assessment, we investigated a series of notorious 1786 gold coins, bearing Louis XVI's `horned' effigy, and allegedly minted in Strasbourg. Scanning electron microscopy as well as WLI-DP observations unambiguously indicate that both previously differentiated `single'- and `double'-horned varieties originated from a unique minting tool. Moreover, from topological measurements, we infer that `single-horned' coins, rather than wearing out into `double-horned' coins, proceeded from the latter variety during minting by progressive failure of an already altered die. Whereas present observations do not exclude initial forgery, they suggest that protrusions resulted from progressive incidental in-service die deterioration.

  1. Adsorption and sub-nanomolar sensing of thioflavin T on colloidal gold nanoparticles, silver nanoparticles and silver-coated films studied using surface-enhanced Raman scattering.

    PubMed

    Maiti, Nandita; Chadha, Ridhima; Das, Abhishek; Kapoor, Sudhir

    2015-01-01

    Raman and surface-enhanced Raman scattering (SERS) studies of thioflavin T (ThT) in solid, solution, gold nanoparticles (GNPs), silver nanoparticles (SNPs) and silver-coated films (SCFs) were investigated. Concentration-dependent SERS spectrum of ThT in GNPs and SNPs indicated the existence of two possible structures, one with the torsional angle (φ) between benzothiazole and dimethylaminobenzene rings being 37° and the other with φ=90°. The SERS spectrum of ThT in SCFs were similar to the Raman spectrum of solid and solution that suggests φ=37°. In this paper, the high sensitivity of the SERS technique was employed for sub-nanomolar (picomolar) sensing of ThT.

  2. Preservation of Thermal Control Specular Gold Baffle Surface on the James Webb Space Telescope (JWST) Integrated Science Instrument Module (ISIM) Electronics Compartment (IEC)

    NASA Technical Reports Server (NTRS)

    MonteedeGarcia, Kristina; Patel, Jignasha; Perry, Radford, III

    2010-01-01

    Extremely tight thermal control property degradation allowances on the vapor-deposited, gold-coated IEC baffle surface, made necessary by the cryogenic JWST Observatory operations, dictate tight contamination requirements on adjacent surfaces. Theoretical degradation in emittance with contaminant thickness was calculated. Maximum allowable source outgassing rates were calculated using worst case view factors from source to baffle surface. Tight requirements pushed the team to change the design of the adjacent surfaces to minimize the outgassing sources

  3. A theoretical investigation of the (0001) covellite surfaces

    SciTech Connect

    Gaspari, Roberto; Manna, Liberato; Cavalli, Andrea

    2014-07-28

    We report on the properties of the (0001) covellites surfaces, which we investigate by periodic slab density functional theory calculations. The absolute surface energies have been computed for all bulk terminations, showing that surfaces terminated by the flat CuS layer are associated with the lowest surface energy. Cleavage is predicted to occur across the [0001] interlayer Cu–S bond. The surfaces obtained by lowest energy cleavage are analyzed in terms of the atomic vertical relaxation, workfunction, and surface band structure. Our study predicts the presence of a shallow p{sub z}-derived surface state located 0.26 eV below the Fermi level, which is set to play an important role in the surface reactivity of covellite.

  4. GaN surface states investigated by electrochemical studies

    NASA Astrophysics Data System (ADS)

    Winnerl, Andrea; Garrido, Jose A.; Stutzmann, Martin

    2017-03-01

    We present a systematic study of electrochemically active surface states on MOCVD-grown n-type GaN in aqueous electrolytes using cyclic voltammetry and impedance spectroscopy over a wide range of potentials and frequencies. In order to alter the surface states, the GaN samples are either etched or oxidized, and the influence of the surface treatment on the defect-mediated charge transfer to the electrolyte is investigated. Etching in HCl removes substoichiometric GaO x , and leads to a pronounced density of electrochemically active surface states. Oxidation effectively removes these surface states.

  5. Interaction of the CLPFFD peptide with gold nanospheres. A Raman, surface enhanced Raman scattering and theoretical study

    NASA Astrophysics Data System (ADS)

    Vera, A. M.; Cárcamo, J. J.; Aliaga, A. E.; Gómez-Jeria, J. S.; Kogan, M. J.; Campos-Vallette, M. M.

    2015-01-01

    In a previous work we demonstrated that toxic aggregates of the protein β-amyloid (ATAβ) involved in the Alzheimer's disease (AD) can be destabilized upon electromagnetic irradiation of the peptide Cys-Leu-Pro-Phe-Phe-Asp (CLPFFD) adsorbed on gold nanospheres (AuNSs). For a selective recognition of the therapeutic target (i.e. ATAβ) of AD by the conjugates peptide-nanoparticle it is relevant to understand how the interaction between attached ligands and nanoparticles occurs. In this work a surface enhanced Raman scattering spectroscopy (SERS) study of the interactions of CLPFFD with AuNSs of 10 nm average diameter was carried out. The SERS data suggest that phenylalanine displays its aromatic ring coplanar to the surface which is supported by theoretical data obtained from molecular mechanics (MM) and Extended Hückel Theory (EHT) calculations.

  6. Gold nanoshell-decorated silicone surfaces for the near-infrared (NIR) photothermal destruction of the pathogenic bacterium E. faecalis.

    PubMed

    Khantamat, Orawan; Li, Chien-Hung; Yu, Fei; Jamison, Andrew C; Shih, Wei-Chuan; Cai, Chengzhi; Lee, T Randall

    2015-02-25

    Catheter-related infections (CRIs) are associated with the formation of pathogenic biofilms on the surfaces of silicone catheters, which are ubiquitous in medicine. These biofilms provide protection against antimicrobial agents and facilitate the development of bacterial resistance to antibiotics. The application of photothermal agents on catheter surfaces is an innovative approach to overcoming biofilm-generated CRIs. Gold nanoshells (AuNSs) represent a promising photothermal tool, because they can be used to generate heat upon exposure to near-infrared (NIR) radiation, are biologically inert at physiological temperatures, and can be engineered for the photothermal ablation of cells and tissue. In this study, AuNSs functionalized with carboxylate-terminated organosulfur ligands were attached to model catheter surfaces and tested for their effectiveness at killing adhered Enterococcus faecalis (E. faecalis) bacteria. The morphology of the AuNSs was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), while the elemental composition was characterized by energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Furthermore, optical and photothermal properties were acquired by ultraviolet-visible (UV-vis) spectr