Naked Gold Nanoparticles and hot Electrons in Water.

PubMed

Ghandi, Khashayar; Wang, Furong; Landry, Cody; Mostafavi, Mehran

2018-05-08

The ionizing radiation in aqueous solutions of gold nanoparticles, stabilized by electrostatic non-covalent intermolecular forces and steric interactions, with antimicrobial compounds, are investigated with picosecond pulse radiolysis techniques. Upon pulse radiolysis of an aqueous solution containing very low concentrations of gold nanoparticles with naked surfaces available in water (not obstructed by chemical bonds), a change to Cerenkov spectrum over a large range of wavelengths are observed and pre-solvated electrons are captured by gold nanoparticles exclusively (not by ionic liquid surfactants used to stabilize the nanoparticles). The solvated electrons are also found to decay rapidly compared with the decay kinetics in water. These very fast reactions with electrons in water could provide an enhanced oxidizing zone around gold nanoparticles and this could be the reason for radio sensitizing behavior of gold nanoparticles in radiation therapy.

Ultrafast lattice dynamics of single crystal and polycrystalline gold nanofilms☆

NASA Astrophysics Data System (ADS)

Hu, Jianbo; Karam, Tony E.; Blake, Geoffrey A.; Zewail, Ahmed H.

2017-09-01

Ultrafast electron diffraction is employed to spatiotemporally visualize the lattice dynamics of 11 nm-thick single-crystal and 2 nm-thick polycrystalline gold nanofilms. Surprisingly, the electron-phonon coupling rates derived from two temperature simulations of the data reveal a faster interaction between electrons and the lattice in the case of the single-crystal sample. We interpret this unexpected behavior as arising from quantum confinement of the electrons in the 2 nm-thick gold nanofilm, as supported by absorption spectra, an effect that counteracts the expected increase in the electron scattering off surfaces and grain boundaries in the polycrystalline materials.

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

PubMed

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; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M 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/Pt3M 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/Pt3M 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 Pt3M 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.

Synthesis of netlike gold nanoparticles using ampicillin as a stabilizing reagent and its application

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

Song, Y.Z., E-mail: singyuanzhi@sina.com; Zhou, J.F.; Song, Y., E-mail: songyang@mail.buct.edu.cn

Graphical abstract: Electrochemical deposition of netlike gold nanoparticles (GNPs) on the surface of glassy carbon electrode and preparation of netlike GNPs in aqueous solution using ampicillin as a stabilizing reagent were proposed. The catalytic properties of netlike gold nanoparticles on the glassy carbon electrode for dopamine were demonstrated. The results indicate that the netlike gold nanoparticle modified electrode has an excellent repeatability and reproducibility. Display Omitted Highlights: ► Synthesis of netlike gold nanoparticles using ampicillin as a stabilizing reagent. ► Excellent repeatability and reproducibility of netlike gold nanoparticle modified glassy carbon electrode. ► The catalytic properties of netlike gold nanoparticlemore » for dopamine. -- Abstract: Electrochemical deposition of netlike gold nanoparticles on the surface of glassy carbon electrode and preparation of netlike GNPs in aqueous solution using ampicillin as a stabilizing reagent were proposed. The netlike gold nanoparticles were characterized by scanning electron microscope, transmission electron microscope, infrared spectrometer, UV spectrophotometer, powder X-ray diffractometer and electrochemical analyzer. The catalysis of the netlike gold nanoparticles on the glassy carbon electrode for dopamine was demonstrated. The results indicate that the gold nanoparticle modified electrode has an excellent repeatability and reproducibility.« less

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.

Gold nanoparticles with different capping systems: an electronic and structural XAS analysis.

PubMed

López-Cartes, C; Rojas, T C; Litrán, R; Martínez-Martínez, D; de la Fuente, J M; Penadés, S; Fernández, A

2005-05-12

Gold nanoparticles (NPs) have been prepared with three different capping systems: a tetralkylammonium salt, an alkanethiol, and a thiol-derivatized neoglycoconjugate. Also gold NPs supported on a porous TiO(2) substrate have been investigated. X-ray absorption spectroscopy (XAS) has been used to determine the electronic behavior of the different capped/supported systems regarding the electron/hole density of d states. Surface and size effects, as well as the role of the microstructure, have been also studied through an exhaustive analysis of the EXAFS (extended X-ray absorption fine structure) data. Very small gold NPs functionalized with thiol-derivatized molecules show an increase in d-hole density at the gold site due to Au-S charge transfer. This effect is overcoming size effects (which lead to a slightly increase of the d-electron density) for high S:Au atomic ratios and core-shell microstructures where an atomically abrupt Au-S interface likely does not exist. It has been also shown that thiol functionalization of very small gold NPs is introducing a strong distortion as compared to fcc order. To the contrary, electron transfer from reduced support oxides to gold NPs can produce a higher increase in d-electron density at the gold site, as compared to naked gold clusters.

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.

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.

Gold core@silver semishell Janus nanoparticles prepared by interfacial etching

NASA Astrophysics Data System (ADS)

Chen, Limei; Deming, Christopher P.; Peng, Yi; Hu, Peiguang; Stofan, Jake; Chen, Shaowei

2016-07-01

Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface.Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface. Electronic supplementary information (ESI) available: Additional TEM, UV-vis, XPS, and electrochemical data. See DOI: 10.1039/c6nr03368g

Elucidating Complex Surface Reconstructions with Atomic-Resolution Scanning Tunneling Microscopy: Au(100)-Aqueous Electrochemical Interface

DTIC Science & Technology

1992-05-01

that unusually high-quality STM data of this type 5-7can be obtained at ordered gold -aqueous interfaces. Reconstruction is seen 2 to be triggered on...all three low-index gold surfaces by altering the potential to values corresponding to small (10-15 pC cm-2 ) negative surface electronic 5-7 charges...connections. The former was platinum and the latter was a freshly electrooxidized gold wire. All electrode potentials quoted here, however, are

First-principles study of Au–Cu alloy surface changes induced by gas adsorption of CO, NO, or O{sub 2}

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

Dhifallah, Marwa; Université de Gabes, Unité de recherche environnement, Catalyse et Analyse des Procédés, 6072 Gabes; Dhouib, Adnene

2016-07-14

The surface composition of bimetallics can be strongly altered by adsorbing molecules where the metal with the strongest interaction with the adsorbate segregates into the surface. To investigate the effect of reactive gas on the surface composition of Au–Cu alloy, we examined by means of density functional theory to study the segregation behavior of copper in gold matrices. The adsorption mechanisms of CO, NO, and O{sub 2} gas molecules on gold, copper, and gold-copper low index (111), (100), and (110) surfaces were analyzed from energetic and electronic points of view. Our results show a strong segregation of Cu toward themore » (110) surface in the presence of all adsorbed molecules. Interestingly, the Cu segregation toward the (111) and (100) surface could occur only in the presence of CO and at a lower extent in the presence of NO. The analysis of the electronic structure highlights the different binding characters of adsorbates inducing the Cu segregation.« less

Changing gears from chemical adhesion of cells to flat substrata toward engulfment of micro-protrusions by active mechanisms

NASA Astrophysics Data System (ADS)

Hai, Aviad; Kamber, Dotan; Malkinson, Guy; Erez, Hadas; Mazurski, Noa; Shappir, Joseph; Spira, Micha E.

2009-12-01

Microelectrode arrays increasingly serve to extracellularly record in parallel electrical activity from many excitable cells without inflicting damage to the cells by insertion of microelectrodes. Nevertheless, apart from rare cases they suffer from a low signal to noise ratio. The limiting factor for effective electrical coupling is the low seal resistance formed between the plasma membrane and the electronic device. Using transmission electron microscope analysis we recently reported that cultured Aplysia neurons engulf protruding micron size gold spines forming tight apposition which significantly improves the electrical coupling in comparison with flat electrodes (Hai et al 2009 Spine-shaped gold protrusions improve the adherence and electrical coupling of neurons with the surface of micro-electronic devices J. R. Soc. Interface 6 1153-65). However, the use of a transmission electron microscope to measure the extracellular cleft formed between the plasma membrane and the gold-spine surface may be inaccurate as chemical fixation may generate structural artifacts. Using live confocal microscope imaging we report here that cultured Aplysia neurons engulf protruding spine-shaped gold structures functionalized by an RGD-based peptide and to a significantly lesser extent by poly-l-lysine. The cytoskeletal elements actin and associated protein cortactin are shown to organize around the stalks of the engulfed gold spines in the form of rings. Neurons grown on the gold-spine matrix display varying growth patterns but maintain normal electrophysiological properties and form functioning synapses. It is concluded that the matrices of functionalized gold spines provide an improved substrate for the assembly of neuro-electronic hybrids.

Ultra-fast electron capture by electrosterically-stabilized gold nanoparticles.

PubMed

Ghandi, Khashayar; Findlater, Alexander D; Mahimwalla, Zahid; MacNeil, Connor S; Awoonor-Williams, Ernest; Zahariev, Federico; Gordon, Mark S

2015-07-21

Ultra-fast pre-solvated electron capture has been observed for aqueous solutions of room-temperature ionic liquid (RTIL) surface-stabilized gold nanoparticles (AuNPs; ∼9 nm). The extraordinarily large inverse temperature dependent rate constants (k(e)∼ 5 × 10(14) M(-1) s(-1)) measured for the capture of electrons in solution suggest electron capture by the AuNP surface that is on the timescale of, and therefore in competition with, electron solvation and electron-cation recombination reactions. The observed electron transfer rates challenge the conventional notion that radiation induced biological damage would be enhanced in the presence of AuNPs. On the contrary, AuNPs stabilized by non-covalently bonded ligands demonstrate the potential to quench radiation-induced electrons, indicating potential applications in fields ranging from radiation therapy to heterogeneous catalysis.

Analysis of electromagnetic forces and causality in electron microscopy.

PubMed

Reyes-Coronado, Alejandro; Ortíz-Solano, Carlos Gael; Zabala, Nerea; Rivacoba, Alberto; Esquivel-Sirvent, Raúl

2018-09-01

The non-physical effects on the transverse momentum transfer from fast electrons to gold nanoparticles associated to the use of non-causal dielectric functions are studied. A direct test of the causality based on the surface Kramers-Kronig relations is presented. This test is applied to the different dielectric function used to describe gold nanostructures in electron microscopy. Copyright © 2018. Published by Elsevier B.V.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization.

PubMed

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-12-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 (3-/4-) as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

Mediated Electron Transfer at Vertically Aligned Single-Walled Carbon Nanotube Electrodes During Detection of DNA Hybridization

NASA Astrophysics Data System (ADS)

Wallen, Rachel; Gokarn, Nirmal; Bercea, Priscila; Grzincic, Elissa; Bandyopadhyay, Krisanu

2015-06-01

Vertically aligned single-walled carbon nanotube (VASWCNT) assemblies are generated on cysteamine and 2-mercaptoethanol (2-ME)-functionalized gold surfaces through amide bond formation between carboxylic groups generated at the end of acid-shortened single-walled carbon nanotubes (SWCNTs) and amine groups present on the gold surfaces. Atomic force microscopy (AFM) imaging confirms the vertical alignment mode of SWCNT attachment through significant changes in surface roughness compared to bare gold surfaces and the lack of any horizontally aligned SWCNTs present. These SWCNT assemblies are further modified with an amine-terminated single-stranded probe-DNA. Subsequent hybridization of the surface-bound probe-DNA in the presence of complementary strands in solution is followed using impedance measurements in the presence of Fe(CN)6 3-/4- as the redox probe in solution, which show changes in the interfacial electrochemical properties, specifically the charge-transfer resistance, due to hybridization. In addition, hybridization of the probe-DNA is also compared when it is attached directly to the gold surfaces without any intermediary SWCNTs. Contrary to our expectations, impedance measurements show a decrease in charge-transfer resistance with time due to hybridization with 300 nM complementary DNA in solution with the probe-DNA attached to SWCNTs. In contrast, an increase in charge-transfer resistance is observed with time during hybridization when the probe-DNA is attached directly to the gold surfaces. The decrease in charge-transfer resistance during hybridization in the presence of VASWCNTs indicates an enhancement in the electron transfer process of the redox probe at the VASWCNT-modified electrode. The results suggest that VASWCNTs are acting as mediators of electron transfer, which facilitate the charge transfer of the redox probe at the electrode-solution interface.

From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147

NASA Astrophysics Data System (ADS)

Häberlen, Oliver D.; Chung, Sai-Cheong; Stener, Mauro; Rösch, Notker

1997-03-01

A series of gold clusters spanning the size range from Au6 through Au147 (with diameters from 0.7 to 1.7 nm) in icosahedral, octahedral, and cuboctahedral structure has been theoretically investigated by means of a scalar relativistic all-electron density functional method. One of the main objectives of this work was to analyze the convergence of cluster properties toward the corresponding bulk metal values and to compare the results obtained for the local density approximation (LDA) to those for a generalized gradient approximation (GGA) to the exchange-correlation functional. The average gold-gold distance in the clusters increases with their nuclearity and correlates essentially linearly with the average coordination number in the clusters. An extrapolation to the bulk coordination of 12 yields a gold-gold distance of 289 pm in LDA, very close to the experimental bulk value of 288 pm, while the extrapolated GGA gold-gold distance is 297 pm. The cluster cohesive energy varies linearly with the inverse of the calculated cluster radius, indicating that the surface-to-volume ratio is the primary determinant of the convergence of this quantity toward bulk. The extrapolated LDA binding energy per atom, 4.7 eV, overestimates the experimental bulk value of 3.8 eV, while the GGA value, 3.2 eV, underestimates the experiment by almost the same amount. The calculated ionization potentials and electron affinities of the clusters may be related to the metallic droplet model, although deviations due to the electronic shell structure are noticeable. The GGA extrapolation to bulk values yields 4.8 and 4.9 eV for the ionization potential and the electron affinity, respectively, remarkably close to the experimental polycrystalline work function of bulk gold, 5.1 eV. Gold 4f core level binding energies were calculated for sites with bulk coordination and for different surface sites. The core level shifts for the surface sites are all positive and distinguish among the corner, edge, and face-centered sites; sites in the first subsurface layer show still small positive shifts.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Bottom-up formation of robust gold carbide

PubMed Central

Westenfelder, Benedikt; Biskupek, Johannes; Meyer, Jannik C.; Kurasch, Simon; Lin, Xiaohang; Scholz, Ferdinand; Gross, Axel; Kaiser, Ute

2015-01-01

A new phenomenon of structural reorganization is discovered and characterized for a gold-carbon system by in-situ atomic-resolution imaging at temperatures up to 1300 K. Here, a graphene sheet serves in three ways, as a quasi transparent substrate for aberration-corrected high-resolution transmission electron microscopy, as an in-situ heater, and as carbon supplier. The sheet has been decorated with gold nanoislands beforehand. During electron irradiation at 80 kV and at elevated temperatures, the accumulation of gold atoms has been observed on defective graphene sites or edges as well as at the facets of gold nanocrystals. Both resulted in clustering, forming unusual crystalline structures. Their lattice parameters and surface termination differ significantly from standard gold nanocrystals. The experimental data, supported by electron energy loss spectroscopy and density-functional theory calculations, suggests that isolated gold and carbon atoms form – under conditions of heat and electron irradiation – a novel type of compound crystal, Au-C in zincblende structure. The novel material is metastable, but surprisingly robust, even under annealing condition. PMID:25772348

Ultrafast chemical interface scattering as an additional decay channel for nascent nonthermal electrons in small metal nanoparticles.

PubMed

Bauer, Christophe; Abid, Jean-Pierre; Fermin, David; Girault, Hubert H

2004-05-15

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas.

Surface-plasmon-assisted electron pair formation in strong electromagnetic field

NASA Astrophysics Data System (ADS)

Kroó, N.; Rácz, P.; Varró, S.

2014-03-01

In this work the strong electromagnetic field of femtosecond Ti:Sa lasers was used to excite surface plasmon oscillations (SPOs) in gold films at room temperature in the Kretschmann geometry. Experimental investigations were carried out using a surface plasmon near field scanning tunneling microscope, measuring its response to excitation at SPO hot spots on the gold surface. Furthermore, the spectra of photoelectrons, liberated by multiplasmon absorption, have also been measured by a time-of-flight spectrometer. In both cases new type of anomalies in both the STM and electron TOF signals have been measured in the same laser intensity range. The existence of these anomalies may be qualitatively understood, by using the intensity-dependent expression for the effective electron-electron scattering potential, derived earlier in a different context. In this theoretical work an effective attraction potential has been predicted in the presence of strong inhomogeneous radiation fields.

The effect of alkali metal on the surface properties of potassium doped Au-Beta zeolites

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

Sobczak, Izabela, E-mail: sobiza@amu.edu.pl; Rydz, Michal; Ziolek, Maria

2013-02-15

Graphical abstract: Display Omitted Highlights: ► Interaction of gold with K leads to the change of electronic state and redox properties of gold. ► The amount of potassium incorporated into Au-zeolites determines the size of gold particles. ► K(0.2 wt.%)/Au-Beta exhibits the best performance in decomposition of N{sub 2}O and removal of Bu{sub 2}S. -- Abstract: Beta zeolite was applied as support for gold introduced by gold-precipitation method and potassium added by impregnation or adsorption. The effect of zeolite composition and the amount of potassium introduced on the surface properties of the final materials was considered. Moreover, the interaction ofmore » gold and potassium species was found to be related to the adsorptive and catalytic behaviour of zeolites in NO reduction with propene and deodorization. K/Au-Beta(Impregnated) exhibits the best performance in the above mentioned processes because of the small gold particles (between 2 and 5 nm) and interaction of gold with potassium species leading to the change of electronic properties of the surface (the appearance of cationic gold species). Potassium added as a promoter improves the catalytic properties of Au-zeolite in N{sub 2}O decomposition and also in deodorization (increase of the ability to dibutyl sulphide oxidation). The catalysts prepared were characterized by XRD, XPS, UV–vis, TEM, pyridine adsorption combined with FTIR and test reaction (2-propanol transformation).« less

Laser ablative decoration of micro-diamonds by gold nanoparticles for fabrication of hybrid plasmonic-dielectric antennae

NASA Astrophysics Data System (ADS)

Ivanova, A. K.; Ionin, A. A.; Khmelnitskii, R. A.; Kudryashov, S. I.; Levchenko, A. O.; Mel'nik, N. N.; Rudenko, A. A.; Saraeva, I. N.; Umanskaya, S. P.; Zayarny, D. A.; Nguyen, L. V.; Nguyen, T. T. H.; Pham, M. H.; Pham, D. V.; Do, T. H.

2017-06-01

Hybrid plasmonic-dielectric antennae are fabricated by laser ablation of gold in water sols of micro-diamonds. Electron microscopy and energy-dispersive x-ray spectroscopy of their deposits on a silicon wafer surface indicate close proximity of gold nanoparticles and micro-diamonds, which is supported by photoluminescence studies demonstrating strong (eight-fold) damping of micro-diamond luminescence owing to the attachment of the gold nanoparticles. UV-near-IR spectroscopy of their sols reveals a considerable plasmonic effect, related to red spectral shifts of surface plasmon resonance for the gold nanoparticles in the laser-ablation-fabricated antennae.

Influence of Adsorbed Hydroxyl and Carbon Monoxide on Potential-Induced Reconstruction of Au(100) as Examined by Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

years have witnessed substantial advances in our knowledge of metal reconstruction in electrochemical systems, primarily for low-index gold surfaces in...index gold surfaces, reconstruction can be formed or removed by applying electrode potentials corresponding to negative or positive electronic charge...potential and gold oxidation regions, for Au(100) in 0.1 M KOH, obtained in a conventional electrochemical cell (solid trace). The voltammetric

Fungus-mediated biological synthesis of gold nanoparticles: potential in detection of liver cancer

PubMed Central

Chauhan, Arun; Zubair, Swaleha; Tufail, Saba; Sherwani, Asif; Sajid, Mohammad; Raman, Suri C; Azam, Amir; Owais, Mohammad

2011-01-01

Background Nanomaterials are considered to be the pre-eminent component of the rapidly advancing field of nanotechnology. However, developments in the biologically inspired synthesis of nanoparticles are still in their infancy and consequently attracting the attention of material scientists throughout the world. Keeping in mind the fact that microorganism-assisted synthesis of nanoparticles is a safe and economically viable prospect, in the current study we report Candida albicans-mediated biological synthesis of gold nanoparticles. Methods and results Transmission electron microscopy, atomic force microscopy, and various spectrophotometric analyses were performed to characterize the gold nanoparticles. The morphology of the synthesized gold particles depended on the abundance of C. albicans cytosolic extract. Transmission electron microscopy, nanophox particle analysis, and atomic force microscopy revealed the size of spherical gold nanoparticles to be in the range of 20–40 nm and nonspherical gold particles were found to be 60–80 nm. We also evaluated the potential of biogenic gold nanoparticles to probe liver cancer cells by conjugating them with liver cancer cell surface-specific antibodies. The antibody-conjugated gold particles were found to bind specifically to the surface antigens of the cancer cells. Conclusion The antibody-conjugated gold particles synthesized in this study could successfully differentiate normal cell populations from cancerous cells. PMID:22072868

Surface Functionalization of Diamond Films by Photoreaction of Elemental Sulfur and Their Surface Properties

NASA Astrophysics Data System (ADS)

Nakamura, Takako; Ohana, Tsuguyori

2012-08-01

A useful method for direct sulfurization of diamond film surfaces by photoreaction of elemental sulfur was developed. The introduction of thiol groups onto the diamond films was confirmed by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, and scanning electron microscopy (SEM) analyses. The sulfur-modified diamond films attached to gold nanoparticles by self-assembly. The degrees of thiol group introduction and gold attachment were found to depend on photoirradiation time by monitoring by XPS. The gold-modified diamond film was observed to act as a surface-enhanced Raman scattering substrate for measurement of picric acid.

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.

Using the plasmon linewidth to calculate the time and efficiency of electron transfer between gold nanorods and graphene.

PubMed

Hoggard, Anneli; Wang, Lin-Yung; Ma, Lulu; Fang, Ying; You, Ge; Olson, Jana; Liu, Zheng; Chang, Wei-Shun; Ajayan, Pulickel M; Link, Stephan

2013-12-23

We present a quantitative analysis of the electron transfer between single gold nanorods and monolayer graphene under no electrical bias. Using single-particle dark-field scattering and photoluminescence spectroscopy to access the homogeneous linewidth, we observe broadening of the surface plasmon resonance for gold nanorods on graphene compared to nanorods on a quartz substrate. Because of the absence of spectral plasmon shifts, dielectric interactions between the gold nanorods and graphene are not important and we instead assign the plasmon damping to charge transfer between plasmon-generated hot electrons and the graphene that acts as an efficient acceptor. Analysis of the plasmon linewidth yields an average electron transfer time of 160 ± 30 fs, which is otherwise difficult to measure directly in the time domain with single-particle sensitivity. In comparison to intrinsic hot electron decay and radiative relaxation, we furthermore calculate from the plasmon linewidth that charge transfer between the gold nanorods and the graphene support occurs with an efficiency of ∼10%. Our results are important for future applications of light harvesting with metal nanoparticle plasmons and efficient hot electron acceptors as well as for understanding hot electron transfer in plasmon-assisted chemical reactions.

Synthesis and characterization of mixed monolayer protected gold nanorods and their Raman activities

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

Mlambo, Mbuso; Nanotechnology Innovation Centre, Advanced Materials Division, Mintek, Private Bag X3015, Randburg 2125; Mdluli, Phumlani S.

2013-10-15

Graphical abstract: Gold nanorods surface functionalization. - Highlights: • Mixed monolayer protected gold nanorods. • Surface enhanced Raman spectroscopy. • HS-(CH{sub 2}){sub 11}-NHCO-coumarin as a Raman active compound. - Abstract: The cetyltrimethylammonium bromide (CTAB) gold nanorods (AuNRs) were prepared by seed-mediated route followed by the addition of a Raman active compound (HS-(CH{sub 2}){sub 11}-NHCO-coumarin) on the gold nanorods surfaces. Different stoichiometric mixtures of HS-(CH{sub 2}){sub 11}-NHCO-coumarin and HS-PEG-(CH{sub 2}){sub 11}COOH were evaluated for their Raman activities. The lowest stoichiometric ratio HS-(CH{sub 2}){sub 11}-NHCO-coumarin adsorbed on gold nanorods surface was detected and enhanced by Raman spectroscopy. The produced mixed monolayer protectedmore » gold nanorods were characterized by UV-vis spectrometer for optical properties, transmission electron microscope (TEM) for structural properties (shape and aspect ratio) and their zeta potentials (charges) were obtained from ZetaSizer to determine the stability of the produced mixed monolayer protected gold nanorods. The Raman results showed a surface enhanced Raman scattering (SERS) enhancement at the lowest stoichiometric ratio of 1% HS-(CH{sub 2}){sub 11}-NHCO-coumarin compared to high ratio of 50% HS-(CH{sub 2}){sub 11}-NHCO-coumarin on the surface of gold nanorods.« less

EPR and rheological study of hybrid interfaces in gold-clay-epoxy nanocomposites.

PubMed

Angelov, Verislav; Velichkova, Hristiana; Ivanov, Evgeni; Kotsilkova, Rumiana; Delville, Marie-Hélène; Cangiotti, Michela; Fattori, Alberto; Ottaviani, Maria Francesca

2014-11-11

With the aim to obtain new materials with special properties to be used in various industrial and biomedical applications, ternary "gold-clay-epoxy" nanocomposites and their nanodispersions were prepared using clay decorated with gold nanoparticles (AuNPs), at different gold contents. Nanocomposites structure was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Rheology and electron paramagnetic resonance (EPR) techniques were used in order to evaluate the molecular dynamics in the nanodispersions, as well as dynamics at interfaces in the nanocomposites. The percolation threshold (i.e., the filler content related to the formation of long-range connectivity of particles in the dispersed media) of the gold nanoparticles was determined to be ϕp = 0.6 wt % at a fixed clay content of 3 wt %. The flow activation energy and the relaxation time spectrum illustrated the presence of interfacial interactions in the ternary nanodispersions around and above the percolation threshold of AuNPs; these interfacial interactions suppressed the global molecular dynamics. It was found that below ϕp the free epoxy polymer chains ratio dominated over the chains attracted on the gold surfaces; thus, the rheological behavior was not significantly changed by the presence of AuNPs. While, around and above ϕp, the amount of the bonded epoxy polymer chains on the gold surface was much higher than that of the free chains; thus, a substantial increase in the flow activation energy and shift in the spectra to higher relaxation times appeared. The EPR signals of the nanocomposites depended on the gold nanoparticle contents and the preparation procedure thus providing a fingerprint of the different nanostructures. The EPR results from spin probes indicated that the main effect of the gold nanoparticles above ϕp, was to form a more homogeneous, viscous and polar clay-epoxy mixture at the nanoparticle surface. The knowledge obtained from this study is applicable to understand the role of interfaces in ternary nanocomposites with different combinations of nanofillers.

The Design, Synthesis, and Characterization of Open Sites on Metal Clusters

NASA Astrophysics Data System (ADS)

Nigra, Michael Mark

Coordinatively unsaturated corner and edge atoms have been hypothesized to have the highest activity of sites responsible for many catalytic reactions on a metal surface. Recent studies have validated this hypothesis in varied reaction systems. However, quantification of different types of coordinatively unsaturated sites, and elucidation of their individual catalytic rates has remained a largely unresolved challenge when understanding catalysis on metal surfaces. Yet such structure-function knowledge would be invaluable to the design of more active and selective metal-surface catalysts in the future. I investigated the catalytic contributions of undercoordinated sites such as corner and edge atoms are investigated in a model reaction system using organic ligands bound to the gold nanoparticle surface. The catalyst consisted of 4 nm gold nanoparticles on a metal oxide support, using resazurin to resorufin as a model reaction system. My results demonstrate that in this system, corner atom sites are the most undercoordinated sites, and are over an order of magnitude more active when compared to undercoordinated edge atom sites, while terrace sites remain catalytically inactive for the reduction reaction of resazurin to resorufin. Catalytic activity has been also demonstrated for calixarene-bound gold nanoparticles using the reduction of 4-nitrophenol. With the 4-nitrophenol reduction reaction, a comparative study was undertaken to compare calixarene phosphine and calixarene thiol bound 4 nm gold particles. The results of the study suggested that a leached site was responsible for catalysis and not sites on the original gold nanoparticles. Future experiments with calixarene bound gold clusters could investigate ligand effects in reactions where the active site is not a leached or aggregated gold species, possibly in oxidation reactions, where electron-rich gold is hypothesized to be a good catalyst. The results that emphasize the enhanced catalytic activity of undercoordinated sites led me to synthesize small gold clusters consisting of a high fraction of coordinatively unsaturated open sites. This was enabled through an approach that utilized bulky calix[4]arene ligands that are bound to a gold core. Since the size of the calix[4]arene ligand is commensurate with the size of the gold cluster core, the calix[4]arene ligand does not pack closely together on the gold cluster surface. This in turn results in areas of accessible gold atom sites between ligands. Additionally, these calix[4]arene ligands prevent cluster aggregation and electronically tune the gold core in a manner conceptually similar to enzymes affecting reactivity through organic side-chains acting as ligands. I quantified the number of open sites that result from this packing problem on the gold cluster surface, using fluorescence probe chemisorption experiments. The results of these chemisorption measurements support the mechanical model of accessibility whereby accessibility is not dependent on the identity of the functional group, whether it be calixarene phosphines or N-heterocyclic carbenes, bound to the gold surface, but rather to the relative radii of curvature of bound ligands and the gold cluster core. Additional materials characterization was completed with transmission electron microscopy in both bright-field imaging of zeolites, in MCM-22 and delaminated ITQ-2 and UCB-1 materials, and in dark field imaging of glucan coatings on oxide particles. These materials could prove to be interesting materials as to use as supports for the calixarene-bound metal clusters described above or for other metal clusters.

Reticulated vitreous carbon as a scaffold for enzymatic fuel cell designing.

PubMed

Kizling, Michal; Dzwonek, Maciej; Olszewski, Bartłomiej; Bącal, Paweł; Tymecki, Łukasz; Więckowska, Agnieszka; Stolarczyk, Krzysztof; Bilewicz, Renata

2017-09-15

Three - dimensional (3D) electrodes are successfully used to overcome the limitations of the low space - time yield and low normalized space velocity obtained in electrochemical processes with two - dimensional electrodes. In this study, we developed a three - dimensional reticulated vitreous carbon - gold (RVC-Au) sponge as a scaffold for enzymatic fuel cells (EFC). The structure of gold and the real electrode surface area can be controlled by the parameters of metal electrodeposition. In particular, a 3D RVC-Au sponge provides a large accessible surface area for immobilization of enzyme and electron mediators, moreover, effective mass diffusion can also take place through the uniform macro - porous scaffold. To efficiently bind the enzyme to the electrode and enhance electron transfer parameters the gold surface was modified with ultrasmall gold nanoparticles stabilized with glutathione. These quantum sized nanoparticles exhibit specific electronic properties and also expand the working surface of the electrode. Significantly, at the steady state of power generation, the EFC device with RVC-Au electrodes provided high volumetric power density of 1.18±0.14mWcm -3 (41.3±3.8µWcm -2 ) calculated based on the volume of electrode material with OCV 0.741±0.021V. These new 3D RVC-Au electrodes showed great promise for improving the power generation of EFC devices. Copyright © 2017 Elsevier B.V. All rights reserved.

Aqueous Black Colloids of Reticular Nanostructured Gold

NASA Astrophysics Data System (ADS)

Stanca, S. E.; Fritzsche, W.; Dellith, J.; Froehlich, F.; Undisz, A.; Deckert, V.; Krafft, C.; Popp, J.

2015-01-01

Since ancient times, noble gold has continuously contributed to several aspects of life from medicine to electronics. It perpetually reveals its new features. We report the finding of a unique form of gold, reticular nanostructured gold (RNG), as an aqueous black colloid, for which we present a one-step synthesis. The reticules consist of gold crystals that interconnect to form compact strands. RNG exhibits high conductivity and low reflection, and these features, coupled with the high specific surface area of the material, could prove valuable for applications in electronics and catalysis. Due to high absorption throughout the visible and infrared domain, RNG has the potential to be applied in the construction of sensitive solar cells or as a substrate for Raman spectroscopy.

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

PubMed

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

2016-10-11

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

Near-Infrared Plasmon-Assisted Water Oxidation.

PubMed

Nishijima, Yoshiaki; Ueno, Kosei; Kotake, Yuki; Murakoshi, Kei; Inoue, Haruo; Misawa, Hiroaki

2012-05-17

We report the stoichiometric evolution of oxygen via water oxidation by irradiating a plasmon-enhanced photocurrent generation system with near-infrared light (λ: 1000 nm), in which gold nanostructures were arrayed on the surface of TiO2 electrode. It is considered that multiple electron holes generated by plasmon-induced charge excitation led to the effective recovery of water oxidation after the electron transfer from gold to TiO2. The proposed system containing a gold nanostructured TiO2 electrode may be a promising artificial photosynthetic system using near-infrared light.

Biotin-streptavidin-induced aggregation of gold nanorods: tuning rod-rod orientation.

PubMed

Gole, Anand; Murphy, Catherine J

2005-11-08

We report herein biotin-streptavidin-mediated aggregation studies of long gold nanorods. We have previously demonstrated end-to-end linkages of gold nanorods driven by the biotin-streptavidin interaction (Caswell et al. J. Am. Chem. Soc. 2003, 125, 13914). In that report, the specific binding of biotin disulfide to the gold nanorod edges was achieved due to the preferred binding of thiol molecules to the Au[111] surface (gold nanorod ends) as opposed to the gold nanorod side faces. This led to the end-end linkage of gold nanorods upon subsequent addition of streptavidin. In this report we demonstrate a simple procedure to biotinylate the entire gold nanorod surface and subsequently form a 3-D assembly by addition of streptavidin. Gold nanorods were synthesized by the three-step seeding protocol documented in our previous articles. The surface of gold nanorods was further modified by a layer of a weak polyelectrolyte, poly(acrylic acid), PAA. A biotin molecule which has an amine group at one end (biotin-PEO-amine) was anchored to the carboxylic acid group of the polyelectrolyte using the well-known carbodiimide chemistry. This process biotinylates the entire gold nanorod surface. Addition of streptavidin further leads to aggregation of gold nanorods. A closer look at the aggregates reveals a preferential side-to-side assembly of gold nanorods. The gold nanorods were characterized at each stage by UV-vis spectroscopy, light scattering, and transmission electron microscopy (TEM) measurements.

Mapping atomic contact between pentacene and a Au surface using scanning tunneling spectroscopy.

PubMed

Song, Young Jae; Lee, Kyuho; Kim, Seong Heon; Choi, Byoung-Young; Yu, Jaejun; Kuk, Young

2010-03-10

We mapped spatially varying intramolecular electronic structures on a pentacene-gold interface using scanning tunneling spectroscopy. Along with ab initio calculations based on density functional theory, we found that the directional nature of the d orbitals of Au atoms plays an important role in the interaction at the pentacene-gold contact. The gold-induced interface states are broadened and shifted by various pentacene-gold distances determined by the various registries of a pentacene molecule on a gold substrate.

Comparative electron microscopic study of the surface structure of gold, Teflon, and titanium stapes prostheses.

PubMed

Kwok, P; Fisch, U; Strutz, J; Jacob, P

2001-09-01

The goal of this study was to compare stapes prostheses of different materials with respect to their surface structures and to discuss their suitability for their use in stapes surgery. The surface condition of a stapes prosthesis plays an important role in relation to the type of membrane that forms between the stapes piston and the bony edge of the stapedotomy opening. The quality of this membrane in thickness and mobility is one of the determinants for postoperative hearing improvement. The surface conditions of gold, Teflon/steel, Teflon/platinum, and titanium stapes prostheses were examined with a scanning electron microscope. The loop, shaft, and end of each prosthesis were studied. The gold piston was the smoothest of the four pistons examined. When it was cut with a scalpel, a very smooth surface was achieved at the end area. The Teflon piston had the roughest surface. However, when it was cut, a smooth surface with a parallel arrangement of fibers resulted. Its steel loop was the smoothest, followed by gold and platinum. The titanium shaft had a scaly surface, which remained when the end of the shaft was shortened. Because a certain roughness of the piston surface is necessary for the development of a stable membrane between the piston and the edge of the stapedotomy opening, the titanium prosthesis is considered to be the most suitable for stapes surgery of the three pistons examined.

High yield production of long branched Au nanoparticles characterized by atomic resolution transmission electron microscopy

PubMed Central

Mayoral, Alvaro; Magen, Cesar; Jose-Yacaman, Miguel

2011-01-01

Long multi-branched gold nanoparticles have been synthesized in a very high yield through a facile synthesis combining two different capping agents. The stability of these materials with the time has been tested and their characterization have been performed by diverse advanced electron microscopy techniques, paying special attention to aberration corrected transmission electron microscopy in order to unambiguously analyze the surface structure of the branches and provide insights for the formation of stellated gold nanoparticles. PMID:22125420

A first principles study on the electronic origins of silver segregation at the Ag-Au (111) surface

NASA Astrophysics Data System (ADS)

Hoppe, Sandra; Müller, Stefan

2017-12-01

The special electronic structure of gold gives rise to many interesting phenomena, such as its color. The surface segregation of the silver-gold system has been the subject of numerous experimental and theoretical studies, yielding conflicting results ranging from strong Ag surface enrichment to Au surface segregation. Via a combined approach of density functional theory (DFT) and statistical physics, we have analyzed the segregation at the Ag-Au (111) surface with different Ag bulk concentrations. Interestingly, we observe a moderate Au surface segregation, which is due to a charge transfer from the less electronegative Ag to Au. Canonical Monte Carlo simulations suggest that the calculated concentration profile with a Au-enriched surface layer remains stable up to higher temperatures. However, the presence of adsorbed oxygen reverses the segregation behavior and leads to strong Ag enrichment of the surface layer.

Concentration-dependent photophysical switching in mixed self-assembled monolayers of pentacene and perylenediimide on gold nanoclusters.

PubMed

Kato, Daiki; Sakai, Hayato; Araki, Yasuyuki; Wada, Takehiko; Tkachenko, Nikolai V; Hasobe, Taku

2018-03-28

Photophysical control and switching on organic-inorganic hybrid interfaces are of great interest in diverse fundamental and applicative research areas. 6,13-Bis(triisopropylsilylethynyl)pentacene (TP) is well-known to exhibit efficient singlet fission (SF) for generation of high-yield triplet excited states in aggregated forms, whereas perylenediimide (PDI) ensembles show the characteristic excimer formation. Additionally, a combination of pentacene (electron donor: D) and PDI (electron acceptor: A) is expected to undergo an efficient photoinduced electron transfer (PET), and absorption of two chromophores combined covers the entire visible region. Therefore, the concentration-dependent mixed self-assembled monolayers (SAMs) composed of two chromophores enable us to control and switch the photophysical processes on a surface. In this work, a series of mixed SAMs composed of TP and PDI units on gold nanoclusters (GNCs) were newly synthesized by changing the relative molecular concentration ratios. Structural control of mixed SAMs on a gold surface based on the concentration ratios was successfully achieved. Time-resolved femtosecond and nanosecond transient absorption measurements clearly demonstrate photophysical control and switching of the above competitive reactions such as SF, electron transfer (ET) and excimer formation. The maximum quantum yields of triplet states (ΦT = ∼170%) and electron transfer (ΦET = ∼95%) were quantitatively evaluated by changing the concentration ratios. The rate constants of SF and excimer processes are largely dependent on the concentration ratios, whereas the rate constants of ET processes approximately remain constant. These findings are also discussed based on the statistical framework of the assembly of chromophores on the gold surface.

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

Preservation of thermal control specular gold baffle surface on the James Webb Space Telescope (JWST) integrated science instrument module (ISIM) electronics compartment (IEC)

NASA Astrophysics Data System (ADS)

Montt de Garcia, Kristina; Patel, Jignasha; Perry, Radford, III

2010-08-01

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.

Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters.

PubMed

Perrier, Aurélie; Maurel, François; Aubard, Jean

2007-10-04

In the course of developing electronic devices on a molecular scale, dithienylethenes photochromic molecules constitute promising candidates for optoelectronic applications such as memories and switches. There is thus a great interest to understand and control the switching behavior of photochromic compounds deposited on metallic surfaces or nanoparticles. Within the framework of the density functional theory, we studied the effect of small gold clusters (Au3 and Au9) on the electronic structure and absorption spectrum of a model dithienylethene molecule. The molecular orbital interactions between the photochromic molecule and the gold cluster made it possible to rationalize some experimental findings (Dulic, D.; van der Molen, S. J.; Kudernac, T.; Jonkman, H. T.; de Jong, J. J. D.; Bowden, T. N.; van Esch, J.; Feringa, B. L.; van Wees, B. J. Phys. Rev. Lett. 2003, 91, 207402). For the closed-ring isomer, grafting a photochromic molecule on a small gold cluster does not change the characteristics of the electronic transition involved in the ring-opening reaction. On the opposite, the absorption spectrum of the photochromic open-ring isomer is strongly modified by the inclusion of the metallic cluster. In agreement with experimental results, our study thus showed that the cycloreversion reaction which involves the closed-ring isomer should be still possible, whereas the ring-closure reaction which involves the open-ring isomer should be inhibited. Connecting a dithienylethene molecule to a small gold cluster hence provides a qualitative comprehension of the photochromic activities of dithienylethenes connected to a gold surface.

Modeling the Effect of Surface Modification of Gold Nanoparticles Irradiated with 60Co on the Secondary Particles Emission Spectrum

NASA Astrophysics Data System (ADS)

Belousov, A. V.; Morozov, V. N.; Krusanov, G. A.; Kolyvanova, M. A.; Chernyaev, A. P.; Shtil, A. A.

2018-03-01

The Monte Carlo method (computer simulation) is used to construct a physical model of secondary particles emission induced by the simulated irradiation of a gold nanoparticle with 60Co. It is demonstrated that the modification of the nanoparticle surface with polyethylene glycol affects the spectrum of secondary electrons produced in a nanoparticle and leaving it and its shell. The model takes into account the size and the chemical composition of the shell and provides an opportunity to design antitumor radiosensitizers based on gold nanoparticles.

Green synthesis and characterization of size tunable silica-capped gold core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Wangoo, Nishima; Shekhawat, Gajendra; Wu, Jin-Song; Bhasin, Aman K. K.; Suri, C. R.; Bhasin, K. K.; Dravid, Vinayak

2012-08-01

Silica-coated gold nanoparticles (Au@SiO2) with controlled silica-shell thickness were prepared by a modified Stober's method using 10-nm gold nanoparticles (AuNPs) as seeds. The AuNPs were silica-coated with a sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica source and ammonia as a catalyst. An increase in TEOS concentration resulted in an increase in shell thickness. The NPs were characterized by transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, scanning near-field ultrasound holography and scanning transmission electron microscopy. The method required no surface modification and the synthesized core shell nanoparticles can be used for various types of biological applications.

Effect of gold nanoparticles on the structure and electron-transfer characteristics of glucose oxidase redox polyelectrolyte-surfactant complexes.

PubMed

Cortez, M Lorena; Marmisollé, Waldemar; Pallarola, Diego; Pietrasanta, Lía I; Murgida, Daniel H; Ceolín, Marcelo; Azzaroni, Omar; Battaglini, Fernando

2014-10-06

Efficient electrical communication between redox proteins and electrodes is a critical issue in the operation and development of amperometric biosensors. The present study explores the advantages of a nanostructured redox-active polyelectrolyte-surfactant complex containing [Os(bpy)2Clpy](2+) (bpy=2,2'-bipyridine, py= pyridine) as the redox centers and gold nanoparticles (AuNPs) as nanodomains for boosting the electron-transfer propagation throughout the assembled film in the presence of glucose oxidase (GOx). Film structure was characterized by grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM), GOx incorporation was followed by surface plasmon resonance (SPR) and quartz-crystal microbalance with dissipation (QCM-D), whereas Raman spectroelectrochemistry and electrochemical studies confirmed the ability of the entrapped gold nanoparticles to enhance the electron-transfer processes between the enzyme and the electrode surface. Our results show that nanocomposite films exhibit five-fold increase in current response to glucose compared with analogous supramolecular AuNP-free films. The introduction of colloidal gold promotes drastic mesostructural changes in the film, which in turn leads to a rigid, amorphous interfacial architecture where nanoparticles, redox centers, and GOx remain in close proximity, thus improving the electron-transfer process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical properties of nanostructured porous gold electrodes in biofouling solutions.

PubMed

Patel, Jay; Radhakrishnan, Logudurai; Zhao, Bo; Uppalapati, Badharinadh; Daniels, Rodney C; Ward, Kevin R; Collinson, Maryanne M

2013-12-03

The effect of electrode porosity on the electrochemical response of redox active molecules (potassium ferricyanide, ruthenium(III) hexammine, and ferrocene methanol) in the presence of bovine serum albumin or fibrinogen was studied at macroporous (pore diameter: 1200 nm), hierarchical (1200/60 nm), and nanoporous (<50 nm) gold. These electrodes were prepared using standard templating or dealloying techniques, and cyclic voltammetry (CV) was utilized to evaluate the effect of protein adsorption on the electron transfer of the diffusing redox probes. Following exposure to albumin (or fibrinogen) under near neutral pH conditions, planar gold electrodes showed an immediate reduction in Faradaic peak current and increase in peak splitting for potassium ferricyanide. The rate at which the CV curves changed was highly dependent on the morphology of the electrode. For example, the time required for the Faradaic current to drop to one-half of its original value was 3, 12, and 38 min for planar gold, macroporous gold, and hierarchical gold, respectively. Remarkably, for nanoporous gold, only a few percent drop in the peak Faradaic current was observed after an hour in solution. A similar suppression in the voltammetry at planar gold was also noted for ruthenium hexammine at pH 3 after exposure to albumin for several hours. At nanoporous gold, no significant loss in response was observed. The order of performance of the electrodes as judged by their ability to efficiently transfer electrons in the presence of biofouling agents tracked porosity with the electrode having the smallest pore size and largest surface area, providing near ideal results. Nanoporous gold electrodes when immersed in serum or heparinized blood containing potassium ferricyanide showed ideal voltammetry while significant fouling was evident in the electrochemical response at planar gold. The small nanopores in this 3D open framework are believed to restrict the transport of large biomolecules, thus minimizing passivation of the inner surfaces while permitting access to small redox probes to efficiently exchange electrons.

Particle sensing with confined optical field enhanced fluorescence emission (Cofefe).

PubMed

Kenison, John P; Fast, Alexander; Matthews, Brandon M; Corn, Robert M; Potma, Eric Olaf

2018-05-14

We describe the development and performance of a new type of optical sensor suitable for registering the binding/dissociation of nanoscopic particles near a gold sensing surface. The method shares similarities with surface plasmon resonance microscopy but uses a completely different optical signature for reading out binding events. This new optical read-out mechanism, which we call confined optical field enhanced fluorescence emission (Cofefe), uses pulsed surface plasmon polariton fields at the gold/liquid interface that give rise to confined optical fields upon binding of the target particle to the gold surface. The confined near-fields are sufficient to induce two-photon absorption in the gold sensor surface near the binding site. Subsequent radiative recombination of the electron-hole pairs in the gold produces fluorescence emission, which can be captured by a camera in the far-field. Bound nanoparticles show up as bright confined spots against a dark background on the camera. We show that the Cofefe sensor is capable of detecting gold and silicon nanoparticles, as well as polymer nanospheres and sub-μm lipid droplets in a label-free manner with average illumination powers of less than 10 μW/μm 2 .

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 promoted nor attenuated the activity of monocytes when exposed to zymosan particles or S. epidermidis. PMID:24550671

Construction and direct electrochemistry of orientation controlled laccase electrode.

PubMed

Li, Ying; Zhang, Jiwei; Huang, Xirong; Wang, Tianhong

2014-03-28

A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, using genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O2 reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Functionalization of surfactant wrapped graphenenanosheets with alkylazides for enhanced dispersibility

NASA Astrophysics Data System (ADS)

Vadukumpully, Sajini; Gupta, Jhinuk; Zhang, Yongping; Xu, Guo Qin; Valiyaveettil, Suresh

2011-01-01

A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials.A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials. Electronic Supplementary Information (ESI) available: Synthesis and characterization details of dodecylazide, hexylazide, 11-azidoundecanol (AUO), micrographs (SEM and TEM images) of the various azide functionalized samples and the statistical analysis of the graphene thickness. See 10.1039/c0nr00547a.

Direct visualization of quasi-ordered oxygen chain structures on Au(110)-(1 × 2)

NASA Astrophysics Data System (ADS)

Hiebel, F.; Montemore, M. M.; Kaxiras, E.; Friend, C. M.

2016-08-01

The Au(110) surface offers unique advantages for atomically-resolved model studies of catalytic oxidation processes on gold. We investigate the adsorption of oxygen on Au(110) using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) methods. We identify the typical (empty-states) STM contrast resulting from adsorbed oxygen as atomic-sized dark features of electronic origin. DFT-based image simulations confirm that chemisorbed oxygen is generally detected indirectly, from the binding-induced electronic structure modification of gold. STM images show that adsorption occurs without affecting the general structure of the pristine Au(110) missing-row reconstruction. The tendency to form one-dimensional structures is observed already at low coverage (< 0.05 ML), with oxygen adsorbing on alternate sides of the reconstruction ridges. Consistently, calculations yield preferred adsorption on the (111) facets of the reconstruction, on a 3-fold coordination site, with increased stability when adsorbed in chains. Gold atoms with two oxygen neighbors exhibit enhanced electronic hybridization with the O states. Finally, the species observed are reactive to CO oxidation at 200 K and desorption of CO2 leaves a clean and ordered gold surface.

Room temperature deposition of gold onto the diffuse and sharp diffraction spot Si(111)-( 3 × 3) R30° Au surfaces

NASA Astrophysics Data System (ADS)

Plass, Richard; Marks, Laurence D.

1996-06-01

Room temperature gold depositions onto Si(111)-( 3 × 3) R30° Au surfaces with diffuse and sharp diffraction spots [Surf. Sci. 242 (1991) 73] (diffuse and sharp 3 × 3 Au hereafter) under UHV conditions has been monitored using transmission electron diffraction (TED). Both systems display an increase in surface structure diffraction spot intensities up to the completion of 1.0 monolayer (ML) after which the surface beams display an exponential decrease in intensity with coverage. The exponential decay rate decreases after roughly 1.33 ML. These results can be attributed to gold initially diffusing to and filling 3 × 3 Au gold trimer sites in vacancy type surface domain walls [Surf. Sci. 342 (1995) 233], then filling one of three possible sites on the 3 × 3 Au structure with essentially no surface diffusion, disrupting nearby gold trimers. Gold deposition onto the diffuse type structure caused the formation and expansion of satellite arcs around the strongest 3 × 3 beams similar to those seen by others [Surf. Sci. 242 (1991) 73; Jpn. J. Appl. Phys. 16 (1977) 891; J. Vac. Sci. Technol. A 10 (1992) 3486] at elevated temperatures while the sharp structure displayed only a modest shoulder formation near the strongest 3 × 3 beams.

Antifungal activity of gold nanoparticles prepared by solvothermal method

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

Ahmad, Tokeer, E-mail: tahmad3@jmi.ac.in; Wani, Irshad A.; Lone, Irfan H.

2013-01-15

Graphical abstract: Gold nanoparticles (7 and 15 nm) of very high surface area (329 and 269 m{sup 2}/g) have been successfully synthesized through solvothermal method by using tin chloride and sodium borohydride as reducing agents. As-prepared gold nanoparticles shows very excellent antifungal activity against Candida isolates and activity increases with decrease in the particle size. Display Omitted Highlights: ► Effect of reducing agents on the morphology of gold nanoparticles. ► Highly uniform and monodisperse gold nanoparticles (7 nm). ► Highest surface area of gold nanoparticles (329 m{sup 2/}g). ► Excellent antifungal activity of gold nanoparticles against Candida strains. -- Abstract:more » Gold nanoparticles have been successfully synthesized by solvothermal method using SnCl{sub 2} and NaBH{sub 4} as reducing agents. X-ray diffraction studies show highly crystalline and monophasic nature of the gold nanoparticles with face centred cubic structure. The transmission electron microscopic studies show the formation of nearly spherical gold nanoparticles of average size of 15 nm using SnCl{sub 2}, however, NaBH{sub 4} produced highly uniform, monodispersed and spherical gold nanoparticles of average grain size of 7 nm. A high surface area of 329 m{sup 2}/g for 7 nm and 269 m{sup 2}/g for 15 nm gold nanoparticles was observed. UV–vis studies assert the excitations over the visible region due to transverse and longitudinal surface plasmon modes. The gold nanoparticles exhibit excellent size dependant antifungal activity and greater biocidal action against Candida isolates for 7 nm sized gold nanoparticles restricting the transmembrane H{sup +} efflux of the Candida species than 15 nm sized gold nanoparticles.« less

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy†

PubMed Central

Tan, Yih Horng; Schallom, John R.; Ganesh, N. Vijaya; Fujikawa, Kohki; Demchenko, Alexei V.

2011-01-01

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable. PMID:21750834

Plasmonic properties of gold nanoparticles covered by silicon suboxide thin film

NASA Astrophysics Data System (ADS)

Baranov, Evgeniy; Zamchiy, Alexandr; Safonov, Aleksey; Starinskiy, Sergey; Khmel, Sergey

2017-10-01

The optical properties of nanocomposite material consisting of gold nanoparticles without/with silicon suboxide thin film were obtained. The gold film was deposited by thermal vacuum evaporation and then it was annealed in a vacuum chamber to form gold nanoparticles. The silicon suboxide thin films were deposited by the gas-jet electron beam plasma chemical vapor deposition method. The intensity of the localized surface plasmon resonance increased and the plasmon maximum peak shifted from 520 nm to 537 nm.

An ultrafast nanotip electron gun triggered by grating-coupled surface plasmons

NASA Astrophysics Data System (ADS)

Schröder, Benjamin; Sivis, Murat; Bormann, Reiner; Schäfer, Sascha; Ropers, Claus

2015-12-01

We demonstrate multiphoton photoelectron emission from gold nanotips induced by nanofocusing surface plasmons, resonantly excited on the tip shaft by a grating coupler. The tip is integrated into an electron gun assembly, which facilitates control over the spatial emission sites and allows us to disentangle direct grating emission from plasmon-triggered apex emission. The nanoscale source size of this electron gun concept enables highly coherent electron pulses with applications in ultrafast electron imaging and diffraction.

An ultrafast nanotip electron gun triggered by grating-coupled surface plasmons

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

Schröder, Benjamin; Sivis, Murat; Bormann, Reiner

We demonstrate multiphoton photoelectron emission from gold nanotips induced by nanofocusing surface plasmons, resonantly excited on the tip shaft by a grating coupler. The tip is integrated into an electron gun assembly, which facilitates control over the spatial emission sites and allows us to disentangle direct grating emission from plasmon-triggered apex emission. The nanoscale source size of this electron gun concept enables highly coherent electron pulses with applications in ultrafast electron imaging and diffraction.

High performance membrane-electrode assembly based on a surface-modified membrane

NASA Astrophysics Data System (ADS)

Han, Sangil; Lee, Jang Woo; Kwak, Chan; Chai, Geun Seok; Son, In Hyuk; Jang, Moon Yup; An, Sung Guk; Cho, Sung Yong; Kim, Jun Young; Kim, Hyung Wook; Serov, Alexey Alexandrovych; Yoo, Youngtai; Nam, Kie Hyun

A surface-modified membrane is prepared using a sputtering technique that deposits gold directly on a Nafion ® 115 membrane surface that is roughened with silicon carbide paper. The surface-modified membranes are characterized by means of a scanning electron microscope (SEM), differential scanning calorimetry (DSC), and water contact-angle analysis. A single direct methanol fuel cell (DMFC) with a surface-modified membrane exhibits enhanced performance (160 mW cm -2), while a bare Nafion ® 115 cell yields 113 mW cm -2 at 0.4 V and an operating temperature of 70 °C. From FE-SEM images and CO ad stripping voltammograms, it is also found that the gold layer is composed of clusters of porous nodule-like particles, which indicates that an anode with nodule-like gold leads to the preferential oxidation of carbon monoxide. These results suggest that the topology of gold in the interfacial area and its electrocatalytic nature may be the critical factors that affect DMFC performance.

Gold-implanted shallow conducting layers in polymethylmethacrylate

NASA Astrophysics Data System (ADS)

Teixeira, F. S.; Salvadori, M. C.; Cattani, M.; Brown, I. G.

2009-03-01

PMMA (polymethylmethacrylate) was ion implanted with gold at very low energy and over a range of different doses using a filtered cathodic arc metal plasma system. A nanometer scale conducting layer was formed, fully buried below the polymer surface at low implantation dose, and evolving to include a gold surface layer as the dose was increased. Depth profiles of the implanted material were calculated using the Dynamic TRIM computer simulation program. The electrical conductivity of the gold-implanted PMMA was measured in situ as a function of dose. Samples formed at a number of different doses were subsequently characterized by Rutherford backscattering spectrometry, and test patterns were formed on the polymer by electron beam lithography. Lithographic patterns were imaged by atomic force microscopy and demonstrated that the contrast properties of the lithography were well maintained in the surface-modified PMMA.

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.

Nano-scaling law: geometric foundation of thiolated gold nanomolecules.

PubMed

Dass, Amala

2012-04-07

Thiolated gold nanomolecules show a power correlation between the number of gold atoms and the thiolate ligands with a 2/3 scaling similar to Platonic and Archimedean solids. Nanomolecule stability is influenced by a universal geometric factor that is foundational to its stability through the Euclidean surface rule, in addition to the electronic shell closing factor and staple motif requirements. This journal is © The Royal Society of Chemistry 2012

Substrate decomposition in galvanic displacement reaction: Contrast between gold and silver nanoparticle formation

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

Ghosh, Tapas; Satpati, Biswarup, E-mail: biswarup.satpati@saha.ac.in; Kabiraj, D.

We have investigated substrate decomposition during formation of silver and gold nanoparticles in galvanic displacement reaction on germanium surfaces. Silver and gold nanoparticles were synthesized by electroless deposition on sputter coated germanium thin film (∼ 200 nm) grown initially on silicon substrate. The nanoparticles formation and the substrate corrosion were studied using scanning transmission electron microscopy (STEM) and the energy dispersive X-ray (EDX) spectroscopy.

Photocurrent generation by direct electron transfer using photosynthetic reaction centres

NASA Astrophysics Data System (ADS)

Mahmoudzadeh, A.; Saer, R.; Jun, D.; Mirvakili, S. M.; Takshi, A.; Iranpour, B.; Ouellet, E.; Lagally, E. T.; Madden, J. D. W.; Beatty, J. T.

2011-09-01

Photosynthetic reaction centres (RCs) convert light into separated charges with nearly perfect quantum efficiency, and have been used to generate photocurrent. Previous work has shown that electron tunnelling rates between redox centres in proteins depend exponentially on the tunnelling distance. In this work the RC from Rhodobacter sphaeroides was genetically modified with the aim of achieving the shortest tunnelling distances yet demonstrated between the RC's electron-accepting P site and underlying graphite and gold electrodes, and between the electron donor Q site and graphite electrodes. Opposite charges are carried to counter electrodes using mobile mediators, as in dye-sensitised solar cells. Native RCs are bound to graphite surfaces through N-(1-pyrene)iodoacetamide. Although the linker's length is only 4 Å, the electron transfer pathway between the Q electron donor site on the RC and the electrode surface is still too large for current to be significant. A mutant version with the electron acceptor P side close to the graphite surface produced currents of 15 nA cm-2 upon illumination. Direct binding of RCs to a gold surface is shown, resulting in currents of 5 nA cm-2. In both cases the current was unaffected by mediator concentration but increased with illumination, suggesting that direct electron transfer was achieved. The engineering of an RC to achieve direct electron transfer will help with long term efforts to demonstrate RC-based photovoltaic devices.

Gold core@silver semishell Janus nanoparticles prepared by interfacial etching.

PubMed

Chen, Limei; Deming, Christopher P; Peng, Yi; Hu, Peiguang; Stofan, Jake; Chen, Shaowei

2016-08-14

Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface.

Silk fibroin/gold nanocrystals: a new example of biopolymer-based nanocomposites

NASA Astrophysics Data System (ADS)

Noinville, S.; Garnier, A.; Courty, A.

2017-05-01

The dispersion of nanoparticles in ordered polymer nanostructures can provide control over particle location and orientation, and pave the way for tailored nanomaterials that have enhanced mechanical, electrical, or optical properties. Here we used silk fibroin, a natural biopolymer, to embed gold nanocrystals (NCs), so as to obtain well-ordered structures such as nanowires and self-assembled triangular nanocomposites. Monodisperse gold NCs synthesized in organic media are mixed to silk fibroin and the obtained nanocomposites are characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and Infrared spectroscopy. The optical properties study of gold NCs and silk-gold nanocomposites shows that the Surface Plasmon band is blue shifted compared to gold NCs. The size and shape of NCs gold superlattices can be well controlled by the presence of silk fibroin giving nanowires and also self-assembled triangular nanocomposites as characterized by TEM, FE-SEM and AFM. The strong interaction between gold NCs and silk fibroin is also revealed by the conformation change of silk protein in presence of gold NCs, as shown by FTIR analysis. The formation of such ordered nanocomposites (gold NCs/silk fibroin) will provide new nanoplasmonic devices.

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.

Damage induced to DNA by low-energy (0-30 eV) electrons under vacuum and atmospheric conditions.

PubMed

Brun, Emilie; Cloutier, Pierre; Sicard-Roselli, Cécile; Fromm, Michel; Sanche, Léon

2009-07-23

In this study, we show that it is possible to obtain data on DNA damage induced by low-energy (0-30 eV) electrons under atmospheric conditions. Five monolayer films of plasmid DNA (3197 base pairs) deposited on glass and gold substrates are irradiated with 1.5 keV X-rays in ultrahigh vacuum and under atmospheric conditions. The total damage is analyzed by agarose gel electrophoresis. The damage produced on the glass substrate is attributed to energy absorption from X-rays, whereas that produced on the gold substrate arises from energy absorption from both the X-ray beam and secondary electrons emitted from the gold surface. By analysis of the energy of these secondary electrons, 96% are found to have energies below 30 eV with a distribution peaking at 1.4 eV. The differences in damage yields recorded with the gold and glass substrates is therefore essentially attributed to the interaction of low-energy electrons with DNA under vacuum and hydrated conditions. From these results, the G values for low-energy electrons are determined to be four and six strand breaks per 100 eV, respectively.

Adsorption of the astatine species on a gold surface: A relativistic density functional theory study

NASA Astrophysics Data System (ADS)

Demidov, Yuriy; Zaitsevskii, Andréi

2018-01-01

We report first-principle based studies of the adsorption interaction of astatine species on a gold surface. These studies are aimed primarily at the support and interpretation of gas chromatographic experiments with superheavy elements, tennessine (Ts, Z = 117), a heavier homologue of At, and possibly its pseudo-homologue nihonium (Nh, Z = 113). We use gold clusters with up to 69 atoms to simulate the adsorption sites and estimate the desorption energies of At & AtOH from a stable gold (1 1 1) surface. To describe the electronic structure of At -Aun and AtOH -Aun complexes, we combine accurate shape-consistent relativistic pseudopotentials and non-collinear two-component relativistic density functional theory. The predicted desorption energies of At and AtOH on gold are 130 ± 10 kJ/mol and 90 ± 10 kJ/mol, respectively. These results confirm the validity of the estimates derived from chromatographic data (147 ± 15 kJ/mol for At, and 100-10+20 kJ/mol for AtOH).

Monitoring adsorption of gold nanoparticles on gold nanodisk array using dark-field hyperspectral microscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Zhao, Fusheng; Zenasni, Oussama; Li, Jingting; Shih, Wei-Chuan

2017-02-01

Localized surface plasmon resonance (LSPR) arises from the interaction of light with noble metal nanoparticles, which induces a collective oscillation in the free electrons. The size and shape of the metallic nanostructure significantly impact LSPR frequency and strength. Nanoplasmonic sensor has become a recent research focus due to its significant signal enhancement and robust signal transduction measured by extinction spectroscopy, fluorescence, Raman scattering, and absorption spectroscopy. Dark-field microscopy, in contrast, reports the scattered photons after light-matter interactions. In this case, the nanoparticles can be understood as dipole radiators whose free electrons oscillate in concert. Coupled with spectroscopy, this platform allows the collection of plasmonically scattered spectra from gold nanoparticles. Plasmonic coupling between electron-beam lithography patterned gold nanodisks (AuND) and colloidal gold nanoparticles (AuNP) can change the plasmonic resonance of the original entities, and can be effectively studied by dark-field hyperspectral microscopy. Typically, a pronounced redshift can be observed when plasmonic coupling occurs. When these nano-entities are functionalized with interactive surface moieties, biochemistry and molecular processes can be studied. In this paper, we will present the capability of assessing the process of immobilizing streptavidin-functionalized AuNPs on an array of biotin-terminated AuNDs. By monitoring changes in the LSPR band of AuNDs, we are able to evaluate similar processes in other molecular systems. In addition, plasmon coupling induced scattering intensity variations can be measured by an electron-multiplied charge-coupled device camera for rapid in situ monitoring. This method can potentially be useful in studying dynamic biophysical and biochemical processes in situ.

Surface-plasmon-polariton hybridized cavity modes in submicrometer slits in a thin Au film

NASA Astrophysics Data System (ADS)

Walther, R.; Fritz, S.; Müller, E.; Schneider, R.; Maniv, T.; Cohen, H.; Matyssek, C.; Busch, K.; Gerthsen, D.

2016-06-01

The excitation of cavity standing waves in double-slit structures in thin gold films, with slit lengths between 400 and 2560 nm, was probed with a strongly focused electron beam in a transmission electron microscope. The energies and wavelengths of cavity modes up to the 11 th mode order were measured with electron energy loss spectroscopy to derive the corresponding dispersion relation. For all orders, a significant redshift of mode energies accompanied by a wavelength elongation relative to the expected resonator energies and wavelengths is observed. The resultant dispersion relation is found to closely follow the well-known dispersion law of surface-plasmon polaritons (SPPs) propagating on a gold/air interface, thus providing direct evidence for the hybridized nature of the detected cavity modes with SPPs.

Theoretical predictions for hot-carrier generation from surface plasmon decay

PubMed Central

Sundararaman, Ravishankar; Narang, Prineha; Jermyn, Adam S.; Goddard III, William A.; Atwater, Harry A.

2014-01-01

Decay of surface plasmons to hot carriers finds a wide variety of applications in energy conversion, photocatalysis and photodetection. However, a detailed theoretical description of plasmonic hot-carrier generation in real materials has remained incomplete. Here we report predictions for the prompt distributions of excited ‘hot’ electrons and holes generated by plasmon decay, before inelastic relaxation, using a quantized plasmon model with detailed electronic structure. We find that carrier energy distributions are sensitive to the electronic band structure of the metal: gold and copper produce holes hotter than electrons by 1–2 eV, while silver and aluminium distribute energies more equitably between electrons and holes. Momentum-direction distributions for hot carriers are anisotropic, dominated by the plasmon polarization for aluminium and by the crystal orientation for noble metals. We show that in thin metallic films intraband transitions can alter the carrier distributions, producing hotter electrons in gold, but interband transitions remain dominant. PMID:25511713

Electroplating Gold-Silver Alloys for Spherical Capsules for NIF Double-Shell Targets

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

Bhandarkar, N.; Horwood, C.; Bunn, T.

For Inertial Confinement Fusion (ICF) implosions, a design based on gradients of high and mid Z materials could potentially be more robust than single element capsule systems. To that end, gold and silver alloys were electroplated on 2.0 mm diameter surrogate brass spheres using a new flow–based pulsed plating method specifically designed to minimize surface roughness without reducing plating rates. The coatings were analyzed by scanning electron microscope (SEM) and white light interferometry for surface topography, and by energy dispersive x-ray spectroscopy (EDX) to determine near-surface gold and silver compositions. The alloy range attainable was 15 to 85 weight percentmore » gold using 1:1 and 1:3 silver to gold ratio plating baths at applied potentials of -0.7 volts to -1.8 volts. This range was bounded by the open circuit potential of the system and hydrogen evolution, and in theory could be extended by using ionic liquids or aprotic solutions. Preliminary gradient trials proved constant composition alloy data could be translated to smooth gradient plating, albeit at higher gold compositions.« less

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.

A novel green and template free approach for the synthesis of gold nanorice and its utilization as a catalyst for the degradation of hazardous dye

NASA Astrophysics Data System (ADS)

Sinha, Tanur; Ahmaruzzaman, M.

2015-05-01

Herein, we describe a simple, green and template free method for the production of rice shaped gold nanostructures using an aqueous extract of the egg shells of Anas platyrhynchos. The synthesized nanoparticles were characterized by UV-visible, transmission electron microscopy (TEM), selected area electron diffraction pattern (SAED) and FT-IR studies. The UV-visible spectrum of the synthesized gold nanostructures showed a transverse mode surface plasmon resonance peaks (SPR) at around 540 nm and a longitudinal mode at 880 nm. The TEM and SAED pattern confirmed the morphology, size and crystallographic structure of the synthesized gold nanorice. The synthesized gold nanorice was utilized for the removal of a toxic Eosin Y dye by photodegradation. It was observed that the dye was degraded completely within 1 h and the percentage efficiency was found to be 96.1%.

Ultrathin free-standing close-packed gold nanoparticle films: Conductivity and Raman scattering enhancement

NASA Astrophysics Data System (ADS)

Yu, Qing; Huang, Hongwen; Peng, Xinsheng; Ye, Zhizhen

2011-09-01

A simple filtration technique was developed to prepare large scale free-standing close-packed gold nanoparticle ultrathin films using metal hydroxide nanostrands as both barrier layer and sacrificial layer. As thin as 70 nm, centimeter scale robust free-standing gold nanoparticle thin film was obtained. The thickness of the films could be easily tuned by the filtration volumes. The electronic conductivities of these films varied with the size of the gold nanoparticles, post-treatment temperature, and thickness, respectively. The conductivity of the film prepared from 20 nm gold nanoparticles is higher than that of the film prepared from 40 nm gold nanoparticle by filtering the same filtration volume of their solution, respectively. Their conductivities are comparable to that of the 220 nm thick ITO film. Furthermore, these films demonstrated an average surface Raman scattering enhancement up to 6.59 × 105 for Rhodamine 6 G molecules on the film prepared from 40 nm gold nanoparticles. Due to a lot of nano interspaces generated from the close-packed structures, two abnormal enhancements and relative stronger intensities of the asymmetrical vibrations at 1534 and 1594 cm-1 of R6G were observed, respectively. These robust free-standing gold nanoparticle films could be easily transferred onto various solid substrates and hold the potential application for electrodes and surface enhanced Raman detectors. This method is applicable for preparation of other nanoparticle free-standing thin films.A simple filtration technique was developed to prepare large scale free-standing close-packed gold nanoparticle ultrathin films using metal hydroxide nanostrands as both barrier layer and sacrificial layer. As thin as 70 nm, centimeter scale robust free-standing gold nanoparticle thin film was obtained. The thickness of the films could be easily tuned by the filtration volumes. The electronic conductivities of these films varied with the size of the gold nanoparticles, post-treatment temperature, and thickness, respectively. The conductivity of the film prepared from 20 nm gold nanoparticles is higher than that of the film prepared from 40 nm gold nanoparticle by filtering the same filtration volume of their solution, respectively. Their conductivities are comparable to that of the 220 nm thick ITO film. Furthermore, these films demonstrated an average surface Raman scattering enhancement up to 6.59 × 105 for Rhodamine 6 G molecules on the film prepared from 40 nm gold nanoparticles. Due to a lot of nano interspaces generated from the close-packed structures, two abnormal enhancements and relative stronger intensities of the asymmetrical vibrations at 1534 and 1594 cm-1 of R6G were observed, respectively. These robust free-standing gold nanoparticle films could be easily transferred onto various solid substrates and hold the potential application for electrodes and surface enhanced Raman detectors. This method is applicable for preparation of other nanoparticle free-standing thin films. Electronic supplementary information (ESI) available: Figure S1, the SEM images and photograph of the films prepared from 10 ml, 20 nm gold nanoparticles. Scheme S1, the vibrations of 1534 and 1594 cm-1 of R6G. See DOI: 10.1039/c1nr10578g

Tuning Surface Chemistry of Polyetheretherketone by Gold Coating and Plasma Treatment

NASA Astrophysics Data System (ADS)

Novotná, Zdeňka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdeňka; Hubáček, Tomáš; Borovec, Jakub; Švorčík, Václav

2017-06-01

Polyetheretherketone (PEEK) has good chemical and biomechanical properties that are excellent for biomedical applications. However, PEEK exhibits hydrophobic and other surface characteristics which cause limited cell adhesion. We have investigated the potential of Ar plasma treatment for the formation of a nanostructured PEEK surface in order to enhance cell adhesion. The specific aim of this study was to reveal the effect of the interface of plasma-treated and gold-coated PEEK matrices on adhesion and spreading of mouse embryonic fibroblasts. The surface characteristics (polarity, surface chemistry, and structure) before and after treatment were evaluated by various experimental techniques (gravimetry, goniometry, X-ray photoelectron spectroscopy (XPS), and electrokinetic analysis). Further, atomic force microscopy (AFM) was employed to examine PEEK surface morphology and roughness. The biological response of cells towards nanostructured PEEK was evaluated in terms of cell adhesion, spreading, and proliferation. Detailed cell morphology was evaluated by scanning electron microscopy (SEM). Compared to plasma treatment, gold coating improved PEEK wettability. The XPS method showed a decrease in the carbon concentration with increasing time of plasma treatment. Cell adhesion determined on the interface between plasma-treated and gold-coated PEEK matrices was directly proportional to the thickness of a gold layer on a sample. Our results suggest that plasma treatment in a combination with gold coating could be used in biomedical applications requiring enhanced cell adhesion.

Seeds mediated synthesis of giant gold particles on the glass surface

NASA Astrophysics Data System (ADS)

Vasko, A. A.; Borodinova, T. I.; Marchenko, O. A.; Snegir, S. V.

2018-03-01

Herein, we present the protocols of synthesis of two types of gold particles which are in the great interest for the purpose of molecular electronics. The first type is the flat prisms with a triangular/hexagonal shape and a lateral size up to 80 µm. They were synthesized directly on a glass surface pretreated with (3-aminopropyl)-triethoxysilane molecules. The second type of particles was synthesized with using gold seeds with diameter of 18 nm. These seeds were deposited on a glass surface coated with APTES. The resulted three-dimensional structures with a form close to spherical increase in size up to 0.5-0.08 µm. Moreover, these particles grew up separately and did not merge during 48 h of synthesis.

Excited-state dynamics of size-dependent colloidal TiO2-Au nanocomposites

NASA Astrophysics Data System (ADS)

Karam, Tony E.; Khoury, Rami A.; Haber, Louis H.

2016-03-01

The ultrafast excited-state dynamics of size-dependent TiO2-Au nanocomposites synthesized by reducing gold nanoclusters to the surface of colloidal TiO2 nanoparticles are studied using pump-probe transient absorption spectroscopy with 400 nm excitation pulses. The results show that the relaxation processes of the plasmon depletion band, which are described by electron-phonon and phonon-phonon scattering lifetimes, are independent of the gold nanocluster shell size surrounding the TiO2 nanoparticle core. The dynamics corresponding to interfacial electron transfer between the gold nanoclusters and the TiO2 bandgap are observed to spectrally overlap with the gold interband transition signal, and the electron transfer lifetimes are shown to significantly decrease as the nanocluster shell size increases. Additionally, size-dependent periodic oscillations are observed and are attributed to acoustic phonons of a porous shell composed of aggregated gold nanoclusters around the TiO2 core, with frequencies that decrease and damping times that remain constant as the nanocluster shell size increases. These results are important for the development of improved catalytic nanomaterial applications.

Increased cellular uptake of peptide-modified PEGylated gold nanoparticles.

PubMed

He, Bo; Yang, Dan; Qin, Mengmeng; Zhang, Yuan; He, Bing; Dai, Wenbing; Wang, Xueqing; Zhang, Qiang; Zhang, Hua; Yin, Changcheng

2017-12-09

Gold nanoparticles are promising drug delivery vehicles for nucleic acids, small molecules, and proteins, allowing various modifications on the particle surface. However, the instability and low bioavailability of gold nanoparticles compromise their clinical application. Here, we functionalized gold nanoparticles with CPP fragments (CALNNPFVYLI, CALRRRRRRRR) through sulfhydryl PEG to increase their stability and bioavailability. The resulting gold nanoparticles were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), UV-visible spectrometry and X-ray photoelectron spectroscopy (XPS), and the stability in biological solutions was evaluated. Comparing to PEGylated gold nanoparticles, CPP (CALNNPFVYLI, CALRRRRRRRR)-modified gold nanoparticles showed 46 folds increase in cellular uptake in A549 and B16 cell lines, as evidenced by the inductively coupled plasma atomic emission spectroscopy (ICP-AES). The interactions between gold nanoparticles and liposomes indicated CPP-modified gold nanoparticles bind to cell membrane more effectively than PEGylated gold nanoparticles. Surface plasmon resonance (SPR) was used to measure interactions between nanoparticles and the membrane. TEM and uptake inhibitor experiments indicated that the cellular entry of gold nanoparticles was mediated by clathrin and macropinocytosis. Other energy independent endocytosis pathways were also identified. Our work revealed a new strategy to modify gold nanoparticles with CPP and illustrated the cellular uptake pathway of CPP-modified gold nanoparticles. Copyright © 2017 Elsevier Inc. All rights reserved.

Ultrafast spatiotemporal relaxation dynamics of excited electrons in a metal nanostructure detected by femtosecond-SNOM.

PubMed

Li, Zhi; Yue, Song; Chen, Jianjun; Gong, Qihuang

2010-06-21

Ultrahigh spatiotemporal resolved pump-probe signal near a gold nano-slit is detected by femtosecond-SNOM. By employing two-color pump-probe configuration and probing at the interband transition wavelength of the gold, signal contributed by surface plasmon polariton is avoided and spatiotemporal evolvement of excited electrons is successfully observed. From the contrast decaying of the periodical distribution of the pump-probe signal, ultrafast diffusion of excited electrons with a time scale of a few hundred femtoseconds is clearly identified. For comparison, such phenomenon cannot be observed by the one-color pump-probe configuration.

Short range orders of an adsorbed layer: gold on the Si(111)7 × 7 surface

NASA Astrophysics Data System (ADS)

Takahashi, S.; Tanishiro, Y.; Takayanagi, K.

1991-02-01

Ordered phases of 5 × 2, 3× 3 and 6 × 6 structures formed by gold deposition on a Si(11)7 × 7 surface were observed by transmission electron diffraction (TED). Short-range orders of the 3× 3 phase of low and high coverages are analyzed from diffuse TED intensities. Phasons which displace the adsorption site by a at every translation of 6 a are found to be introduced in the 3× 3 structure of the saturation coverage. The phasons, which create 2 a correlation between gold clusters, prohibit formation of a completely ordered 3× 3 phase.

Electrophoretic separation of gold nanoparticles according to bifunctional molecules-induced charge and size.

PubMed

Kim, Jong-Yeob; Kim, Hyung-Bae; Jang, Du-Jeon

2013-03-01

Gold nanospheres modified with bifunctional molecules have been separated and characterized by using agarose gel electrophoresis as well as optical spectroscopy and electron microscopy. The electrophoretic mobility of a gold nanosphere capped with 11-mercaptoundecanoic acid (MUA) has been found to depend on the number of MUA molecules per gold nanosphere, indicating that it increases with the surface charge of the nanoparticle. The extinction spectrum of gold nanospheres capped with MUA at an MUA molecules per gold nanosphere value of 1000 and connected via 1,6-hexanedithiol (HDT) decreases by 33% in magnitude and shifts to the red as largely as 22 nm with the increase of the molar ratio of HDT to MUA (R(HM)). Gold nanospheres capped with MUA and connected via HDT have been separated successfully using gel electrophoresis and characterized by measuring reflectance spectra of discrete electrophoretic bands directly in the gel and by monitoring transmission electron microscope images of gold nanoparticles collected from the discrete bands. Electrophoretic mobility has been found to decrease substantially with the increment of HDT to MUA, indicating that the size of aggregated gold nanoparticles increases with the concentration of HDT. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size tunable gold nanorods evenly distributed in the channels of mesoporous silica.

PubMed

Li, Zhi; Kübel, Christian; Pârvulescu, Vasile I; Richards, Ryan

2008-06-01

Uniformly distributed gold nanorods in mesoporous silica were synthesized in situ by performing a seed-mediated growth process in the channels of SBA-15 which functions as a hard-template to confine the diameter of gold nanorods. By changing the amount of gold precursor, gold nanorods were prepared with a fixed diameter (6-7 nm) and tunable aspect ratios from 3 to 30. Transmission electron microscope and electron tomography were utilized to visualize the gold nanorods supported on one piece of SBA-15 segment and showed a fairly uniform 3-dimensional distribution of gold nanorods within the SBA-15 channels. The longitudinal plasmon resonances of the gold nanorods/SBA-15 composites analyzed by diffuse reflectance UV-vis spectra were found to be tunable depending on the length of gold nanorods. No significant decrease in surface area and/or pore size of the composite was found after growth, indicating the growth process did not disrupt the open mesoporous structure of SBA-15. The combination of the tunable size of the nanorods and their 3-dimensional distribution within the open supporting matrix makes the gold nanorods/SBA-15 composites interesting candidates to systematically study the influence of the aspect ratio of gold nanorods on their properties and potential applications, i.e., catalyst, optical polarizer, and ultrasensitive medical imaging technique.

Gold leaf counter electrodes for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Shimada, Kazuhiro; Toyoda, Takeshi

2018-03-01

In this study, a gold leaf 100 nm thin film is used as the counter electrode in dye-sensitized solar cells. The traditional method of hammering gold foil to obtain a thin gold leaf, which requires only small amounts of gold, was employed. The gold leaf was then attached to the substrate using an adhesive to produce the gold electrode. The proposed approach for fabricating counter electrodes is demonstrated to be facile and cost-effective, as opposed to existing techniques. Compared with electrodes prepared with gold foil and sputtered gold, the gold leaf counter electrode demonstrates higher catalytic activity with a cobalt-complex electrolyte and higher cell efficiency. The origin of the improved performance was investigated by surface morphology examination (scanning electron microscopy), various electrochemical analyses (cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy), and crystalline analysis (X-ray diffractometry).

Quantitative Transmission Electron Microscopy of Nanoparticles and Thin-Film Formation in Electroless Metallization of Polymeric Surfaces

NASA Astrophysics Data System (ADS)

Dutta, Aniruddha; Heinrich, Helge; Kuebler, Stephen; Grabill, Chris; Bhattacharya, Aniket

2011-03-01

Gold nanoparticles(Au-NPs) act as nucleation sites for electroless deposition of silver on functionalized SU8 polymeric surfaces. Here we report the nanoscale morphology of Au and Ag nanoparticles as studied by Transmission Electron Microscopy (TEM). Scanning TEM with a high-angle annular dark-field detector is used to obtain atomic number contrast. From the intensity-calibrated plan-view scanning TEM images we determine the mean thickness and the volume distribution of the Au-NPs on the surface of the functionalized polymer. We also report the height and the radius distribution of the gold nanoparticles obtained from STEM images taking into consideration the experimental errors. The cross sectional TEM images yield the density and the average distance of the Au and Ag nanoparticles on the surface of the polymer. Supported by grant NSF, Chemistry Division.

Highly conductive and pure gold nanostructures grown by electron beam induced deposition

PubMed Central

Shawrav, Mostafa M.; Taus, Philipp; Wanzenboeck, Heinz D.; Schinnerl, M.; Stöger-Pollach, M.; Schwarz, S.; Steiger-Thirsfeld, A.; Bertagnolli, Emmerich

2016-01-01

This work introduces an additive direct-write nanofabrication technique for producing extremely conductive gold nanostructures from a commercial metalorganic precursor. Gold content of 91 atomic % (at. %) was achieved by using water as an oxidative enhancer during direct-write deposition. A model was developed based on the deposition rate and the chemical composition, and it explains the surface processes that lead to the increases in gold purity and deposition yield. Co-injection of an oxidative enhancer enabled Focused Electron Beam Induced Deposition (FEBID)—a maskless, resistless deposition method for three dimensional (3D) nanostructures—to directly yield pure gold in a single process step, without post-deposition purification. Gold nanowires displayed resistivity down to 8.8 μΩ cm. This is the highest conductivity achieved so far from FEBID and it opens the possibility of applications in nanoelectronics, such as direct-write contacts to nanomaterials. The increased gold deposition yield and the ultralow carbon level will facilitate future applications such as the fabrication of 3D nanostructures in nanoplasmonics and biomolecule immobilization. PMID:27666531

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface.

PubMed

Sykes, Matthew E; Stewart, Jon W; Akselrod, Gleb M; Kong, Xiang-Tian; Wang, Zhiming; Gosztola, David J; Martinson, Alex B F; Rosenmann, Daniel; Mikkelsen, Maiken H; Govorov, Alexander O; Wiederrecht, Gary P

2017-10-17

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers, which we propose arise from anisotropic electron-electron scattering within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold, whereas the quantum process of hot electron generation takes place in both components. Our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.The creation of energetic electrons through plasmon excitation has implications in optical energy conversion and ultrafast nanophotonics. Here, the authors find evidence for three subpopulations of nonthermal carriers which arise from anisotropic electron-electron scattering near the Fermi surface.

Gold coated metal nanostructures grown by glancing angle deposition and pulsed electroplating

NASA Astrophysics Data System (ADS)

Grüner, Christoph; Reeck, Pascal; Jacobs, Paul-Philipp; Liedtke, Susann; Lotnyk, Andriy; Rauschenbach, Bernd

2018-05-01

Nickel based nanostructures are grown by glancing angle deposition (GLAD) on flat and pre-patterned substrates. These fabricated porous thin films were subsequently coated by pulsed electroplating with gold. The morphology and conformity of the gold coating were investigated by scanning electron microscopy and X-ray diffraction. Controlled growth of closed gold layers on the nanostructures could be achieved, while the open-pore structure of the nanosculptured thin films was preserved. Such gold coated nanostructures are a candidate for optical sensing and catalysis applications. The demonstrated method can be applied for numerous material combinations, allowing to provide GLAD thin films with new surface properties.

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

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

Lin, Yuyuan; Wu, Zili; Wen, Jianguo

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 nanorodmore » 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.« less

Auger measurements on T-027 samples exposed during the Skylab 2 mission. [indicating low rate of deposition on nickel and gold surfaces

NASA Technical Reports Server (NTRS)

Peters, P. N.

1974-01-01

Auger electron spectroscopy measurements performed on Skylab 2 indicate a low rate of deposition of permanent, continuous film contamination on nickel and gold surfaces positioned on the antisolar side of the spacecraft. These measurements and supportive evidence indicate that for the particular locations and orientations of these samples permanent films of less than 3 nm (30 A) thickness were deposited during an exposure of 40 hours at a temperature of approximately -32 C.

Effects of electron relaxation on multiple harmonic generation from metal surfaces with femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Karatzas, N. E.; Georges, A. T.

2006-11-01

Calculations are presented for the first four (odd and even) harmonics of an 800 nm laser from a gold surface, with pulse widths ranging from 100 down to 14 fs. For peak laser intensities above 1 GW/cm 2 the harmonics are enhanced because of a partial depletion of the initial electron states. At 10 11 W/cm 2 of peak laser intensity the calculated conversion efficiency for 2nd-harmonic generation is 3 × 10 -9, while for the 5th-harmonic it is 10 -10. The generated harmonic pulses are broadened and delayed relative to the laser pulse because of the finite relaxation times of the excited electronic states. The finite electron relaxation times cause also the broadening of the autocorrelations of the laser pulses obtained from surface harmonic generation by two time-delayed identical pulses. Comparison with recent experimental results shows that the response time of an autocorrelator using nonlinear optical processes in a gold surface is shorter than the electron relaxation times. This seems to indicate that for laser pulses shorter than ˜30 fs, the fast nonresonant channel for multiphoton excitation via continuum-continuum transitions in metals becomes important as the resonant channel becomes slow (relative to the laser pulse) and less efficient.

Hybrid framework with cobalt-chromium alloy and gold cylinder for implant superstructure: Bond strength and corrosion resistance.

PubMed

Yoshinari, Masao; Uzawa, Shinobu; Komiyama, Yataro

2016-10-01

The aim of this in vitro study was to evaluate tensile bond strengths and corrosion resistance of CoCr alloys joined with gold cylinder by a soldering system in comparison with the conventional cast-joining system. CoCr alloys joined with gold cylinder by a soldering system using a high-fusing gold solder (CoCr/Solder/Gold cylinder), gold alloy joined with gold cylinder by a cast joining system (Gold alloy/Gold cylinder) and CoCr castings were fabricated. The tensile bond strength and corrosion resistance in 0.9% NaCl solution (pH 7.4 and pH 2.3) were evaluated. Scanning electron microscopy (SEM) of the fractured surface and electron probe microanalysis (EPMA) of the joined interfaces were also performed. The tensile bond strengths of the CoCr/Solder/Gold cylinder specimens showed similar values as the Gold alloy/Gold cylinder specimens. SEM observation and EPMA analyses suggested firm bonding between the CoCr alloy and gold cylinder. The released elements from the CoCr/Solder/Gold cylinder specimens were similar to ones from CoCr castings. Results showed that superstructures made of CoCr alloys joined with the gold cylinder using a high-fusing gold solder had sufficient bond strength and high corrosion resistance. These hybrid frameworks with cobalt-chromium alloy and gold cylinder are promising prosthesis for implant superstructures with the low cost and favorable mechanical properties instead of conventional high-gold alloys. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Gum ghatti mediated, one pot green synthesis of optimized gold nanoparticles: Investigation of process-variables impact using Box-Behnken based statistical design.

PubMed

Alam, Md Sabir; Garg, Arun; Pottoo, Faheem Hyder; Saifullah, Mohammad Khalid; Tareq, Abu Izneid; Manzoor, Ovais; Mohsin, Mohd; Javed, Md Noushad

2017-11-01

Due to unique inherent catalytic characteristics of different size, shape and surface functionalized gold nanoparticles, their potential applications, are being explored in various fields such as drug delivery, biosensor, diagnosis and theranostics. However conventional process for synthesis of these metallic nanoparticles utilizes toxic reagents as reducing agents, additional capping agent for stability as well as surface functionalization for drug delivery purposes. Hence, in this work suitability of gum Ghatti for reducing, capping and surface functionalization during the synthesis of stable Gold nanoparticles were duly explored. Role and impact of key process variables i.e. volume of chloroauric acid solution, gum solution and temperature at their respective three different levels, as well as mechanism of formation of optimized gold nanoparticles were also investigated using Box- Behnken design. These novel synthesized optimized Gold nanoparticles were further characterized by UV spectrophotometer for its surface plasmon resonance (SPR) at around ∼530nm, dynamic light scattering (DLS) for its hydrodynamic size (112.5nm), PDI (0.222) and zeta potential (-21.3mV) while, transmission electron microscopy (TEM) further revealed surface geometry of these nanoparticles being spherical in shape. Copyright © 2017 Elsevier B.V. All rights reserved.

The structure and binding mode of citrate in the stabilization of gold nanoparticles

NASA Astrophysics Data System (ADS)

Al-Johani, Hind; Abou-Hamad, Edy; Jedidi, Abdesslem; Widdifield, Cory M.; Viger-Gravel, Jasmine; Sangaru, Shiv Shankar; Gajan, David; Anjum, Dalaver H.; Ould-Chikh, Samy; Hedhili, Mohamed Nejib; Gurinov, Andrei; Kelly, Michael J.; El Eter, Mohamad; Cavallo, Luigi; Emsley, Lyndon; Basset, Jean-Marie

2017-09-01

Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e- L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

Location on chitin in the cyst wall of Entamoeba invadens with colloidal gold tracers.

PubMed

Arroyo-Begovich, A; Cárabez-Trejo, A

1982-04-01

Chitin was located in the cyst wall of Entamoeba invadens with colloidal gold-linked wheat germ agglutinin. Cysts stained differentially from trophozoites when encysting cultures were treated with the gold tracer; cysts acquired a wine-red coloration while, in general trophozoites remained unstained. Observation of cells with the electron microscope revealed that the tracer particles were bound specifically to the walls of the surface of the cyst when cells were exposed in suspension, and to the cyst wall cross-section, when cells were exposed to the tracer in thin section, indicating that chitin fibers were distributed on the surface as well as throughout the matrix of the cyst wall.

Unimolecular Logic Gate with Classical Input by Single Gold Atoms.

PubMed

Skidin, Dmitry; Faizy, Omid; Krüger, Justus; Eisenhut, Frank; Jancarik, Andrej; Nguyen, Khanh-Hung; Cuniberti, Gianaurelio; Gourdon, Andre; Moresco, Francesca; Joachim, Christian

2018-02-27

By a combination of solution and on-surface chemistry, we synthesized an asymmetric starphene molecule with two long anthracenyl input branches and a short naphthyl output branch on the Au(111) surface. Starting from this molecule, we could demonstrate the working principle of a single molecule NAND logic gate by selectively contacting single gold atoms by atomic manipulation to the longer branches of the molecule. The logical input "1" ("0") is defined by the interaction (noninteraction) of a gold atom with one of the input branches. The output is measured by scanning tunneling spectroscopy following the shift in energy of the electronic tunneling resonances at the end of the short branch of the molecule.

Modeling the electrical resistance of gold film conductors on uniaxially stretched elastomeric substrates

NASA Astrophysics Data System (ADS)

Cao, Wenzhe; Görrn, Patrick; Wagner, Sigurd

2011-05-01

The electrical resistance of gold film conductors on polydimethyl siloxane substrates at stages of uniaxial stretching is measured and modeled. The surface area of a gold conductor is assumed constant during stretching so that the exposed substrate takes up all strain. Sheet resistances are calculated from frames of scanning electron micrographs by numerically solving for the electrical potentials of all pixels in a frame. These sheet resistances agree sufficiently well with values measured on the same conductors to give credence to the model of a stretchable network of gold links defined by microcracks.

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode.

PubMed

Yang, Haifeng; Liu, Yanli; Liu, Zhimin; Yang, Yu; Jiang, Jianhui; Zhang, Zongrang; Shen, Guoli; Yu, Ruqin

2005-02-24

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.

Ablation of gold irradiated by femtosecond laser pulse: Experiment and modeling

NASA Astrophysics Data System (ADS)

Ashitkov, S. I.; Komarov, P. S.; Zhakhovsky, V. V.; Petrov, Yu V.; Khokhlov, V. A.; Yurkevich, A. A.; Ilnitsky, D. K.; Inogamov, N. A.; Agranat, M. B.

2016-11-01

We report on the ablation phenomena in gold sample irradiated by femtosecond laser pulses of moderate intensity. Dynamics of optical constants and expansion of a heated surface layer was investigated in a range from picosecond up to subnanosecond using ultrafast interferometry. Also morphology of the ablation craters and value of an ablation threshold (for absorbed fluence) were measured. The experimental data are compared with simulations of mass flows obtained by two-temperature hydrodynamics and molecular dynamics methods. Simulation shows evolution of a thin surface layer pressurized by a laser pulse. Unloading of the pressurized layer proceeds together with electron-ion thermalization, melting, cavitation and spallation of a part of surface liquid layer. The experimental and simulation results on two-temperature physics and on a fracture, surface morphology and strength of liquid gold at a strain rate ∼ 109 s-1 are discussed.

Synthesis and characterization of core-shell gold nanoparticles with poly(vinyl pyrrolidone) from a new precursor salt

NASA Astrophysics Data System (ADS)

Behera, M.; Ram, S.

2013-02-01

In this article, we report a facile one-step chemical synthesis of gold (Au) nanoparticles (GNPs) from a new precursor salt i.e., gold hydroxide in the presence of poly(vinyl pyrrolidone) (PVP) polymer. The non-aqueous dispersion of GNPs was comprehensively characterized by UV-Visible, FTIR, zeta potential, and transmission electron microscope (TEM). A strong surface plasmon resonance band at 529 nm in the UV-Visible spectrum confirms the formation of GNPs in the Au colloid. The FTIR spectroscopic results showed that PVP molecules get chemisorbed onto the surface of GNP via O-atom of carbonyl group. A negative zeta potential of (-)16 mV reveals accumulation of nonbonding electrons of O-atom of carbonyl group of PVP molecules on the nanosurface of GNP. TEM images demonstrate a core-shell nanostructure with an Au-crystalline core covered by a thin amorphous PVP-shell. PVP-capped GNPs could be a potential candidate for bio-sensing, catalysis, and other applications.

Gold-Coated M13 Bacteriophage as a Template for Glucose Oxidase Biofuel Cells with Direct Electron Transfer.

PubMed

Blaik, Rita A; Lan, Esther; Huang, Yu; Dunn, Bruce

2016-01-26

Glucose oxidase-based biofuel cells are a promising source of alternative energy for small device applications, but still face the challenge of achieving robust electrical contact between the redox enzymes and the current collector. This paper reports on the design of an electrode consisting of glucose oxidase covalently attached to gold nanoparticles that are assembled onto a genetically engineered M13 bacteriophage using EDC-NHS chemistry. The engineered phage is modified at the pIII protein to attach onto a gold substrate and serves as a high-surface-area template. The resulting "nanomesh" architecture exhibits direct electron transfer (DET) and achieves a higher peak current per unit area of 1.2 mA/cm(2) compared to most other DET attachment schemes. The final enzyme surface coverage on the electrode was calculated to be approximately 4.74 × 10(-8) mol/cm(2), which is a significant improvement over most current glucose oxidase (GOx) DET attachment methods.

Walking peptide on Au(110) surface: Origin and nature of interfacial process

NASA Astrophysics Data System (ADS)

Humblot, V.; Tejeda, A.; Landoulsi, J.; Vallée, A.; Naitabdi, A.; Taleb, A.; Pradier, C.-M.

2014-10-01

IGF tri-peptide adsorption on Au(110)-(1 × 2) under Ultra High Vacuum (UHV) conditions has been investigated using surface science techniques such as synchrotron based Angle Resolved X-ray Photoemission Spectroscopy (AR-PES or AR-XPS), Low Energy Electron Diffraction (LEED) and Scanning Tunnelling Microscopy (STM). The behaviour of IGF molecules has been revealed to be coverage dependent; at low coverage, there is formation of islands presenting a chiral self-organised molecular network with a (4 2, - 3 2) symmetry as shown by Low Energy Electron Diffraction (LEED) and Scanning Tunnelling Microscopy (STM) on the unaltered Au(110)-(1 × 2) reconstruction, suggesting significant intermolecular interactions. When the coverage is increased, the islands grow bigger, and one can observe the disappearance of the self-organised network, along with a remarkable destruction of the (1 × 2) substrate reconstruction, as shown by STM. The effect of IGF on the surface gold atoms has been further confirmed by angle-resolved photoemission measurements which suggest a modification of the electronic states with the (1 × 2) symmetry. The resulting molecular organisation, and overall the gold surface disorganisation, prove a strong surface-molecule interaction, which may be probably be explained by a covalent bonding.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Spectroscopic study of gold nanoparticle formation through high intensity laser irradiation of solution

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

Nakamura, Takahiro, E-mail: nakamu@tagen.tohoku.ac.jp; Sato, Shunichi; Herbani, Yuliati

A spectroscopic study of the gold nanoparticle (NP) formation by high-intensity femtosecond laser irradiation of a gold ion solution was reported. The effect of varying energy density of the laser on the formation of gold NPs was also investigated. The surface plasmon resonance (SPR) peak of the gold nanocolloid in real-time UV-visible absorption spectra during laser irradiation showed a distinctive progress; the SPR absorption peak intensity increased after a certain irradiation time, reached a maximum and then gradually decreased. During this absorption variation, at the same time, the peak wavelength changed from 530 to 507 nm. According to an empiricalmore » equation derived from a large volume of experimental data, the estimated mean size of the gold NPs varied from 43.4 to 3.2 nm during the laser irradiation. The mean size of gold NPs formed at specific irradiation times by transmission electron microscopy showed the similar trend as that obtained in the spectroscopic analysis. From these observations, the formation mechanism of gold NPs during laser irradiation was considered to have two steps. The first is a reduction of gold ions by reactive species produced through a non-linear reaction during high intensity laser irradiation of the solution; the second is the laser fragmentation of produced gold particles into smaller pieces. The gold nanocolloid produced after the fragmentation by excess irradiation showed high stability for at least a week without the addition of any dispersant because of the negative charge on the surface of the nanoparticles probably due to the surface oxidation of gold nanoparticles. A higher laser intensity resulted in a higher efficiency of gold NPs fabrication, which was attributed to a larger effective volume of the reaction.« less

Gold/silver coated nanoporous ceramic membranes: a new substrate for SERS studies

NASA Astrophysics Data System (ADS)

Kassu, A.; Robinson, P.; Sharma, A.; Ruffin, P. B.; Brantley, C.; Edwards, E.

2010-08-01

Surface Enhanced Raman Scattering (SERS) is a recently discovered powerful technique which has demonstrated sensitivity and selectivity for detecting single molecules of certain chemical species. This is due to an enhancement of Raman scattered light by factors as large as 1015. Gold and Silver-coated substrates fabricated by electron-beam lithography on Silicon are widely used in SERS technique. In this paper, we report the use of nanoporous ceramic membranes for SERS studies. Nanoporous membranes are widely used as a separation membrane in medical devices, fuel cells and other studies. Three different pore diameter sizes of commercially available nanoporous ceramic membranes: 35 nm, 55nm and 80nm are used in the study. To make the membranes SERS active, they are coated with gold/silver using sputtering techniques. We have seen that the membranes coated with gold layer remain unaffected even when immersed in water for several days. The results show that gold coated nanoporous membranes have sensitivity comparable to substrates fabricated by electron-beam lithography on Silicon substrates.

Synthesis and characterization of gold graphene composite with dyes as model substrates for decolorization: A surfactant free laser ablation approach

NASA Astrophysics Data System (ADS)

Sai Siddhardha, R. S.; Lakshman Kumar, V.; Kaniyoor, Adarsh; Sai Muthukumar, V.; Ramaprabhu, S.; Podila, Ramakrishna; Rao, A. M.; Ramamurthy, Sai Sathish

2014-12-01

A facile surfactant free laser ablation mediated synthesis (LAMS) of gold-graphene composite is reported here. The material was characterized using transmission electron microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, powdered X-ray diffraction, Raman spectroscopy, Zeta potential measurements and UV-Visible spectroscopic techniques. The as-synthesized gold-graphene composite was effectively utilized as catalyst for decolorization of 4 important textile and laser dyes. The integration of gold nanoparticles (AuNPs) with high surface area graphene has enhanced the catalytic activity of AuNPs. This enhanced activity is attributed to the synergistic interplay of pristine gold's electronic relay and π-π stacking of graphene with the dyes. This is evident when the Rhodamine B (RB) reduction rate of the composite is nearly twice faster than that of commercial citrate capped AuNPs of similar size. In case of Methylene blue (MB) the rate of reduction is 17,000 times faster than uncatalyzed reaction. This synthetic method opens door to laser ablation based fabrication of metal catalysts on graphene for improved performance without the aid of linkers and surfactants.

Multifunctional gold coated iron oxide core-shell nanoparticles stabilized using thiolated sodium alginate for biomedical applications.

PubMed

Sood, Ankur; Arora, Varun; Shah, Jyoti; Kotnala, R K; Jain, Tapan K

2017-11-01

In this paper we report synthesis of aqueous based gold coated iron oxide nanoparticles to integrate the localized surface plasma resonance (SPR) properties of gold and magnetic properties of iron oxide in a single system. Iron oxide-gold core shell nanoparticles were stabilized by attachment of thiolated sodium alginate to the surface of nanoparticles. Transmission electron microscope (TEM) micrograph presents an average elementary particle size of 8.1±2.1nm. High resolution TEM (HR-TEM) and X-ray photon spectroscopy further confirms the presence of gold shell around iron oxide core. Gold coating is responsible for reducing saturation magnetization (M s ) value from ~41emu/g to ~24emu/g - in thiolated sodium alginate stabilized gold coated iron oxide core-shell nanoparticles. The drug (curcumin) loading efficiency for the prepared nanocomposites was estimated to be around 7.2wt% (72μgdrug/mg nanoparticles) with encapsulation efficiency of 72.8%. Gold-coated iron oxide core-shell nanoparticles could be of immense importance in the field of targeted drug delivery along with capability to be used as contrast agent for MRI & CT. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrodeposition of gold nanoparticles on mesoporous TiO{sub 2} photoelectrode to enhance visible region photocurrent

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

Supriyono,; Krisnandi, Yuni Krisyuningsih; Gunlazuardi, Jarnuzi, E-mail: jarnuzi@ui.ac.id

2016-04-19

Electrodeposition of gold nanoparticles (Au NPs) on the mesoporous TiO{sub 2} photoelectrode to enchance visible region photocurrent have been investigated. Mesoporous TiO{sub 2} was prepared by a sol gel method and immobilized to the fluorine doped tin oxide (FTO) substrate by dip coating technique. Gold nanoparticles were electrodeposited on the TiO{sub 2} surface and the result FTO/TiO{sub 2}/Au was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), UV-Vis diffuse reflectance spectroscopy (DRS), and X-ray diffraction (XRD). The generated photocurrent was evaluated with an electrochemical workstation (e-DAQ/e-recorder 401) using 60 W wolfram lamp as visible lightmore » source. The photoelectrochemical evaluation indicated that the presence of gold nanoparticles on TiO{sub 2} photoelectrode shall enhance the photocurrent up to 50%.« less

Tunneling-Electron-Induced Light Emission from Single Gold Nanoclusters.

PubMed

Yu, Arthur; Li, Shaowei; Czap, Gregory; Ho, W

2016-09-14

The coupling of tunneling electrons with the tip-nanocluster-substrate junction plasmon was investigated by monitoring light emission in a scanning tunneling microscope (STM). Gold atoms were evaporated onto the ∼5 Å thick Al2O3 thin film grown on the NiAl (110) surface where they formed nanoclusters 3-7 nm wide. Scanning tunneling spectroscopy (STS) of these nanoclusters revealed quantum-confined electronic states. Spatially resolved photon imaging showed localized emission hot spots. Size dependent study and light emission from nanocluster dimers further support the viewpoint that coupling of tunneling electrons to the junction plasmon is the main radiative mechanism. These results showed the potential of the STM to reveal the electronic and optical properties of nanoscale metallic systems in the confined geometry of the tunnel junction.

Glucose biosensor from covalent immobilization of chitosan-coupled carbon nanotubes on polyaniline-modified gold electrode.

PubMed

Wan, Dong; Yuan, Shaojun; Li, G L; Neoh, K G; Kang, E T

2010-11-01

An amperometric glucose biosensor was prepared using polyaniline (PANI) and chitosan-coupled carbon nanotubes (CS-CNTs) as the signal amplifiers and glucose oxidase (GOD) as the glucose detector on a gold electrode (the Au-g-PANI-c-(CS-CNTs)-GOD biosensor). The PANI layer was prepared via oxidative graft polymerization of aniline from the gold electrode surface premodified by self-assembled monolayer of 4-aminothiophenol. CS-CNTs were covalently coupled to the PANI-modified gold substrate using glutaradehyde as a bifunctional linker. GOD was then covalently bonded to the pendant hydroxyl groups of chitosan using 1,4-carbonyldiimidazole as the bifunctional linker. The surface functionalization processes were ascertained by X-ray photoelectron spectroscopy (XPS) analyses. The field emission scanning electron microscopy (FESEM) images of the Au-g-PANI-c-(CS-CNTs) electrode revealed the formation of a three-dimensional surface network structure. The electrode could thus provide a more spatially biocompatible microenvironment to enhance the amount and biocatalytic activity of the immobilized enzyme and to better mediate the electron transfer. The resulting Au-g-PANI-c-(CS-CNTs)-GOD biosensor exhibited a linear response to glucose in the concentration range of 1-20 mM, good sensitivity (21 μA/(mM·cm(2))), good reproducibility, and retention of >80% of the initial response current after 2 months of storage.

Comparison of the surfaces and interfaces formed for sputter and electroless deposited gold contacts on CdZnTe

NASA Astrophysics Data System (ADS)

Bell, Steven J.; Baker, Mark A.; Duarte, Diana D.; Schneider, Andreas; Seller, Paul; Sellin, Paul J.; Veale, Matthew C.; Wilson, Matthew D.

2018-01-01

Cadmium zinc telluride (CdZnTe) is a leading sensor material for spectroscopic X/γ-ray imaging in the fields of homeland security, medical imaging, industrial analysis and astrophysics. The metal-semiconductor interface formed during contact deposition is of fundamental importance to the spectroscopic performance of the detector and is primarily determined by the deposition method. A multi-technique analysis of the metal-semiconductor interface formed by sputter and electroless deposition of gold onto (111) aligned CdZnTe is presented. Focused ion beam (FIB) cross section imaging, X-ray photoelectron spectroscopy (XPS) depth profiling and current-voltage (IV) analysis have been applied to determine the structural, chemical and electronic properties of the gold contacts. In a novel approach, principal component analysis has been employed on the XPS depth profiles to extract detailed chemical state information from different depths within the profile. It was found that electroless deposition forms a complicated, graded interface comprised of tellurium oxide, gold/gold telluride particulates, and cadmium chloride. This compared with a sharp transition from surface gold to bulk CdZnTe observed for the interface formed by sputter deposition. The electronic (IV) response for the detector with electroless deposited contacts was symmetric, but was asymmetric for the detector with sputtered gold contacts. This is due to the electroless deposition degrading the difference between the Cd- and Te-faces of the CdZnTe (111) crystal, whilst these differences are maintained for the sputter deposited gold contacts. This work represents an important step in the optimisation of the metal-semiconductor interface which currently is a limiting factor in the development of high resolution CdZnTe detectors.

Self-assembly patterning of organic molecules on a surface

DOEpatents

Pan, Minghu; Fuentes-Cabrera, Miguel; Maksymovych, Petro; Sumpter, Bobby G.; Li, Qing

2017-04-04

The embodiments disclosed herein include all-electron control over a chemical attachment and the subsequent self-assembly of an organic molecule into a well-ordered three-dimensional monolayer on a metal surface. The ordering or assembly of the organic molecule may be through electron excitation. Hot-electron and hot-hole excitation enables tethering of the organic molecule to a metal substrate, such as an alkyne group to a gold surface. All-electron reactions may allow a direct control over the size and shape of the self-assembly, defect structures and the reverse process of molecular disassembly from single molecular level to mesoscopic scale.

Synthesis and pH-dependent assembly of isotropic and anisotropic gold nanoparticles functionalized with hydroxyl-bearing amino acids

NASA Astrophysics Data System (ADS)

Swami, Anuradha; Mittal, Sherry; Chopra, Adity; Sharma, Rohit K.; Wangoo, Nishima

2018-03-01

In recent years, the synthesis of gold nanostructures of controllable shapes and dimensions has become a subject of intensive and interesting studies. Especially, anisotropic gold nanostructures such as nanoplates, nanoribbons, nanoprisms and nanorods have attracted much attention due to their striking optical properties and promising applications in electronics, photonics, sensing and biomedicine. Keeping this in mind, in the present report, an unprecedented, facile and one pot synthesis of isotropic (spherical) and anisotropic (triangular, pentagonal, hexagonal, rod shaped) gold nanomaterials via pH controlled shape modulation using hydroxyl moeity containing α-amino acids (Serine, Threonine, Tyrosine) as both reducing and capping agents is reported. The synthesized nanostructures have been further characterized by UV-Vis spectroscopy and transmission electron microscopy. It was deduced from these studies that pH played a key role in the anisotropic growth of gold nanostructures. These gold nanoparticles can be further used for applications in biosensing, plasmonics, and electrocatalysis and others involving surface enhanced raman scattering. This study is therefore, important from the point of view of using amino acids for the synthesis of gold nanoparticles of different shapes and sizes leading towards the development of inventive biosensors and biocompatible nanoconstructs.

Heat- and electron-beam-induced transport of gold particles into silicon oxide and silicon studied by in situ high-resolution transmission electron microscopy.

PubMed

Biskupek, Johannes; Kaiser, Ute; Falk, Fritz

2008-06-01

In this study, we describe the transport of gold (Au) nanoparticles from the surface into crystalline silicon (Si) covered by silicon oxide (SiO(2)) as revealed by in situ high-resolution transmission electron microscopy. Complete crystalline Au nanoparticles sink through the SiO(2) layer into the Si substrate when high-dose electron irradiation is applied and temperature is raised above 150 degrees C. Above temperatures of 250 degrees C, the Au nanoparticles finally dissolve into fragments accompanied by crystallization of the amorphized Si substrate around these fragments. The transport process is explained by a wetting process followed by Stokes motion. Modelling this process yields boundaries for the interface energies involved.

Surface potential on gold nanodisc arrays fabricated on silicon under light irradiation

NASA Astrophysics Data System (ADS)

Ezaki, Tomotarou; Matsutani, Akihiro; Nishioka, Kunio; Shoji, Dai; Sato, Mina; Okamoto, Takayuki; Isobe, Toshihiro; Nakajima, Akira; Matsushita, Sachiko

2018-06-01

This paper proposes Kelvin probe force microscopy (KFM) as a new measurement method of plasmon phenomenon. The surface potential of two arrays, namely, a monomeric array and a tetrameric array, of gold nanodiscs (600 nm diameter) on a silicon substrate fabricated by electron beam lithography was investigated by KFM with the view point of irradiation light wavelength change. In terms of the value of the surface potential, contrasting behaviour, a negative shift in the monomeric disc array and a positive shift in the tetrameric disc array, was observed by light irradiation. This interesting behaviour is thought to be related to a difference in localised plasmons caused by the disc arrangement and was investigated from various viewpoints, including Rayleigh anomalies. Finally, this paper reveals that KFM is powerful not only to investigate the plasmonic behaviour but also to predict the electron transportation.

Ultra-high sensitive substrates for surface enhanced Raman scattering, made of 3 nm gold nanoparticles embedded on SiO2 nanospheres

NASA Astrophysics Data System (ADS)

Phatangare, A. B.; Dhole, S. D.; Dahiwale, S. S.; Bhoraskar, V. N.

2018-05-01

The surface properties of substrates made of 3 nm gold nanoparticles embedded on SiO2 nanospheres enabled fingerprint detection of thiabendazole (TBZ), crystal violet (CV) and 4-Aminothiophenol (4-ATP) at an ultralow concentration of ∼10-18 M by surface enhanced Raman spectroscopy (SERS). Gold nanoparticles of an average size of ∼3 nm were synthesized and simultaneously embedded on SiO2 nanospheres by the electron irradiation method. The substrates made from the 3 nm gold nanoparticles embedded on SiO2 nanospheres were successfully used for recording fingerprint SERS spectra of TBZ, CV and 4-ATP over a wide range of concentrations from 10-6 M to 10-18 M using 785 nm laser. The unique features of these substrates are roughness near the surface due to the inherent structural defects of 3 nm gold nanoparticles, nanogaps of ≤ 1 nm between the embedded nanoparticles and their high number. These produced an abundance of nanocavities which act as active centers of hot-spots and provided a high electric field at the reporter molecules and thus an enhancement factor required to record the SERS spectra at ultra low concentration of 10-18 M. The SERS spectra recorded by the substrates of 4 nm and 6 nm gold nanoparticles are discussed.

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 adenine bases. However, the results reported here contradict the previously reported data. Future prospectives on this work are outlined.

Ultrafast Imaging of Surface Plasmons Propagating on a Gold Surface

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

Gong, Yu; Joly, Alan G.; Hu, Dehong

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,more » 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.« less

High spatial resolution mapping of surface plasmon resonance modes in single and aggregated gold nanoparticles assembled on DNA strands

NASA Astrophysics Data System (ADS)

Diaz-Egea, Carlos; Sigle, Wilfried; van Aken, Peter A.; Molina, Sergio I.

2013-07-01

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.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2015-07-21

example, H adsorbed alone on an oxide surface will bind to oxygen to form a hydroxide . However, if a Lewis base (e.g. any electron donor) is...that on a gold surface, which is not surprising considering the bonding character between the cluster and metal surfaces. The high mobility verifies

Tuning the interaction between propagating and localized surface plasmons for surface enhanced Raman scattering in water for biomedical and environmental applications

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

Shioi, Masahiko, E-mail: shioi.masahiko@jp.panasonic.com; Department of Electric and Electronic Engineering, Graduate School of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501; Jans, Hilde

With a view to biomedical and environmental applications, we investigate the plasmonic properties of a rectangular gold nanodisk array in water to boost surface enhanced Raman scattering (SERS) effects. To control the resonance wavelengths of the surface plasmon polariton and the localized surface plasmon, their dependence on the array period and diameter in water is studied in detail using a finite difference time domain method. A good agreement is obtained between calculated resonant wavelengths and those of gold nanodisk arrays fabricated using electron beam lithography. For the optimized structure, a SERS enhancement factor of 7.8 × 10{sup 7} is achieved in watermore » experimentally.« less

Nanoparticle Treated Stainless Steel Filters for Metal Vapor Sequestration

NASA Astrophysics Data System (ADS)

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul; Coopersmith, Kaitlin J.; Summer, Ansley J.; Lewis, Rebecca

2017-02-01

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown onto various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. The effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.

Significance of Graphitic Surfaces in Aurodicyanide Adsorption by Activated Carbon: Experimental and Computational Approach

NASA Astrophysics Data System (ADS)

Bhattacharyya, Dhiman; Depci, Tolga; Prisbrey, Keith; Miller, Jan D.

Despite tremendous developments in industrial use of activated carbon (AC) for gold adsorption, specific aurodicyanide [Au(CN)2-] adsorption sites on the carbon have intrigued researchers. The graphitic structure of AC has been well established. Previously radiochemical and now, XPS and Raman characterizations have demonstrated higher site-specific gold adsorption on graphitic edges. Morphological characterizations have revealed the presence of slit-pores (5-10 Å). Molecular-dynamics-simulation (MDS) performed on graphitic slit-pores illustrated gold-cyanide ion-pair preferentially adsorbs on edges. Ab-initio simulations predicted lower barrier for electron sharing in pores with aurodic yanide, indicating tighter bonding than graphitic surface and was well supported by Gibbs energy calculations too. Interaction energy as function of the separation distance indicated tighter bonding of gold cyanide to the graphite edges than water molecules. Selective adsorption of aurodicyanide ion-pair seems to be related to low polarity of gold complex and its accommodation at graphitic edges.

Aluminum and gold deposition on cleaved single crystals of Bi2CaSr2Cu2O8 superconductor

NASA Astrophysics Data System (ADS)

Wells, B. O.; Lindberg, P. A. P.; Shen, Z.-X.; Dessau, D. S.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Kapitulnik, A.

1989-02-01

We have used photoelectron spectroscopy to study the changes in the electronic structure of cleaved, single crystal Bi2CaSr2Cu2O8 caused by deposition of aluminum and gold. Al reacts strongly with the superconductor surface. Even the lowest coverages of Al reduces the valency of Cu in the superconductor, draws oxygen out of the bulk, and strongly modifies the electronic states in the valence band. The Au shows little reaction with the superconductor surface. Underneath Au, the Cu valency is unchanged and the core peaks show no chemically shifted components. Au appears to passivate the surface of the superconductor and thus may aid in the processing of the Bi-Ca-Sr-Cu-O material. These results are consistent with earlier studies of Al and Au interfaces with other, polycrystalline oxide superconductors. Comparing with our own previous results, we conclude that Au is superior to Ag in passivating the Bi-Ca-Sr-Cu-O surface.

[Preparation of polyelectrolyte microcapsules contained gold nanoparticles].

PubMed

Sun, Ya-jie; Zhu, Jia-bi; Zheng, Chun-li

2010-03-01

In this work, polyelectrolyte microcapsules containing gold nanoparticles were prepared via layer by layer assembly. Gold nanoparticles and poly (allyamine hydrochloride) (PAH) were coated on the CaCO3 microparticles. And then EDTA was used to remove the CaCO3 core. Scanning electron microscopy (SEM) was used to characterize the surface of microcapsules. SEM images indicate that the microcapsules and the polyelectrolyte multilayer were deposited on the surface of CaCO3 microparticles. FITC-bovine serum albumin (FITC-BSA, 2 mg) was incorporated in the CaCO3 microparticles by co-precipitation. Fluorescence microscopy was used to observe the fluorescence intensity of microcapsules. The encapsulation efficiency was (34.31 +/- 2.44) %. The drug loading was (43.75 +/- 3.12) mg g(-1).

Hardness and Elastic Modulus on Six-Fold Symmetry Gold Nanoparticles

PubMed Central

Ramos, Manuel; Ortiz-Jordan, Luis; Hurtado-Macias, Abel; Flores, Sergio; Elizalde-Galindo, José T.; Rocha, Carmen; Torres, Brenda; Zarei-Chaleshtori, Maryam; Chianelli, Russell R.

2013-01-01

The chemical synthesis of gold nanoparticles (NP) by using gold (III) chloride trihydrate (HAuCl∙3H2O) and sodium citrate as a reducing agent in aqueous conditions at 100 °C is presented here. Gold nanoparticles areformed by a galvanic replacement mechanism as described by Lee and Messiel. Morphology of gold-NP was analyzed by way of high-resolution transmission electron microscopy; results indicate a six-fold icosahedral symmetry with an average size distribution of 22 nm. In order to understand the mechanical behaviors, like hardness and elastic moduli, gold-NP were subjected to nanoindentation measurements—obtaining a hardness value of 1.72 GPa and elastic modulus of 100 GPa in a 3–5 nm of displacement at the nanoparticle’s surface. PMID:28809302

Quantum sized gold nanoclusters with atomic precision.

PubMed

Qian, Huifeng; Zhu, Manzhou; Wu, Zhikun; Jin, Rongchao

2012-09-18

Gold nanoparticles typically have a metallic core, and the electronic conduction band consists of quasicontinuous energy levels (i.e. spacing δ ≪ k(B)T, where k(B)T is the thermal energy at temperature T (typically room temperature) and k(B) is the Boltzmann constant). Electrons in the conduction band roam throughout the metal core, and light can collectively excite these electrons to give rise to plasmonic responses. This plasmon resonance accounts for the beautiful ruby-red color of colloidal gold first observed by Faraday back in 1857. On the other hand, when gold nanoparticles become extremely small (<2 nm in diameter), significant quantization occurs to the conduction band. These quantum-sized nanoparticles constitute a new class of nanomaterial and have received much attention in recent years. To differentiate quantum-sized nanoparticles from conventional plasmonic gold nanoparticles, researchers often refer to the ultrasmall nanoparticles as nanoclusters. In this Account, we chose several typical sizes of gold nanoclusters, including Au(25)(SR)(18), Au(38)(SR)(24), Au(102)(SR)(44), and Au(144)(SR)(60), to illustrate the novel properties of metal nanoclusters imparted by quantum size effects. In the nanocluster size regime, many of the physical and chemical properties of gold nanoparticles are fundamentally altered. Gold nanoclusters have discrete electronic energy levels as opposed to the continuous band in plasmonic nanoparticles. Quantum-sized nanoparticles also show multiple optical absorption peaks in the optical spectrum versus a single surface plasmon resonance (SPR) peak at 520 nm for spherical gold nanocrystals. Although larger nanocrystals show an fcc structure, nanoclusters often have non-fcc atomic packing structures. Nanoclusters also have unique fluorescent, chiral, and magnetic properties. Due to the strong quantum confinement effect, adding or removing one gold atom significantly changes the structure and the electronic and optical properties of the nanocluster. Therefore, precise atomic control of nanoclusters is critically important: the nanometer precision typical of conventional nanoparticles is not sufficient. Atomically precise nanoclusters are represented by molecular formulas (e.g. Au(n)(SR)(m) for thiolate-protected ones, where n and m denote the respective number of gold atoms and ligands). Recently, major advances in the synthesis and structural characterization of molecular purity gold nanoclusters have made in-depth investigations of the size evolution of metal nanoclusters possible. Metal nanoclusters lie in the intermediate regime between localized atomic states and delocalized band structure in terms of electronic properties. We anticipate that future research on quantum-sized nanoclusters will stimulate broad scientific and technological interests in this special type of metal nanomaterial.

Synthesis of gold nanoparticles with graphene oxide.

PubMed

Wang, Wenshuo; He, Dawei; Zhang, Xiqing; Duan, Jiahua; Wu, Hongpeng; Xu, Haiteng; Wang, Yongsheng

2014-05-01

Single sheets of functionalized graphene oxide are derived through chemical exfoliation of natural flake graphite. We present an effective synthetic method of graphene-gold nanoparticles hybrid nanocomposites. AFM (Atomic Force Microscope) was used to measure the thickness of the individual GO nanosheet. FTIR (Fourier transform infrared) spectroscopy was used to verify the attachment of oxygen functionalities on the surface of graphene oxide. TEM (Transmission Electron Microscope) data revealed the average diameters of the gold colloids and characterized the composite particles situation. Absorption spectroscopy showed that before and after synthesis the gold particle size did not change. Our studies indicate that the hybrid is potential substrates for catalysts and biosensors.

Gold nanostar synthesis with a silver seed mediated growth method.

PubMed

Kereselidze, Zurab; Romero, Victor H; Peralta, Xomalin G; Santamaria, Fidel

2012-01-15

The physical, chemical and optical properties of nano-scale colloids depend on their material composition, size and shape. There is a great interest in using nano-colloids for photo-thermal ablation, drug delivery and many other biomedical applications. Gold is particularly used because of its low toxicity. A property of metal nano-colloids is that they can have a strong surface plasmon resonance. The peak of the surface plasmon resonance mode depends on the structure and composition of the metal nano-colloids. Since the surface plasmon resonance mode is stimulated with light there is a need to have the peak absorbance in the near infrared where biological tissue transmissivity is maximal. We present a method to synthesize star shaped colloidal gold, also known as star shaped nanoparticles or nanostars. This method is based on a solution containing silver seeds that are used as the nucleating agent for anisotropic growth of gold colloids. Scanning electron microscopy (SEM) analysis of the resulting gold colloid showed that 70 % of the nanostructures were nanostars. The other 30 % of the particles were amorphous clusters of decahedra and rhomboids. The absorbance peak of the nanostars was detected to be in the near infrared (840 nm). Thus, our method produces gold nanostars suitable for biomedical applications, particularly for photo-thermal ablation.

Effects of surface tension and viscosity on gold and silver sputtered onto liquid substrates

NASA Astrophysics Data System (ADS)

De Luna, Mark M.; Gupta, Malancha

2018-05-01

In this paper, we study DC magnetron sputtering of gold and silver onto liquid substrates of varying viscosities and surface tensions. We were able to separate the effects of viscosity from surface tension by depositing the metals onto silicone oils with a range of viscosities. The effects of surface tension were studied by depositing the metals onto squalene, poly(ethylene glycol), and glycerol. It was found that dispersed nanoparticles were formed on liquids with low surface tension and low viscosity whereas dense films were formed on liquids with low surface tension and high viscosity. Nanoparticles were formed on both the liquid surface and within the bulk liquid for high surface tension liquids. Our results can be used to tailor the metal and liquid interaction to fabricate particles and films for various applications in optics, electronics, and catalysis.

Enzymes immobilization on Fe 3O 4-gold nanoparticles

NASA Astrophysics Data System (ADS)

Kalska-Szostko, B.; Rogowska, M.; Dubis, A.; Szymański, K.

2012-01-01

In the present study Fe3O4 magnetic nanoparticles were synthesized by coprecipitation of Fe2+ and Fe3+ from chlorides. In the next step magnetite-gold core-shell nanoparticles were synthesized from HAuCl4 using an ethanol as a reducing agent. Finally, magnetic nanoparticles were functionalized by hexadecanethiol. The immobilization of biological molecules (trypsin and glucose oxidase) to the thiol-modified and unmodified magnetite-gold nanoparticles surface was tested. The resulting nanoparticles were characterized by infrared spectroscopy, differential scanning calorimetry, Mössbauer spectroscopy and transmission electron microscopy.

Biosynthesis, structural characterization and antimicrobial activity of gold and silver nanoparticles.

PubMed

Ahmad, Tokeer; Wani, Irshad A; Manzoor, Nikhat; Ahmed, Jahangeer; Asiri, Abdullah M

2013-07-01

An eco friendly simple biosynthetic route was used for the preparation of monodisperse and highly crystalline gold and silver nanoparticles using cell free extract of fungus, Candida albicans. Transmission electron microscopic studies show the formation of gold and silver nanocrystals of average size of 5 nm and 30 nm with the specific surface areas of 18.9 m(2)/g and 184.4 m(2)/g respectively. The interaction of gold and silver nanoparticles with proteins has been formulated by FT-IR spectroscopy and thermal gravimetric analysis. The formation of gold and silver nanoparticles was also confirmed by the appearance of a surface plasmon band at 540 nm and 450 nm respectively. The antimicrobial activity of the synthesized gold and silver nanoparticles was investigated against both Staphylococcus aureus and Escherichia coli. The results suggest that these nanoparticles can be used as effective growth inhibitors against the test microorganisms. Greater bactericidal activity was observed for silver nanoparticles. The E. coli, a gram negative bacterium was found to be more susceptible to gold and silver nanoparticles than the S. aureus, a gram positive bacterium. Copyright © 2013 Elsevier B.V. All rights reserved.

Diazonium-derived aryl films on gold nanoparticles: evidence for a carbon-gold covalent bond.

PubMed

Laurentius, Lars; Stoyanov, Stanislav R; Gusarov, Sergey; Kovalenko, Andriy; Du, Rongbing; Lopinski, Gregory P; McDermott, Mark T

2011-05-24

Tailoring the surface chemistry of metallic nanoparticles is generally a key step for their use in a wide range of applications. There are few examples of organic films covalently bound to metal nanoparticles. We demonstrate here that aryl films are formed on gold nanoparticles from the spontaneous reduction of diazonium salts. The structure and the bonding of the film is probed with surface-enhanced Raman scattering (SERS). Extinction spectroscopy and SERS show that a nitrobenzene film forms on gold nanoparticles from the corresponding diazonium salt. Comparison of the SERS spectrum with spectra computed from density functional theory models reveals a band characteristic of a Au-C stretch. The observation of this stretch is direct evidence of a covalent bond. A similar band is observed in high-resolution electron energy loss spectra of nitrobenzene layers on planar gold. The bonding of these types of films through a covalent interaction on gold is consistent with their enhanced stability observed in other studies. These findings provide motivation for the use of diazonium-derived films on gold and other metals in applications where high stability and/or strong adsorbate-substrate coupling are required.

Visualizing gold nanoparticle uptake in live cells with liquid scanning transmission electron microscopy.

PubMed

Peckys, Diana B; de Jonge, Niels

2011-04-13

The intracellular uptake of 30 nm diameter gold nanoparticles (Au-NPs) was studied at the nanoscale in pristine eukaryotic cells. Live COS-7 cells were maintained in a microfluidic chamber and imaged using scanning transmission electron microscopy. A quantitative image analysis showed that Au-NPs bound to the membranes of vesicles, possibly lysosomes, and occupied 67% of the available surface area. The vesicles accumulated to form a micrometer-sized cluster after 24 h of incubation. Two clusters were analyzed and found to consist of 117 ± 9 and 164 ± 4 NP-filled vesicles.

Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard-Jones potential.

PubMed

Geada, Isidro Lorenzo; Ramezani-Dakhel, Hadi; Jamil, Tariq; Sulpizi, Marialore; Heinz, Hendrik

2018-02-19

Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

NASA Astrophysics Data System (ADS)

Alizadeh, Elahe; Massey, Sylvain; Sanche, Léon; Rowntree, Paul A.

2016-04-01

Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH2-) and 15 amu (CH3-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films. Contribution to the Topical Issue "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic, B. Sivaraman.

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.

Functional and Selective Bacterial Interfaces Using Cross-Scaffold Gold Binding Peptides

NASA Astrophysics Data System (ADS)

Adams, Bryn L.; Hurley, Margaret M.; Jahnke, Justin P.; Stratis-Cullum, Dimitra N.

2015-11-01

We investigated the functional and selective activity of three phage-derived gold-binding peptides on the Escherichia coli ( E. coli) bacterial cell surface display scaffold (eCPX) for the first time. Gold-binding peptides, p3-Au12 (LKAHLPPSRLPS), p8#9 (VSGSSPDS), and Midas-2 (TGTSVLIATPYV), were compared side-by-side through experiment and simulation. All exhibited strong binding to an evaporated gold film, with approximately a 4-log difference in binding between each peptide and the control sample. The increased affinity for gold was also confirmed by direct visualization of samples using Scanning Electron Microscopy (SEM). Peptide dynamics in solution were performed to analyze innate structure, and all three were found to have a high degree of flexibility. Preferential binding to gold over silicon for all three peptides was demonstrated, with up to four orders of magnitude selectivity exhibited by p3-Au12. The selectivity was also clearly evident through SEM analysis of the boundary between the gold film and silicon substrate. Functional activity of bound E. coli cells was further demonstrated by stimulating filamentation and all three peptides were characterized as prolific relative to control samples. This work shows great promise towards functional and active bacterial-hybrid gold surfaces and the potential to enable the next generation living material interfaces.

Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence.

PubMed

Chmielewski, Adrian; Nelayah, Jaysen; Amara, Hakim; Creuze, Jérôme; Alloyeau, Damien; Wang, Guillaume; Ricolleau, Christian

2018-01-12

We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu_{50}Au_{50}, and Cu_{25}Au_{75} nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N-body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence

NASA Astrophysics Data System (ADS)

Chmielewski, Adrian; Nelayah, Jaysen; Amara, Hakim; Creuze, Jérôme; Alloyeau, Damien; Wang, Guillaume; Ricolleau, Christian

2018-01-01

We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu50 Au50 , and Cu25 Au75 nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N -body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

Transfer of molybdenum disulfide to various metals

NASA Technical Reports Server (NTRS)

Barton, G. C.; Pepper, S. V.

1977-01-01

Sliding friction experiments were conducted with molybdenum disulfide single crystals in contact with sputter cleaned surfaces of copper, nickel, gold, and 304 stainless steel. Transfer of the molybdenum disulfide to the metals was monitored with Auger electron spectroscopy. Results of the investigation indicate molybdenum disulfide transfers to all clean metal surfaces after a single pass over the metal surface with film thickness observed to increase with repeated passes over the same surfaces. Large particle transfer occurs when the orientation of the crystallites is other than basal. This is frequently accompanied by abrasion of the metal. Adhesion of molybdenum disulfide films occurred readily to copper and nickel, less readily to 304 stainless steel, and even less effectively to the gold, which indicates a chemical effect.

Selective Binding, Self-Assembly and Nanopatterning of the Creutz-Taube Ion on Surfaces

PubMed Central

Wang, Yuliang; Lieberman, Marya; Hang, Qingling; Bernstein, Gary

2009-01-01

The surface attachment properties of the Creutz-Taube ion, i.e., [(NH3)5Ru(pyrazine)Ru(NH3)5]5+, on both hydrophilic and hydrophobic types of surfaces were investigated using X-ray photoelectron spectroscopy (XPS). The results indicated that the Creutz-Taube ions only bound to hydrophilic surfaces, such as SiO2 and –OH terminated organic SAMs on gold substrates. No attachment of the ions on hydrophobic surfaces such as –CH3 terminated organic SAMs and poly(methylmethacrylate) (PMMA) thin films covered gold or SiO2 substrates was observed. Further ellipsometric, atomic force microscopy (AFM) and time-dependent XPS studies suggested that the attached cations could form an inorganic analog of the self-assembled monolayer on SiO2 substrate with a “lying-down” orientation. The strong electrostatic interaction between the highly charged cations and the anionic SiO2 surface was believed to account for these observations. Based on its selective binding property, patterning of wide (∼200 nm) and narrow (∼35 nm) lines of the Creutz-Taube ions on SiO2 surface were demonstrated through PMMA electron resist masks written by electron beam lithography (EBL). PMID:19333420

Synthesis of Crooked Gold Nanocrystals by Electrochemical Technique

NASA Astrophysics Data System (ADS)

Huang, Chien-Jung; Chiu, Pin-Hsiang; Chen, Ming-Da; Meen, Teen-Hang

2005-07-01

In this article, we demonstrate the synthesis of crooked gold nanocrystals (CGNCs) by an electrochemical technique using micelle templates formed by two surfactants with different amounts of isopropanol solvent, the primary surfactant being hexadecyltrimethylammonium bromide (C16TABr) and the cosurfactant being tetradodecylammonium bromide (TC12ABr). To investigate the influence of isopropanol solvent on the CGNCs, the amount of isopropanol was varied in the range from 50 to 300 μL. It was found that the aspect ratios (γ) of CGNCs were in the range from 1.06 to 1.46, and the UV--vis optical absorption measurement revealed a pronounced redshift of the surface plasmon band from 532 to 560 nm. The CGNCs were composed of many large gold grains with small gold nuclei, and it was determined that several grains are present within each of the CGNCs using a dark-field transmission electron microscopy (TEM) image. It is suggested that the CGNCs have a polycrystalline structure. The CGNCs have been determined to be pure gold with a face-centered cubic (fcc) structure by electron diffraction (ED) analysis.

Optimization and stabilization of gold nanoparticles by using herbal plant extract with microwave heating

NASA Astrophysics Data System (ADS)

Yasmin, Akbar; Ramesh, Kumaraswamy; Rajeshkumar, Shanmugam

2014-04-01

In this study, we have synthesized the gold nanoparticles by using Hibiscus rosa-sinensis, a medicinal plant. The gold nanoparticles were synthesized rapidly by the involvement of microwave heating. By changing of plant extract concentration, gold solution concentration, microwave heating time and power of microwave heating the optimized condition was identified. The surface Plasmon resonance found at 520 nm confirmed the gold nanoparticles synthesis. The spherical sized nanoparticles in the size range of 16-30 nm were confirmed by Transmission Electron Microscope (TEM). The stability of the nanoparticles is very well proved in the invitro stability tests. The biochemical like alkaloids and flavonoids play a vital role in the nanoparticles synthesis was identified using the Fourier Transform Infrared Spectroscopy (FTIR). Combining the phytochemical and microwave heating, the rapid synthesis of gold nanoparticles is the novel process for the medically applicable gold nanoparticles production.

Hepatic Subcellular Compartmentation of Cytoplasmic Phosphoenolpyruvate Carboxykinase Determined by Immunogold Electron Microscopy

NASA Astrophysics Data System (ADS)

Gao, Kuixiong; Cardell, Emma Lou; Morris, Randal E.; Giffin, Bruce F.; Cardell, Robert R.

1995-08-01

Phosphoenolpyruvate carboxykinase (PEPCK) is the rate-limiting gluconeogenic enzyme and in liver occurs in a lobular gradient from periportal to pericentral regions. The subcellular distribution of cytoplasmic PEPCK molecules within hepatocytes and its relationship to organelles have not been determined previously. In this study, we have used immunogold electron microscopy to evaluate the subcellar distribution of the enzyme, in addition to brightfield and epipolarized light microscopy. Cryosections (10 [mu]m) of perfusion-fixed rat liver were collected on silanated slides and immunostained using goat anti-rat PEPCK followed by 5-nm gold-labeled secondary and tertiary antibodies. Additionally, free-floating vibratome sections (25, 50, and 100 [mu]m) of perfusion-immersion-fixed rat liver were immunogold stained using goat anti-rat PEPCK and 5-nm gold-labeled secondary antibody, with and without silver enhancement. The immunogold labeled sections from both procedures were embedded in epoxy resin for the preparation of thin sections for electron microscopy. The results showed that the gold-labeled antibodies penetrated the entire thickness of cryosections, resulting in a high signal for PEPCK, but membranes in general, the smooth endoplasmic reticulum in particular, were not identifiable as electron dense unit membranes. On the other hand, the vibratome sections of well-fixed tissue allowed good visualization of the ultrastructure of cellular organelles, with the smooth endoplasmic reticulum appearing as vesicles and tubules with electron dense unit membranes; however, the penetration of the gold-labeled antibody was limited to cells at the surface of the vibratome sections. In both procedures, PEPCK, as indicated by gold particles, is predominantly in the glycogen areas of the cytosome and not in mitochondria, nuclei, Golgi apparatus, or other cell organelles. Hepatocytes in periportal regions have a compact subcellular distribution of PEPCK shown by gold particles; hepatocytes in pericentral regions have a diffuse subcellular distribution of PEPCK and thus more scattered gold particles. When normal serum replaced the first antibody in the immunogold staining procedures, the background was very low.

Investigating the use of in situ liquid cell scanning transmission electron microscopy

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

Nguy, Amanda

2016-02-19

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 achievedmore » 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 adenine bases. However, the results reported here contradict the previously reported data. Future prospectives on this work are outlined.« less

Synthesis and catalytic activity of the metastable phase of gold phosphide

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

Fernando, Deshani; Nigro, Toni A.E.; Dyer, I.D.

Recently, transition metal phosphides have found new applications as catalysts for the hydrogen evolution reaction that has generated an impetus to synthesize these materials at the nanoscale. In this work, Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous. Gold nanorods were used as morphological templates with the aim of controlling the shape and size of the resulting gold phosphide particles. We demonstrate that the surface capping ligand of the gold nanoparticle precursors can influence the purity and extent to which the gold phosphide phase will form. Gold nanorods functionalized withmore » 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanorods are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Graphical abstract: Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous and gold nanoparticles as reactants. We demonstrate that the surface capping ligand of the gold nanoparticle precursors influence the purity and extent to which the Au{sub 2}P{sub 3} phase will form. Gold nanorods functionalized with 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanoparticles are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Highlights: • The surface chemistry of gold affects the synthetic yields of Au{sub 2}P{sub 3}. • Imaging of Au{sub 2}P{sub 3} with transmission electron microscopy results in decomposition. • Au{sub 2}P{sub 3} nanoparticles exhibit activity towards the hydrogen evolution reaction.« less

Gold Nanomaterials in Consumer Cosmetics Nanoproducts: Analyses, Characterization, and Dermal Safety Assessment.

PubMed

Cao, Mingjing; Li, Jiayang; Tang, Jinglong; Chen, Chunying; Zhao, Yuliang

2016-10-01

Establishment of analytical methods of engineered nanomaterials in consumer products for their human and environmental risk assessment becomes urgent for both academic and industrial needs. Owing to the difficulties and challenges around nanomaterials in complex media, proper chemical separation and biological assays of nanomaterials from nanoproducts needs to be firstly developed. Herein, a facile and rapid method to separate and analyze gold nanomaterials in cosmetics is reported. Gold nanomaterials are successfully separated from different facial or eye creams and their physiochemical properties are analyzed by quantitative and qualitative state-of-the art techniques with high sensitivity or high spatial resolution. In turn, a protocol including quantification of gold by inductively coupled plasma mass spectrometry and thorough characterization of morphology, size distribution, and surface property by electron microscopes, atomic force microscope, and X-ray photoelectron spectroscope is developed. Subsequently, the preliminary toxicity assessment indicates that gold nanomaterials in cosmetic creams have no observable toxicity to human keratinocytes even after 24 h exposure up to a concentration of 200 μg mL -1 . The environmental scanning electron microscope reveals that gold nanomaterials are mostly attached on the cell membrane. Thus, the present study provides a full analysis protocol for toxicity assessment of gold nanomaterials in consumer products (cosmetic creams). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel fullerene lipoic acid derivative: Synthesis and preparation of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Viana, A. S.; Leupold, S.; Eberle, C.; Shokati, T.; Montforts, F.-P.; Abrantes, L. M.

2007-11-01

Synthesis and preparation of self-assembled monolayers of a novel fullerene lipoic acid derivative on gold are reported. The presence of densely packed SAMs was confirmed by ellipsometry and cyclic voltammetry. The electrochemical response of the modified electrode in organic media exhibits the first two redox peaks characteristic of the extended π-electron system of fullerene. C 60 surface coverage (1.4 × 10 -10 mol cm -2) has been electrochemically determined by the redox process of the adsorbed fullerene moiety and by reductive desorption of the SAM in strong alkaline solution. Electrochemical data indicate that all four sulphur atoms are involved in the self-assembly process, providing an increase of SAM stability in comparison to mono or di-thiolated appended molecules. Visualisation of discrete fullerene molecules by scanning tunnelling microscopy supplied further evidence for gold modification and molecular distribution on the surface. Mixed monolayers of hexanethiol and fullerene derivatives in a proportion of 1:2 have been also studied with the purpose of controlling the amount and distribution of fullerene units on the gold surface.

Catalase coupled gold nanoparticles: Comparison between carbodiimide and biotin-streptavidin methods

PubMed Central

Chirra, Hariharasudhan D.; Sexton, Travis; Biswal, Dipti; Hersh, Louis B.; Hilt, J. Zach

2011-01-01

The use of proteins for therapeutic applications requires the protein to maintain sufficient activity for the period of in vivo treatment. Many proteins exhibit a short half-life in vivo and, thus, require delivery systems for them to be applied as therapeutics. The relative biocompatibility and the ability to form functionalized bioconjugates via simple chemistry make gold nanoparticles excellent candidates as protein delivery systems. Herein, two protocols for coupling proteins to gold nanoparticles were compared. In the first, the strong biomolecular binding between biotin and streptavidin was used to couple catalase to the surface of gold nanoparticles. In the second protocol, the formation of an amide bond between carboxylic acid coated gold nanoparticles and free surface amines of catalase using carbodiimide chemistry was performed. The stability and kinetics of the different steps involved in these protocols were studied using UV-Visible spectroscopy, dynamic light scattering, and transmission electron microscopy. The addition of mercaptoundecanoic acid in conjugation with (N-(6-(biotinamido)hexyl)-3′-(2′-pyridyldithio)-propionamide increased the stability of biotinylated gold nanoparticles. Although the carbodiimide chemistry based bioconjugation approach exhibited a decrease in catalase activity, the carbodiimide chemistry based bioconjugation approach resulted in more active catalase per gold nanoparticle compared to that of mercaptoundecanoic acid stabilized biotinylated gold nanoparticles. Both coupling protocols resulted in gold nanoparticles loaded with active catalase. Thus, these gold nanoparticle systems and coupling protocols represent promising methods for the application of gold nanoparticles for protein delivery. PMID:21232642

High resolution SEM imaging of gold nanoparticles in cells and tissues.

PubMed

Goldstein, A; Soroka, Y; Frušić-Zlotkin, M; Popov, I; Kohen, R

2014-12-01

The growing demand of gold nanoparticles in medical applications increases the need for simple and efficient characterization methods of the interaction between the nanoparticles and biological systems. Due to its nanometre resolution, modern scanning electron microscopy (SEM) offers straightforward visualization of metallic nanoparticles down to a few nanometre size, almost without any special preparation step. However, visualization of biological materials in SEM requires complicated preparation procedure, which is typically finished by metal coating needed to decrease charging artefacts and quick radiation damage of biomaterials in the course of SEM imaging. The finest conductive metal coating available is usually composed of a few nanometre size clusters, which are almost identical to the metal nanoparticles employed in medical applications. Therefore, SEM monitoring of metal nanoparticles within cells and tissues is incompatible with the conventional preparation methods. In this work, we show that charging artefacts related to non-conductive biological specimen can be successfully eliminated by placing the uncoated biological sample on a conductive substrate. By growing the cells on glass pre-coated with a chromium layer, we were able to observe the uptake of 10 nm gold nanoparticles inside uncoated and unstained macrophages and keratinocytes cells. Imaging in back scattered electrons allowed observation of gold nanoparticles located inside the cells, while imaging in secondary electron gave information on gold nanoparticles located on the surface of the cells. By mounting a skin cross-section on an improved conductive holder, consisting of a silicon substrate coated with copper, we were able to observe penetration of gold nanoparticles of only 5 nm size through the skin barrier in an uncoated skin tissue. The described method offers a convenient modification in preparation procedure for biological samples to be analyzed in SEM. The method provides high conductivity without application of surface coating and requires less time and a reduced use of toxic chemicals. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

Preparation of glucose sensors using gold nanoparticles modified diamond electrode

NASA Astrophysics Data System (ADS)

Fachrurrazie; Ivandini, T. A.; Wibowo, W.

2017-04-01

A glucose sensor was successfully developed by immobilizing glucose oxidase (GOx) at boron-doped diamond (BDD) electrodes. Prior to GOx immobilization, the BDD was modified with gold nanoparticles (AuNPs). To immobilize AuNPs, the gold surface was modified to nitrogen termination. The characterization of the electrode surface was performed using an X-ray photoelectron spectroscopy and a scanning electron microscope, while the electrochemical properties of the enzyme electrode were characterized using cyclic voltammetry. Cyclic voltammograms of the prepared electrode for D-glucose in phosphate buffer solution pH 7 showed a new reduction peak at +0.16 V. The currents of the peak were linear in the concentration range of 0.1 M to 0.9 M, indicated that the GOx-AuNP-BDD can be applied for electrochemical glucose detection.

Gold surface plasmon crystal structure based-on polystyrene template for biosensor application.

PubMed

Cheng, Min-Zhuo; Zhang, Jing; Bao, Dequan; Huang, Xiwei

2018-05-21

In this communication, we assembled ordered polystyrene (PS) microsphere array as a template with the drop-coating method, and the oxygen plasma was used to etch the template to adjust the spacing between the PS microspheres. Nano-triangular gold array and silver nano-pyramid array were obtained by ion beam sputtering to deposit precious metal gold and silver. We observed the surface morphology of Au and Au/Ag composite films by scanning electron microscope and characterized the films by X-ray diffraction and ultraviolet/visible light spectrophotometer. The results show that the etching time of oxygen plasma has an obvious effect in adjusting the spacing between PSs and has a significant effect on the morphology of Au structure. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exceptionally Slow Movement of Gold Nanoparticles at a Solid/Liquid Interface Investigated by Scanning Transmission Electron Microscopy.

PubMed

Verch, Andreas; Pfaff, Marina; de Jonge, Niels

2015-06-30

Gold nanoparticles were observed to move at a liquid/solid interface 3 orders of magnitude slower than expected for the movement in a bulk liquid by Brownian motion. The nanoscale movement was studied with scanning transmission electron microscopy (STEM) using a liquid enclosure consisting of microchips with silicon nitride windows. The experiments involved a variation of the electron dose, the coating of the nanoparticles, the surface charge of the enclosing membrane, the viscosity, and the liquid thickness. The observed slow movement was not a result of hydrodynamic hindrance near a wall but instead explained by the presence of a layer of ordered liquid exhibiting a viscosity 5 orders of magnitude larger than a bulk liquid. The increased viscosity presumably led to a dramatic slowdown of the movement. The layer was formed as a result of the surface charge of the silicon nitride windows. The exceptionally slow motion is a crucial aspect of electron microscopy of specimens in liquid, enabling a direct observation of the movement and agglomeration of nanoscale objects in liquid.

Nanoscale imaging of whole cells using a liquid enclosure and a scanning transmission electron microscope.

PubMed

Peckys, Diana B; Veith, Gabriel M; Joy, David C; de Jonge, Niels

2009-12-14

Nanoscale imaging techniques are needed to investigate cellular function at the level of individual proteins and to study the interaction of nanomaterials with biological systems. We imaged whole fixed cells in liquid state with a scanning transmission electron microscope (STEM) using a micrometer-sized liquid enclosure with electron transparent windows providing a wet specimen environment. Wet-STEM images were obtained of fixed E. coli bacteria labeled with gold nanoparticles attached to surface membrane proteins. Mammalian cells (COS7) were incubated with gold-tagged epidermal growth factor and fixed. STEM imaging of these cells resulted in a resolution of 3 nm for the gold nanoparticles. The wet-STEM method has several advantages over conventional imaging techniques. Most important is the capability to image whole fixed cells in a wet environment with nanometer resolution, which can be used, e.g., to map individual protein distributions in/on whole cells. The sample preparation is compatible with that used for fluorescent microscopy on fixed cells for experiments involving nanoparticles. Thirdly, the system is rather simple and involves only minimal new equipment in an electron microscopy (EM) laboratory.

In situ fabrication of quasi-free-standing epitaxial graphene nanoflakes on gold.

PubMed

Leicht, Philipp; Zielke, Lukas; Bouvron, Samuel; Moroni, Riko; Voloshina, Elena; Hammerschmidt, Lukas; Dedkov, Yuriy S; Fonin, Mikhail

2014-04-22

Addressing the multitude of electronic phenomena theoretically predicted for confined graphene structures requires appropriate in situ fabrication procedures yielding graphene nanoflakes (GNFs) with well-defined geometries and accessible electronic properties. Here, we present a simple strategy to fabricate quasi-free-standing GNFs of variable sizes, performing temperature programmed growth of graphene flakes on the Ir(111) surface and subsequent intercalation of gold. Using scanning tunneling microscopy (STM), we show that epitaxial GNFs on a perfectly ordered Au(111) surface are formed while maintaining an unreconstructed, singly hydrogen-terminated edge structure, as confirmed by the accompanying density functional theory (DFT) calculations. Using tip-induced lateral displacement of GNFs, we demonstrate that GNFs on Au(111) are to a large extent decoupled from the Au(111) substrate. The direct accessibility of the electronic states of a single GNF is demonstrated upon analysis of the quasiparticle interference patterns obtained by low-temperature STM. These findings open up an interesting playground for diverse investigations of graphene nanostructures with possible implications for device fabrication.

Hydrogen-Mediated Electron Doping of Gold Clusters As Revealed by In Situ X-ray and UV-vis Absorption Spectroscopy.

PubMed

Ishida, Ryo; Hayashi, Shun; Yamazoe, Seiji; Kato, Kazuo; Tsukuda, Tatsuya

2017-06-01

We previously reported that small (∼1.2 nm) gold clusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) exhibited a localized surface plasmon resonance (LSPR) band at ∼520 nm in the presence of NaBH 4 . To reveal the mechanism of this phenomenon, the electronic structure of Au:PVP during the reaction with NaBH 4 in air was examined by means of in situ X-ray absorption spectroscopy at Au L 3 -edge and UV-vis spectroscopy. These measurements indicated that the appearance of the LSPR band is not associated with the growth in size but is ascribed to electron doping to the Au sp band by the adsorbed H atoms.

Recovery of gold from waste electrical and electronic equipment (WEEE) using ammonium persulfate.

PubMed

Alzate, Andrea; López, Maria Esperanza; Serna, Claudia

2016-11-01

This paper presents a novel methodology to recover gold from waste electrical and electronic equipment (WEEE) using ammonium persulfate ((NH 4 ) 2 S 2 O 8 ). Gold was recovered as a fine coating using substrate oxidation without shredding or grinding process. The WEEE sample was characterized giving values of Au: 1.05g/kg, Fe: 86.00g/kg, Ni: 73.64g/kg, Cu: 26.65g/kg. The effect of (NH 4 ) 2 S 2 O 8 concentration (0.22-1.10M), oxygen (0.0-1.4L/min) and L/S ratio (10-30mL/g) on the main responses (substrate oxidation and Au recovery) was investigated implementing response surface methodology with numerical optimization. A quadratic model was developed and quantities greater than 98% of Au were recovered. The findings presented suggest that, optimized quantities of ammonium persulfate in aqueous highly oxygenated media could be used to extract superficial gold from WEEE. Copyright © 2016 Elsevier Ltd. All rights reserved.

MicroED Structure of Au146(p-MBA)57 at Subatomic Resolution Reveals a Twinned FCC Cluster.

PubMed

Vergara, Sandra; Lukes, Dylan A; Martynowycz, Michael W; Santiago, Ulises; Plascencia-Villa, Germán; Weiss, Simon C; de la Cruz, M Jason; Black, David M; Alvarez, Marcos M; López-Lozano, Xochitl; Barnes, Christopher O; Lin, Guowu; Weissker, Hans-Christian; Whetten, Robert L; Gonen, Tamir; Yacaman, Miguel Jose; Calero, Guillermo

2017-11-16

Solving the atomic structure of metallic clusters is fundamental to understanding their optical, electronic, and chemical properties. Herein we present the structure of the largest aqueous gold cluster, Au 146 (p-MBA) 57 (p-MBA: para-mercaptobenzoic acid), solved by electron micro-diffraction (MicroED) to subatomic resolution (0.85 Å) and by X-ray diffraction at atomic resolution (1.3 Å). The 146 gold atoms may be decomposed into two constituent sets consisting of 119 core and 27 peripheral atoms. The core atoms are organized in a twinned FCC structure, whereas the surface gold atoms follow a C 2 rotational symmetry about an axis bisecting the twinning plane. The protective layer of 57 p-MBAs fully encloses the cluster and comprises bridging, monomeric, and dimeric staple motifs. Au 146 (p-MBA) 57 is the largest cluster observed exhibiting a bulk-like FCC structure as well as the smallest gold particle exhibiting a stacking fault.

MicroED structure of Au146(p-MBA)57 at subatomic resolution reveals a twinned FCC cluster

PubMed Central

Vergara, Sandra; Lukes, Dylan A.; Martynowycz, Michael W.; Santiago, Ulises; Plascencia-Villa, German; Weiss, Simon C.; de la Cruz, M. Jason; Black, David M.; Alvarez, Marcos M.; Lopez-Lozano, Xochitl; Barnes, Christopher O.; Lin, Guowu; Weissker, Hans-Christian; Whetten, Robert L.; Gonen, Tamir; Jose-Yacaman, Miguel; Calero, Guillermo

2018-01-01

Solving the atomic structure of metallic clusters is fundamental to understanding their optical, electronic, and chemical properties. Herein we present the structure of the largest aqueous gold cluster, Au146(p-MBA)57 (p-MBA: para-mercaptobenzoic acid), solved by electron diffraction (MicroED) to subatomic resolution (0.85 Å) and by X-ray diffraction at atomic resolution (1.3 Å). The 146 gold atoms may be decomposed into two constituent sets consisting of 119 core and 27 peripheral atoms. The core atoms are organized in a twinned FCC structure whereas the surface gold atoms follow a C2 rotational symmetry about an axis bisecting the twinning plane. The protective layer of 57 p-MBAs fully encloses the cluster and comprises bridging, monomeric, and dimeric staple motifs. Au146(p-MBA)57 is the largest cluster observed exhibiting a bulk-like FCC structure as well as the smallest gold particle exhibiting a stacking fault. PMID:29072840

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface

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

Sykes, Matthew E.; Stewart, Jon W.; Akselrod, Gleb M.

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers which we propose arise from anisotropic electron-electron scatteringmore » within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold whereas the quantum process of hot electron generation takes place in both components. As a result, our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.« less

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface

DOE PAGES

Sykes, Matthew E.; Stewart, Jon W.; Akselrod, Gleb M.; ...

2017-10-17

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers which we propose arise from anisotropic electron-electron scatteringmore » within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold whereas the quantum process of hot electron generation takes place in both components. As a result, our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.« less

The interplay of plasma treatment and gold coating and ultra-high molecular weight polyethylene: On the cytocompatibility.

PubMed

Novotná, Zdenka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdenka; Hubáček, Tomáš; Ruml, Tomáš; Švorčík, Václav

2017-02-01

We have investigated the application of Ar plasma for creation of nanostructured ultra high molecular weight polyethylene (PE) surface in order to enhance adhesion of mouse embryonic fibroblasts (L929). The aim of this study was to investigate the effect of the interface between plasma-treated and gold-coated PE on adhesion and spreading of cells. The surface properties of pristine samples and its modified counterparts were studied by different experimental techniques (gravimetry, goniometry and X-ray photoelectron spectroscopy (XPS), electrokinetic analysis), which were used for characterization of treated and sputtered layers, polarity and surface chemical structure, respectively. Further, atomic force microscopy (AFM) was employed to study the surface morphology and roughness. Biological responses of cells seeded on PE samples were evaluated in terms of cell adhesion, spreading, morphology and proliferation. Detailed cell morphology and intercellular connections were followed by scanning electron microscopy (SEM). As it was expected the thickness of a deposited gold film was an increasing function of the sputtering time. Despite the fact that plasma treatment proceeded in inert plasma, oxidized degradation products were formed on the PE surface which would contribute to increased hydrophilicity (wettability) of the plasma treated polymer. The XPS method showed a decrease in carbon concentration with increasing plasma treatment. Cell adhesion measured on the interface between plasma treated and gold coated PE was inversely proportional to the thickness of a gold layer on a sample. Copyright © 2016. Published by Elsevier B.V.

A facile synthesis of lipid stabilized gold nanoparticles: a step towards biodegradable biosensors.

PubMed

Abraham, Sinoj; Narine, Suresh S

2011-08-01

A new class of polylactone was successfully synthesized and utilized for the encapsulation and stabilization of gold nanoparticles. Core/shell nanoparticle architecture, in which a layer of this polymer surrounds the nanoparticle core have been investigated both as a means to improve the stability and surface chemistry and as a way of accessing unique physical properties that are not possible from one nano-material alone. Given the fact that only few systems has so far been developed for the encapsulation of nanoparticles, our success in using a new biodegradable biopolymer with inbuilt functionality reveals the robustness of this work. The biodegradability of this polylactone was evaluated using scanning electron microscopy (SEM). The morphology and stability of these gold-polymer hybrids were evaluated by using the transmission electron microscopy (TEM) and UV-VIS spectroscopy.

Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES).

PubMed

Konishi, Yasuhiro; Tsukiyama, Takeshi; Saitoh, Norizoh; Nomura, Toshiyuki; Nagamine, Shinsuke; Takahashi, Yoshio; Uruga, Tomoya

2007-06-01

X-ray absorption near-edge structure spectroscopy (XANES) was successfully employed to determine the gold valence in the metal-reducing bacterium Shewanella algae after exposure to a 1 mM aqueous HAuCl4 solution for 10-120 min. XANES spectra revealed the oxidation state of gold in the bacterial cells to be Au(0) without any contribution from Au(III), demonstrating that S. algae cells can reduce AuCl4- ions to elemental gold. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis confirmed that gold nanoparticles 5-15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable, cell surface location for the easy recovery of biogenic nanoparticles.

The effect of oil-water partition coefficient on the distribution and cellular uptake of liposome-encapsulated gold nanoparticles.

PubMed

Bao, Quan-Ying; Liu, Ai-Yun; Ma, Yu; Chen, Huan; Hong, Jin; Shen, Wen-Bin; Zhang, Can; Ding, Ya

2016-10-01

The shape, size, and surface features of nanoparticles greatly influence the structure and properties of resulting hybrid nanosystems. In this work, gold nanoparticles (GNPs) were modified via S-Au covalent bonding by glycol monomethyl ether thioctate with poly(ethylene glycol) methyl ether of different molecular weights (i.e., 350, 550, and 750Da). These modified GNPs (i.e., GNP350, GNP550, and GNP750) showed different oil-water partition coefficients (Kp), as detected using inductively coupled plasma-atomic emission spectroscopy. The different Kp values of the gold conjugates (i.e., 13.98, 2.11, and 0.036 for GNP350, GNP550, and GNP750, respectively) resulted in different conjugate localization within liposomes, as observed by transmission electron microscopy. In addition, the cellular uptake of hybrid liposomes co-encapsulating gold conjugates and Nile red was evaluated using intracellular fluorescence intensity. The results indicated that precise GNP localization in the hydrophilic or hydrophobic liposome cavity could be achieved by regulating the GNP oil-water partition coefficient via surface modification; such localization could further affect the properties and functions of hybrid liposomes, including their cellular uptake profiles. This study furthers the understanding not only of the interaction between liposomes and inorganic nanoparticles but also of adjusting liposome-gold hybrid nanostructure properties via the surface chemistry of gold materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Silica sacrificial layer-assisted in-plane incorporation of Au nanoparticles into mesoporous titania thin films through different reduction methods.

PubMed

Liang, Chih-Peng; Yamauchi, Yusuke; Liu, Chia-Hung; Wu, Kevin C-W

2013-06-28

This study focuses on the incorporation of gold nanoparticles (Au NPs) into our previously synthesized mesoporous titania thin films consisting of titania nanopillars and inverse mesospace (C. W. Wu, T. Ohsuna, M. Kuwabara and K. Kuroda, J. Am. Chem. Soc., 2006, 128, 4544-4545, denoted as MTTFs). Recently, mesoporous titania materials doped with noble metals such as gold have attracted considerable attention because noble metals can enhance the efficiency of mesoporous titania-based devices. In this research, we attempted to use four different reduction methods (i.e., thermal treatment, photo irradiation, liquid immersion, and vapor contacting) to introduce gold nanoparticles (Au NPs) into MTTFs. The synthesized Au@MTTFs were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). We further systematically investigated the formation mechanism of gold nanoparticles on the external and internal surfaces of the MTTFs. With the assistance of a silica sacrificial layer, well-dispersed Au NPs with sizes of 4.1 nm were obtained inside the MTTF by photo irradiation. The synthesized Au@MTTF materials show great potential in various photo-electronic and photo-catalytic applications.

Nanoparticle treated stainless steel filters for metal vapor sequestration

DOE PAGES

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul; ...

2016-12-07

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown ontomore » various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. Furthermore, the effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.« less

Nanoparticle treated stainless steel filters for metal vapor sequestration

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

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown ontomore » various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. Furthermore, the effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.« less

Dynamics of charge clouds ejected from laser-induced warm dense gold nanofilms

DOE PAGES

Zhou, Jun; Li, Junjie; Correa, Alfredo A.; ...

2014-10-24

We report the first systematic study of the ejected charge dynamics surrounding laser-produced 30-nm warm dense gold films using single-shot femtosecond electron shadow imaging and deflectometry. The results reveal a two-step dynamical process of the ejected electrons under the high pump fluence conditions: an initial emission and accumulation of a large amount of electrons near the pumped surface region followed by the formation of hemispherical clouds of electrons on both sides of the film, which are escaping into the vacuum at a nearly isotropic and constant velocity with an unusually high kinetic energy of more than 300 eV. We alsomore » developed a model of the escaping charge distribution that not only reproduces the main features of the observed charge expansion dynamics but also allows us to extract the number of ejected electrons remaining in the cloud.« less

Dynamics of charge clouds ejected from laser-induced warm dense gold nanofilms

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

Zhou, Jun; Li, Junjie; Correa, Alfredo A.

We report the first systematic study of the ejected charge dynamics surrounding laser-produced 30-nm warm dense gold films using single-shot femtosecond electron shadow imaging and deflectometry. The results reveal a two-step dynamical process of the ejected electrons under the high pump fluence conditions: an initial emission and accumulation of a large amount of electrons near the pumped surface region followed by the formation of hemispherical clouds of electrons on both sides of the film, which are escaping into the vacuum at a nearly isotropic and constant velocity with an unusually high kinetic energy of more than 300 eV. We alsomore » developed a model of the escaping charge distribution that not only reproduces the main features of the observed charge expansion dynamics but also allows us to extract the number of ejected electrons remaining in the cloud.« less

Ensemble of electrophoretically captured gold nanoparticles as a fingerprint of Boltzmann velocity distribution

NASA Astrophysics Data System (ADS)

Hong, S. H.; Kang, M. G.; Lim, J. H.; Hwang, S. W.

2008-07-01

An ensemble of electrophoretically captured gold nanoparticles is exploited to fingerprint their velocity distribution in solution. The electrophoretic capture is performed using a dc biased nanogap electrode, and panoramic scanning electron microscopic images are inspected to obtain the regional density of the captured gold nanoparticles. The regional density profile along the surface of the electrode is in a quantitative agreement with the calculated density of the captured nanoparticles. The calculated density is obtained by counting, in the Boltzmann distribution, the number of nanoparticles whose thermal velocity is smaller than the electrophoretic velocity.

Gold nanoparticles in breast cancer treatment: Promise and potential pitfalls

PubMed Central

Lee, Jihyoun; Chatterjee, Dev Kumar; Lee, Min Hyuk; Krishnan, Sunil

2014-01-01

Despite remarkable achievements in the treatment of breast cancer, some obstacles still remain. Gold nanoparticles may prove valuable in addressing these problems owing to their unique characteristics, including their enhanced permeability and retention in tumor tissue, their light absorbance and surface plasmon resonance in near-infrared light, their interaction with radiation to generate secondary electrons, and their ability to be conjugated with drugs or other agents. Herein, we discuss some basic concepts of gold nanoparticles, and early results from studies regarding their use in breast cancer, including toxicity and side effects. We also discuss these particles’ potential clinical applications. PMID:24556077

Dipole-like electrostatic asymmetry of gold nanorods

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

Kim, Ji -Young; Han, Myung -Geun; Lien, Miao -Bin

The symmetry of metallic nanocolloids, typically envisaged as simple geometrical shapes, is rarely questioned. However, the symmetry considerations are so essential for understanding their electronic structure, optical properties, and biological effects that it is important to reexamine these foundational assumptions for nanocolloids. Gold nanorods (AuNRs) are generally presumed to have nearly perfect geometry of a cylinder and therefore are centrosymmetric. We show that AuNRs, in fact, have a built-in electrostatic potential gradient on their surface and behave as noncentrosymmetric particles. The electrostatic potential gradient of 0.11 to 0.07 V/nm along the long axes of nanorods is observed by off-axis electronmore » holography. Kelvin probe microscopy, secondary electron imaging, energy-filtered transmission electron microscopy, and plasmon mapping reveal that the axial asymmetry is associated with a consistently unequal number of cetyltrimethylammonium bromide moieties capping the two ends of the AuNRs. Electrostatic field maps simulated for the AuNR surface reproduce the holography images. The dipole-like surface potential gradient explains previously puzzling discrepancies in nonlinear optical effects originating from the noncentrosymmetric nature of AuNRs. Furthermore, similar considerations of symmetry breaking are applicable to other nanoscale structures for which the property-governing symmetry of the organic shell may differ from the apparent symmetry of inorganic core observed in standard electron microscopy images.« less

Dipole-like electrostatic asymmetry of gold nanorods

DOE PAGES

Kim, Ji -Young; Han, Myung -Geun; Lien, Miao -Bin; ...

2018-02-09

The symmetry of metallic nanocolloids, typically envisaged as simple geometrical shapes, is rarely questioned. However, the symmetry considerations are so essential for understanding their electronic structure, optical properties, and biological effects that it is important to reexamine these foundational assumptions for nanocolloids. Gold nanorods (AuNRs) are generally presumed to have nearly perfect geometry of a cylinder and therefore are centrosymmetric. We show that AuNRs, in fact, have a built-in electrostatic potential gradient on their surface and behave as noncentrosymmetric particles. The electrostatic potential gradient of 0.11 to 0.07 V/nm along the long axes of nanorods is observed by off-axis electronmore » holography. Kelvin probe microscopy, secondary electron imaging, energy-filtered transmission electron microscopy, and plasmon mapping reveal that the axial asymmetry is associated with a consistently unequal number of cetyltrimethylammonium bromide moieties capping the two ends of the AuNRs. Electrostatic field maps simulated for the AuNR surface reproduce the holography images. The dipole-like surface potential gradient explains previously puzzling discrepancies in nonlinear optical effects originating from the noncentrosymmetric nature of AuNRs. Furthermore, similar considerations of symmetry breaking are applicable to other nanoscale structures for which the property-governing symmetry of the organic shell may differ from the apparent symmetry of inorganic core observed in standard electron microscopy images.« less

Mutual promotion of electrochemical-localized surface plasmon resonance on nanochip for sensitive sialic acid detection.

PubMed

Li, Shuang; Liu, Jinglong; Lu, Yanli; Zhu, Long; Li, Candong; Hu, Lijiang; Li, Jun; Jiang, Jing; Low, Szeshin; Liu, Qingjun

2018-06-01

Localized surface plasmon resonance (LSPR) induced charge separation were concentrated on the metal nanoparticles surface, which made it sensitive to the surface refractive index changes during optical sensing. Similarly, electrochemical detection was based on the electron transformation on the electrode surface. Herein, we fabricated a nanochip by decorating a nanocone-array substrate with gold nanoparticles and silver nanoparticles for dynamic electro-optical spectroscopy. Mercaptophenyl boronic acid (MPBA) was immobilized firmly on the nanochip by the metal-S bond for sensitive sialic acid sensing. Owing to the high stability of gold nanoparticles and the high sensitivity of silver nanoparticles, the nanochip showed good performance in LSPR detection with rich and high responses. Besides, the nanochip also showed sensitive electrical signals during electrochemical detection due to the excitation of the energetic charges from the nanoparticles surface to the reaction system. The dynamic electro-optical spectroscopy was based on a unique combination of LSPR and linear sweep voltammetry (LSV). On the one hand, electrochemical signals activated the electrons on the nanochip to promote the propagation and resonance of surface plasmon. On the other hand, LSPR concentrated the electrons on the nanochip surface, which made the electrons easily driven to enhance the current in electrochemical detection. Results showed that mutual promotion of electrochemical-LSPR on nanochip covered a linear dynamic range from 0.05 mM to 5 mM on selective sialic acid detection with a low detection limit of 17 μM. The synchronous amplification of the electro-optical response during electrochemical-LSPR, opened up a new perspective for efficient and sensitive biochemical detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Extremely thin layer plastification for focused-ion beam scanning electron microscopy: an improved method to study cell surfaces and organelles of cultured cells.

PubMed

VAN Donselaar, E G; Dorresteijn, B; Popov-Čeleketić, D; VAN DE Wetering, W J; Verrips, T C; Boekhout, T; Schneijdenberg, C T W M; Xenaki, A T; VAN DER Krift, T P; Müller, W H

2018-03-25

Since the recent boost in the usage of electron microscopy in life-science research, there is a great need for new methods. Recently minimal resin embedding methods have been successfully introduced in the sample preparation for focused-ion beam scanning electron microscopy (FIB-SEM). In these methods several possibilities are given to remove as much resin as possible from the surface of cultured cells or multicellular organisms. Here we introduce an alternative way in the minimal resin embedding method to remove excess of resin from two widely different cell types by the use of Mascotte filter paper. Our goal in correlative light and electron microscopic studies of immunogold-labelled breast cancer SKBR3 cells was to visualise gold-labelled HER2 plasma membrane proteins as well as the intracellular structures of flat and round cells. We found a significant difference (p < 0.001) in the number of gold particles of selected cells per 0.6 μm 2 cell surface: on average a flat cell contained 2.46 ± 1.98 gold particles, and a round cell 5.66 ± 2.92 gold particles. Moreover, there was a clear difference in the subcellular organisation of these two cells. The round SKBR3 cell contained many organelles, such as mitochondria, Golgi and endoplasmic reticulum, when compared with flat SKBR3 cells. Our next goal was to visualise crosswall associated organelles, septal pore caps, of Rhizoctonia solani fungal cells by the combined use of a heavy metal staining and our extremely thin layer plastification (ETLP) method. At low magnifications this resulted into easily finding septa which appeared as bright crosswalls in the back-scattered electron mode in the scanning electron microscope. Then, a septum was selected for FIB-SEM. Cross-sectioned views clearly revealed the perforate septal pore cap of R. solani next to other structures, such as mitochondria, endoplasmic reticulum, lipid bodies, dolipore septum, and the pore channel. As the ETLP method was applied on two widely different cell types, the use of the ETLP method will be beneficial to correlative studies of other cell model systems and multicellular organisms. © 2018 The Authors. Journal of Microscopy published by JohnWiley & Sons Ltd on behalf of Royal Microscopical Society.

Surface-enhanced localized surface plasmon resonance biosensing of avian influenza DNA hybridization using subwavelength metallic nanoarrays

NASA Astrophysics Data System (ADS)

Kim, Shin Ae; Byun, Kyung Min; Kim, Kyujung; Jang, Sung Min; Ma, Kyungjae; Oh, Youngjin; Kim, Donghyun; Kim, Sung Guk; Shuler, Michael L.; Kim, Sung June

2010-09-01

We demonstrated enhanced localized surface plasmon resonance (SPR) biosensing based on subwavelength gold nanoarrays built on a thin gold film. Arrays of nanogratings (1D) and nanoholes (2D) with a period of 200 nm were fabricated by electron-beam lithography and used for the detection of avian influenza DNA hybridization. Experimental results showed that both nanoarrays provided significant sensitivity improvement and, especially, 1D nanogratings exhibited higher SPR signal amplification compared with 2D nanohole arrays. The sensitivity enhancement is associated with changes in surface-limited reaction area and strong interactions between bound molecules and localized plasmon fields. Our approach is expected to improve both the sensitivity and sensing resolution and can be applicable to label-free detection of DNA without amplification by polymerase chain reaction.

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. Copyright © 2012 Elsevier B.V. All rights reserved.

Ultrathin free-standing close-packed gold nanoparticle films: conductivity and Raman scattering enhancement.

PubMed

Yu, Qing; Huang, Hongwen; Peng, Xinsheng; Ye, Zhizhen

2011-09-01

A simple filtration technique was developed to prepare large scale free-standing close-packed gold nanoparticle ultrathin films using metal hydroxide nanostrands as both barrier layer and sacrificial layer. As thin as 70 nm, centimeter scale robust free-standing gold nanoparticle thin film was obtained. The thickness of the films could be easily tuned by the filtration volumes. The electronic conductivities of these films varied with the size of the gold nanoparticles, post-treatment temperature, and thickness, respectively. The conductivity of the film prepared from 20 nm gold nanoparticles is higher than that of the film prepared from 40 nm gold nanoparticle by filtering the same filtration volume of their solution, respectively. Their conductivities are comparable to that of the 220 nm thick ITO film. Furthermore, these films demonstrated an average surface Raman scattering enhancement up to 6.59 × 10(5) for Rhodamine 6 G molecules on the film prepared from 40 nm gold nanoparticles. Due to a lot of nano interspaces generated from the close-packed structures, two abnormal enhancements and relative stronger intensities of the asymmetrical vibrations at 1534 and 1594 cm(-1) of R6G were observed, respectively. These robust free-standing gold nanoparticle films could be easily transferred onto various solid substrates and hold the potential application for electrodes and surface enhanced Raman detectors. This method is applicable for preparation of other nanoparticle free-standing thin films.

Can para-aryl-dithiols cross-link two plasmonic noble nanoparticles as monolayer dithiolate spacers

USDA-ARS?s Scientific Manuscript database

Para-aryl-dithiols (PADTs, HS-(C6H4)n-SH, n = 1, 2, and 3) have been used extensively in molecular electronics, surface-enhanced Raman spectroscopy (SERS), and quantum electron tunneling between two gold or silver nanoparticles (AuNPs and AgNPs). One popular belief is that these dithiols cross-link ...

Experimental and DFT studies of gold nanoparticles supported on MgO(111) nano-sheets and their catalytic activity.

PubMed

Li, Zhi; Ciobanu, Cristian V; Hu, Juncheng; Palomares-Báez, Juan-Pedro; Rodríguez-López, José-Luis; Richards, Ryan

2011-02-21

A wet chemical preparation of MgO with the (111) facet as the primary surface has recently been reported and with alternating layers of oxygen anions and magnesium cations, this material shows unique chemical and physical properties. The potential to utilize the MgO(111) surface for the immobilization of metal particles is intriguing because the surface itself offers a very different environment for the metal particle with an all oxygen interface, as opposed to the typical (100) facet that possesses alternating oxygen anion and magnesium cation sites on the surface. Gold nanoparticles have demonstrated a broad range of interesting catalytic properties, but are often susceptible to aggregation at high temperatures and are very sensitive to substrate effects. Here, we investigate gold-supported on MgO(111) nanosheets as a catalyst system for the aerobic oxidation of benzyl alcohol. Gold nanoparticles deposited on MgO(111) show an increased level of activity in the solvent-free benzyl alcohol aerobic oxidation as compared to gold nanoparticles deposited on a typical MgO aerogel. TEM studies reveal that the gold nanoparticles have a hemispherical shape while sitting on the main surface of MgO(111) nanosheets, with a large Au-MgO interface. Given that the gold nanoparticles deposited on the two types of MgO have similar size, and that the two types of unmodified MgO show almost the same activities in the blank reaction, we infer that the high activity of Au/MgO(111) is due to the properties of the (111) support and/or those of the gold-support interface. To understand the binding of Au on low-index MgO surfaces and the charge distribution at the surface of the support, we have performed density functional theory (DFT) calculations on all low-index MgO substrates (with and without gold), using a model Au(10) cluster. Due to similar lattice constants of Au(111) and MgO(111) planes, the Au cluster retains its structural integrity and binds strongly on MgO(111) with either oxygen or magnesium termination. Furthermore, we have found that for the (001) and (110) substrates the charges of the ions in the top surface layer have similar values as in bulk MgO, but that on (111) surfaces these charges are significantly different. This difference in surface charge determines the direction of the electronic transfer upon adsorption of gold, such transfer occurring so as to restore the bulk MgO charge values. Using the results from theoretical calculations, we provide an explanation of our observations of increased catalytic activity in the case of the Au/MgO(111) system.

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.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Adhesion between polymers and evaporated gold and nickel films

NASA Technical Reports Server (NTRS)

Yamada, Y.; Wheeler, D. R.; Buckley, D. H.

1984-01-01

To obtain information on the adhesion between metal films and polymeric solids, the adhesion force was measured by means of a tensile pull test. It was found that the adhesion strengths between polymeric solids and gold films evaporated on polymer substrates were (1.11 + or - 0.53) multiplied by 10(6) N/M(2) on PTFE, about 5.49 multiplied by 10(6) N/m(2) on UHMWPE, and 6.54x10(6) on 6/6 nylon. The adhesion strengths for nickel films evaporated on PTFE, UHMWPE, and 6/6 nylon were found to be a factor of 1.7 higher than those for the gold coated PTFE, UHMWPE, and 6/6 nylon. To confirm quantitatively the effect of electron irradiation on the adhesion strength between a PTFE solid and metal films, a tensile pull test was performed on the irradiated PTFE specimens, which were prepared by evaporating nickel or gold on PTFE surfaces irradiated by 2-keV electrons for various times. After irradiation, the adhesion strength increased to (4.92 + or - 0.92)x10(6) N/m(2) for nickel coated PTFE and (1.82 + or - 0.48)x10(6) N/m(2) for gold coated PTFE. The improvement in adhesion for nickel is higher than that for gold.

Electron microscopy study of gold nanoparticles deposited on transition metal oxides.

PubMed

Akita, Tomoki; Kohyama, Masanori; Haruta, Masatake

2013-08-20

Many researchers have investigated the catalytic performance of gold nanoparticles (GNPs) supported on metal oxides for various catalytic reactions of industrial importance. These studies have consistently shown that the catalytic activity and selectivity depend on the size of GNPs, the kind of metal oxide supports, and the gold/metal oxide interface structure. Although researchers have proposed several structural models for the catalytically active sites and have identified the specific electronic structures of GNPs induced by the quantum effect, recent experimental and theoretical studies indicate that the perimeter around GNPs in contact with the metal oxide supports acts as an active site in many reactions. Thus, it is of immense importance to investigate the detailed structures of the perimeters and the contact interfaces of gold/metal oxide systems by using electron microscopy at an atomic scale. This Account describes our investigation, at the atomic scale using electron microscopy, of GNPs deposited on metal oxides. In particular, high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) are valuable tools to observe local atomic structures, as has been successfully demonstrated for various nanoparticles, surfaces, and material interfaces. TEM can be applied to real powder catalysts as received without making special specimens, in contrast to what is typically necessary to observe bulk materials. For precise structure analyses at an atomic scale, model catalysts prepared by using well-defined single-crystalline substrates are also adopted for TEM observations. Moreover, aberration-corrected TEM, which has high spatial resolution under 0.1 nm, is a promising tool to observe the interface structure between GNPs and metal oxide supports including oxygen atoms at the interfaces. The oxygen atoms in particular play an important role in the behavior of gold/metal oxide interfaces, because they may participate in catalytic reaction steps. Detailed information about the interfacial structures between GNPs and metal oxides provides valuable structure models for theoretical calculations which can elucidate the local electronic structure effective for activating a reactant molecule. Based on our observations with HRTEM and HAADF-STEM, we report the detailed structure of gold/metal oxide interfaces.

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.

PubMed

Yuan, D W; Wang, Yang; Zeng, Zhi

2005-03-15

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.

Structure and properties of polyaniline nanocomposite coatings containing gold nanoparticles formed by low-energy electron beam deposition

NASA Astrophysics Data System (ADS)

Wang, Surui; Rogachev, A. A.; Yarmolenko, M. A.; Rogachev, A. V.; Xiaohong, Jiang; Gaur, M. S.; Luchnikov, P. A.; Galtseva, O. V.; Chizhik, S. A.

2018-01-01

Highly ordered conductive polyaniline (PANI) coatings containing gold nanoparticles were prepared by low-energy electron beam deposition method, with emeraldine base and chloroauric acid used as target materials. The molecular and chemical structure of the layers was studied by Fourier transform infrared, Raman, UV-vis and X-ray photoelectron spectroscopy. The morphology of the coatings was investigated by atomic force and transmission electron microscopy. Conductive properties were obtained by impedance spectroscopy method and scanning spreading resistance microscopy mode at the micro- and nanoscale. It was found that the emeraldine base layers formed from the products of electron-beam dispersion have extended, non-conductive polymer chains with partially reduced structure, with the ratio of imine and amine groups equal to 0.54. In case of electron-beam dispersion of the emeraldine base and chloroauric acid, a protoemeraldine structure is formed with conductivity 0.1 S/cm. The doping of this structure was carried out due to hydrochloric acid vapor and gold nanoparticles formed by decomposition of chloroauric acid, which have a narrow size distribution, with the most probable diameter about 40 nm. These gold nanoparticles improve the conductivity of the thin layers of PANI + Au composite, promoting intra- and intermolecular charge transfer of the PANI macromolecules aligned along the coating surface both at direct and alternating voltage. The proposed deposition method of highly oriented, conductive nanocomposite PANI-based coatings may be used in the direct formation of functional layers on conductive and non-conductive substrates.

Combined photothermo-chemotherapy using gold nanoshells on drug-loaded micelles for colorectal cancer treatment

NASA Astrophysics Data System (ADS)

Lee, Shin-Yu; Shieh, Ming-Jium

2018-02-01

Combined photothermo-chemotherapy is a new strategy for cancer treatment which improves the therapeutic outcome by synergistic effects of both therapies. Here, we presented a multifunctional gold nanoshell that exhibited excellent photothermal conversion and delivered the hydrophobic chemotherapy drug, SN-38. The positively charged SN-38-loaded PDMA-PCL micelles were decorated with a gold layer by in situ reduction of chloroauric acid on the surface of micelles. Scanning and transmission electron microscopy images proved micelles were successfully decorated and the resulting gold nanoshells had a spherical morphology with a narrow size distribution. The synthesized gold nanoshells displayed a broad surface plasmon resonance peak in the near-infrared wavelength region and a great photothermal conversion ability. After pegylation, gold nanoshells were stable in biological media and appeared highly biocompatible in the absence of laser irradiation. Upon near-infrared laser irradiation, incident energy was converted into heat by gold nanoshells on SN-38-loaded micelles (SN-38@pGNS), which causes local temperature increase and triggers the release of encapsulated drug. Compared to SN-38, SN-38-loaded micelles, or laser with drug-free gold nanoshells alone, combined photothermo-chemotherapy using SN-38@pGNS with laser irradiation killed colorectal cancer cells with higher efficacy in vitro and demonstrated significant tumor suppression in vivo, suggesting that gold nanoshells on drug-loaded micelles delivered SN-38 and photothermal therapy in synergistic actions and might be a potential candidate for future colorectal cancer therapy.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-05-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01006c

Probing the Sulfur-Modified Capping Layer of Gold Nanoparticles Using Surface Enhanced Raman Spectroscopy (SERS) Effects.

PubMed

Prado, Adilson R; Souza, Danilo Oliveira de; Oliveira, Jairo P; Pereira, Rayssa H A; Guimarães, Marco C C; Nogueira, Breno V; Dixini, Pedro V; Ribeiro, Moisés R N; Pontes, Maria J

2017-12-01

Gold nanoparticles (AuNP) exhibit particular plasmonic properties when stimulated by visible light, which makes them a promising tool to many applications in sensor technology and biomedical applications, especially when associated to sulfur-based compounds. Sulfur species form a great variety of self-assembled structures that cap AuNP and this interaction rules the optical and plasmonic properties of the system. Here, we report the behavior of citrate-stabilized gold nanospheres in two distinct sulfur colloidal solutions, namely, thiocyanate and sulfide ionic solutions. Citrate-capped gold nanospheres were characterized using ultraviolet-visible (UV-Vis) absorption, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). In the presence of sulfur species, we have observed the formation of NP clusters and chain-like structures, giving rise to surface-enhanced effects. Surface-enhanced Raman spectroscopy (SERS) pointed to a modification in citrate vibrational modes, which suggests substitution of citrate by either thiocyanate or sulfide ions with distinct dynamics, as showed by in situ fluorescence. Moreover, we report the emergence of surface-enhanced infrared absorption (SEIRA) effect, which corroborates SERS conclusions. Further, SEIRA shows a great potential as a tool for specification of sulfur compounds in colloidal solutions, which is particularly useful when dealing with sensor technology.

Detoxification of gold nanorods by conjugation with thiolated poly(ethylene glycol) and their assessment as SERS-active carriers of Raman tags

NASA Astrophysics Data System (ADS)

Boca, Sanda C.; Astilean, Simion

2010-06-01

We present an effective, low cost protocol to reduce the toxicity of gold nanorods induced by the presence of cetyltrimethylammonium bromide (CTAB) on their lateral surface as a result of the synthesis process. Here, we use thiolated methoxy-poly(ethylene) glycol (mPEG-SH) polymer to displace most of the CTAB bilayer cap from the particle surface. The detoxification process, chemical and structural stability of as-prepared mPEG-SH-conjugated gold nanorods were characterized using a number of techniques including localized surface plasmon resonance (LSPR), transmission electron microscopy (TEM) and surface-enhanced Raman spectroscopy (SERS). In view of future applications as near-infrared (NIR) nanoheaters in localized photothermal therapy of cancer, we investigated the thermal behaviour of mPEG-SH-conjugated gold nanorods above room temperature. We found a critical temperature at around 40 °C at which the adsorbed polymer layer is susceptible to undergo conformational changes. Additionally, we believe that such plasmonic nanoprobes could act as SERS-active carriers of Raman tags for application in cellular imaging. In this sense we successfully tested them as effective SERS substrates at 785 nm laser line with p-aminothiophenol (pATP) as a tag molecule.

Low-resistance noble metal contacts to high-temperature superconductors

NASA Technical Reports Server (NTRS)

Selim, R.; Caton, R.; Buoncristiani, A. M.; Byvik, C. E.; Edahl, R. A., Jr.

1990-01-01

Low-resistance contacts were made to both YBa2Cu3O(7-x) and Bi2BaSr2Cu2O8, and to related superconducting compounds by melting gold or silver pads onto the samples before the final oxygen treatment. Scanning electron microscope studies show that both gold and silver do not diffuse far from the contact area. The surface contact resistivity of the best contacts made by the melting technique has an upper limit value in the 10 to the -8th ohm sq cm range at 77 K. This contact resistivity shows no significant change in its value over a period of 17 months. Furthermore, an electron radiation dose of 5.7 x 10 to the 17th electron/sq cm only doubled the contact resistivity.

Gold(III) biosorption and bioreduction with the brown alga Fucus vesiculosus.

PubMed

Mata, Y N; Torres, E; Blázquez, M L; Ballester, A; González, F; Muñoz, J A

2009-07-30

In this paper, the bioreduction of Au(III) to Au(0) using biomass of the brown alga Fucus vesiculosus was investigated. The recovery and reduction process took place in two stages with an optimum pH range of 4-9 with a maximum uptake obtained at pH 7. In the first stage, an induction period previous to gold reduction, the variation of pH, redox potential and gold concentration in solution was practically negligible and no color change was observed. In the second stage, the gold reduction was followed by a sharp decrease of gold concentration, pH and redox potential of solution and a color change from yellow to reddish purple. Hydroxyl groups present in the algal polysaccharides were involved in the gold bioreduction. Metallic gold was detected as microprecipitates on the biomass surface and in colloidal form as nanoparticles in the solution. Bioreduction with F. vesiculosus could be an alternative and environmentally friendly process that can be used for recovering gold from dilute hydrometallurgical solutions and leachates of electronic scraps, and for the synthesis of gold nanoparticles of different size and shape.

Time-resolved spectroscopy of self-assembly of CCMV protein capsids

NASA Astrophysics Data System (ADS)

Moore, Jelyn; Aronzon, Dina; Manoharan, V. N.

2008-10-01

In order to gain a deeper understanding of the process a virus undergoes to assemble; the purpose of this study to time resolve the self-assembly of a virus. Cowpea Chlorotic Mottle virus (CCMV), an icosahedral type virus, can assemble without its genetic code (RNA) depending on its chemical and physical surroundings. The surface plasmon resonance (SPR) of colloidal gold particles is known to display a shift when the gold interacts with the proteins of a virus. Surface plasmon resonance is the free electron oscillation occurring at the surface of the gold particle resulting in a characteristic peak location at maximal absorbance and peak width. The shift results from the change in the refractive index of the particles as induced by the presence of the proteins. We hope to detect this shift through total internal reflection microscopy (TIRM). The accomplishments of this research are the completion of the TIR setup and the purification of the virus and its proteins.

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis.

PubMed

Wörner, Michael; Lioubashevski, Oleg; Basel, Matthew T; Niebler, Sandra; Gogritchiani, Eliso; Egner, Nicole; Heinz, Christian; Hoferer, Jürgen; Cipolloni, Michela; Janik, Katharine; Katz, Evgeny; Braun, Andre M; Willner, Itamar; Niederweis, Michael; Bossmann, Stefan H

2007-06-01

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.

Mussel-Inspired Polydopamine Functionalized Plasmonic Nanocomposites for Single-Particle Catalysis.

PubMed

Wang, Jun-Gang; Hua, Xin; Li, Meng; Long, Yi-Tao

2017-01-25

Polydopamine functionalized plasmonic nanocomposites with well-distributed catalytically active small gold nanoislands around large gold core were fabricated without using any chemical reductant or surfactant. The optical properties, surface molecular structures, and ensemble catalytic activity of the gold nanocomposites were investigated by time-of-flight secondary ion mass spectrometry and UV-vis spectroscopy, respectively. Moreover, the considerable catalytic activity of the nanocomposites toward 4-nitrophenol reduction was real time monitored by dark-field spectroscopy techniques at the single-nanoparticle level avoiding averaging effects in bulk systems. According to the obtained plasmonic signals from individual nanocomposites, the electron charging and discharging rates for these nanocomposites during the catalytic process were calculated. Our results offer new insights into the design and synthesis of plasmonic nanocomposites for future catalytic applications as well as a further mechanistic understanding of the electron transfer during the catalytic process at the single-nanoparticle level.

Dark-field microscopy studies of single metal nanoparticles: understanding the factors that influence the linewidth of the localized surface plasmon resonance.

PubMed

Hu, Min; Novo, Carolina; Funston, Alison; Wang, Haining; Staleva, Hristina; Zou, Shengli; Mulvaney, Paul; Xia, Younan; Hartland, Gregory V

2008-01-01

This article provides a review of our recent Rayleigh scattering measurements on single metal nanoparticles. Two different systems will be discussed in detail: gold nanorods with lengths between 30 and 80 nm, and widths between 8 and 30 nm; and hollow gold-silver nanocubes (termed nanoboxes or nanocages depending on their exact morphology) with edge lengths between 100 and 160 nm, and wall thicknesses of the order of 10 nm. The goal of this work is to understand how the linewidth of the localized surface plasmon resonance depends on the size, shape, and environment of the nanoparticles. Specifically, the relative contributions from bulk dephasing, electron-surface scattering, and radiation damping (energy loss via coupling to the radiation field) have been determined by examining particles with different dimensions. This separation is possible because the magnitude of the radiation damping effect is proportional to the particle volume, whereas, the electron-surface scattering contribution is inversely proportional to the dimensions. For the nanorods, radiation damping is the dominant effect for thick rods (widths greater than 20 nm), while electron-surface scattering is dominant for thin rods (widths less than 10 nm). Rods with widths in between these limits have narrow resonances-approaching the value determined by the bulk contribution. For nanoboxes and nanocages, both radiation damping and electron-surface scattering are significant at all sizes. This is because these materials have thin walls, but large edge lengths and, therefore, relatively large volumes. The effect of the environment on the localized surface plasmon resonance has also been studied for nanoboxes. Increasing the dielectric constant of the surroundings causes a red-shift and an increase in the linewidth of the plasmon band. The increase in linewidth is attributed to enhanced radiation damping.

Mecanismes d'ablation du silicium par laser ultrarapide amplifie par des nanostructures plasmoniques

NASA Astrophysics Data System (ADS)

Robitaille, Alexandre

Ultrafast laser interaction with gold nanostructures deposited onto a silicon surface produces considerable field amplification that can result in the ablation of features with dimensions smaller than the diffraction limit. This field amplification in the near field of the nanostructures has been thoroughly investigated in the literature. However, while this is the main phenomenon that permits this nanoablation, energy deposition and diffusion processes cannot be neglected to interpret experimental results. In this work, we study plasmon-enhanced femtosecond laser ablation of silicon using gold nanorods and gold nanospheres to produce sub-diffraction limit holes. Atomic force microscopy and scanning electron microscopy of such features are done and hole depth as a function of fluence is measured. Especially for gold nanorods, hole shape is inconsistent with calculated field distribution. Field distribution alone would let us believe that each nanorod would produce two holes at its both ends. We show that using a model based on a differential equations system describing carriers excitation and diffusion, both shape and depth of the nanoholes can be predicted. Importance of the diffusion process is shown to arise from the extreme localization of the deposited energy around the nanostructure, compared to what is usually the case for conventional ablation of a surface. The characteristic shape of holes is revealed as a striking signature of the energy distribution through the electron-phonon carrier density dependant interaction.

Orange pectin mediated growth and stability of aqueous gold and silver nanocolloids

NASA Astrophysics Data System (ADS)

Nigoghossian, Karina; dos Santos, Molíria V.; Barud, Hernane S.; da Silva, Robson R.; Rocha, Lucas A.; Caiut, José M. A.; de Assunção, Rosana M. N.; Spanhel, Lubomir; Poulain, Marcel; Messaddeq, Younes; Ribeiro, Sidney J. L.

2015-06-01

The role of orange based pectin in the nucleation and growth of silver and gold nanoparticles is addressed. Pectin is a complex polysaccharide found in fruits such as oranges, lemons, passion fruits or apples. It displays smooth and hairy chain regions containing hydroxyl-, ester-, carboxylate- and eventually amine groups that can act as surface ligands interacting under various pH conditions more or less efficiently with growing nanometals. Here, a high methoxy pectin (>50% esterified) was used as a stabilizer/reducing agent in the preparation of gold, silver and silver-gold nanoparticles. Commercial pectin (CP) and pectin extracted from orange bagasse (OP) were used. Optionally, trisodium citrate or oxalic acid we used to reduce AgNO3 and HAuCl4 in aqueous environment. Characterization methods included UV-vis absorption spectroscopy, transmission electron microscopy, electron diffraction and energy-dispersive X-ray spectroscopy. The results show that under different pH conditions, pectin and reducing agents allow producing various nanostructures shapes (triangles, spheres, rods, octahedrons and decahedrons) often with high polydispersity and sizes ranging between 5 nm and 30 nm. In addition, depending on Ag/Au-ratio and pH, the surface plasmon bands can be continuously shifted between 410 nm and 600 nm. Finally, pectin seems to be a highly efficient stabilizer of the colloidal systems that show a remarkable stability and unchanged optical spectral response even after five years.

Diastase induced green synthesis of bilayered reduced graphene oxide and its decoration with gold nanoparticles.

PubMed

Maddinedi, Sireesh Babu; Mandal, Badal Kumar; Patil, Sagar Hindurao; Andhalkar, Vaibhav Vilas; Ranjan, Shivendu; Dasgupta, Nandita

2017-01-01

In this paper, we report an enzyme dependent, green one-pot deoxygenation cum decoration method to synthesize diastase-conjugated reduced graphene oxide (DRG) nanosheets, DRG/gold nanoparticles (DRG/Au) composite. The DRG synthesis was completed in 7h under heating at 90°C on water bath. Selected area electron diffraction (SAED) and Atomic force microscopy (AFM) study has revealed the formation of bilayered reduced graphene oxide sheets. Transmission electron microscopy (TEM) images of DRG/Au composite have shown the uniform decoration of gold nanoparticles (AuNPs) onto the DRG nanosheet surface. Fourier transform infrared spectroscopy (FTIR) and Raman results additionally have shown the functionalization of enzyme molecules onto the DRG nanosheet surface after reduction making it as an effective platform towards the efficient binding of gold nanoparticles. In vitro cytotoxicity studies by MTT assay on A549 and HCT116 cell lines exhibited that the cytotoxicity of the prepared graphene oxide (GO), DRG and DRG/Au is dose dependant. These results have shown that this synthetic method is effective for the production of large scale graphene in a low cost, simple and green method. Since this process avoids the use of hazardous and toxic substances, the produced DRG/Au composites are likely to offer various potential applications in biology and medicine. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultrafast nonlinear dynamics of thin gold films due to an intrinsic delayed nonlinearity

NASA Astrophysics Data System (ADS)

Bache, Morten; Lavrinenko, Andrei V.

2017-09-01

Using long-range surface plasmon polaritons light can propagate in metal nano-scale waveguides for ultracompact opto-electronic devices. Gold is an important material for plasmonic waveguides, but although its linear optical properties are fairly well understood, the nonlinear response is still under investigation. We consider the propagation of pulses in ultrathin gold strip waveguides, modeled by the nonlinear Schrödinger equation. The nonlinear response of gold is accounted for by the two-temperature model, revealing it as a delayed nonlinearity intrinsic in gold. The consequence is that the measured nonlinearities are strongly dependent on pulse duration. This issue has so far only been addressed phenomenologically, but we provide an accurate estimate of the quantitative connection as well as a phenomenological theory to understand the enhanced nonlinear response as the gold thickness is reduced. In comparison with previous works, the analytical model for the power-loss equation has been improved, and can be applied now to cases with a high laser peak power. We show new fits to experimental data from the literature and provide updated values for the real and imaginary parts of the nonlinear susceptibility of gold for various pulse durations and gold layer thicknesses. Our simulations show that the nonlinear loss is inhibiting efficient nonlinear interaction with low-power laser pulses. We therefore propose to design waveguides suitable for the mid-IR, where the ponderomotive instantaneous nonlinearity can dominate over the delayed hot-electron nonlinearity and provide a suitable plasmonics platform for efficient ultrafast nonlinear optics.

Acute toxicity and pharmacokinetics of 13 nm-sized PEG-coated gold nanoparticles

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

Cho, Wan-Seob; Cho, Minjung; Jeong, Jinyoung

2009-04-01

In general, gold nanoparticles are recognized as being as nontoxic. Still, there have been some reports on their toxicity, which has been shown to depend on the physical dimension, surface chemistry, and shape of the nanoparticles. In this study, we carry out an in vivo toxicity study using 13 nm-sized gold nanoparticles coated with PEG (MW 5000). In our findings the 13 nm sized PEG-coated gold nanoparticles were seen to induce acute inflammation and apoptosis in the liver. These nanoparticles were found to accumulate in the liver and spleen for up to 7 days after injection and to have longmore » blood circulation times. In addition, transmission electron microscopy showed that numerous cytoplasmic vesicles and lysosomes of liver Kupffer cells and spleen macrophages contained the PEG-coated gold nanoparticles. These findings of toxicity and kinetics of PEG-coated gold nanoparticles may have important clinical implications regarding the safety issue as PEG-coated gold nanoparticles are widely used in biomedical applications.« less

Gold surfaces and nanoparticles are protected by Au(0)-thiyl species and are destroyed when Au(I)-thiolates form.

PubMed

Reimers, Jeffrey R; Ford, Michael J; Halder, Arnab; Ulstrup, Jens; Hush, Noel S

2016-03-15

The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)-thiyl, with Au(I)-thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)-thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s-d hybridization and charge polarization effects that perturbatively mix in some Au(I)-thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)-thiolate involvement. Predictions that Brust-Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)-thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established.

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

PubMed Central

Reimers, Jeffrey R.; Ford, Michael J.; Halder, Arnab; Ulstrup, Jens; Hush, Noel S.

2016-01-01

The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)–thiyl, with Au(I)–thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)–thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s–d hybridization and charge polarization effects that perturbatively mix in some Au(I)–thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)–thiolate involvement. Predictions that Brust–Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)–thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established. PMID:26929334

Adsorption of doxorubicin on citrate-capped gold nanoparticles: insights into engineering potent chemotherapeutic delivery systems

NASA Astrophysics Data System (ADS)

Curry, Dennis; Cameron, Amanda; MacDonald, Bruce; Nganou, Collins; Scheller, Hope; Marsh, James; Beale, Stefanie; Lu, Mingsheng; Shan, Zhi; Kaliaperumal, Rajendran; Xu, Heping; Servos, Mark; Bennett, Craig; Macquarrie, Stephanie; Oakes, Ken D.; Mkandawire, Martin; Zhang, Xu

2015-11-01

Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates.Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates. Electronic supplementary information (ESI) available: DOX-AuNP absorption spectra and colored solution images, citrate displacement data, original DOX-AuNP loading isotherm, XPS data and TEM micrographs, modelling data. See DOI: 10.1039/c5nr05826k

Construction and direct electrochemistry of orientation controlled laccase electrode

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

Li, Ying; Zhang, Jiwei; Huang, Xirong, E-mail: xrhuang@sdu.edu.cn

2014-03-28

Highlights: • A recombinant laccase with Cys-6×His tag at the N or C terminus was generated. • Orientation controlled laccase electrodes were constructed via self assembly. • The electrochemical behavior of laccase electrodes was orientation dependent. • The C terminus tagged laccase was better for bioelectrocatalytic reduction of O{sub 2}. - Abstract: A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, usingmore » genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O{sub 2} reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells.« less

Scanning electron microscopy and X-ray energy dispersive spectroscopy - useful tools in the analysis of pharmaceutical products

NASA Astrophysics Data System (ADS)

Sarecka-Hujar, Beata; Balwierz, Radoslaw; Ostrozka-Cieslik, Aneta; Dyja, Renata; Lukowiec, Dariusz; Jankowski, Andrzej

2017-11-01

The quality of the drug, its purity and identification of degradation products provide the highest quality of pharmaceutical products. The energy dispersive spectroscopy (EDS) method analyses the percentage of each element form as well as their distribution, and morphological characteristics of the drug form. We analysed the usefulness of EDS method in testing orally disintegrating tablets (ODT) with trimetazidine hydrochloride with high resolution scanning electron microscopy (SEM, SUPRA25 Carl Zeiss company) with spectrophotometer equipped with an X-ray energy dispersion (EDAX Company). The samples of the analysed tablets were imaged after applying conductive layers of gold on their surface. In the EDS analysis the compositions of each sample of the obtained tablets were observed to be virtually identical. The differences in the content of carbon and oxygen came from differences in the composition of particular tablets. The presence of gold in the composition resulted from the sputtering the surface of tablets with gold during the analysis. Knowing the composition of the tablet, SEM-EDS method helps to locate and identify the impurities and degradation products of the compounds, leading to a better understanding of the mechanisms of their formation.

Molecular and supramolecular control of the work function of an inorganic electrode with self-assembled monolayer of umbrella-shaped fullerene derivatives.

PubMed

Lacher, Sebastian; Matsuo, Yutaka; Nakamura, Eiichi

2011-10-26

The surface properties of inorganic substrates can be altered by coating with organic molecules, which may result in the improvement of the properties suitable for electronic or biological applications. This article reports a systematic experimental study on the influence of the molecular and supramolecular properties of umbrella-shaped penta(organo)[60]fullerene derivatives, and on the work function and the water contact angle of indium-tin oxide (ITO) and gold surfaces. We could relate these macroscopic characteristics to single-molecular level properties, such as ionization potential and molecular dipole. The results led us to conclude that the formation of a SAM of a polar compound generates an electronic field through intermolecular interaction of the molecular charges, and this field makes the overall dipole of the SAM much smaller than the one expected from the simple sum of the dipoles of all molecules in the SAM. This effect, which was called depolarization and previously discussed theoretically, is now quantitatively probed by experiments. The important physical properties in surface science such as work function, ionization potential, and water contact angles have been mutually correlated at the level of molecular structures and molecular orientations on the substrate surface. We also found that the SAMs on ITO and gold operate under the same principle except that the "push-back" effect operates specifically for gold. The study also illustrates the ability of the photoelectron yield spectroscopy technique to rapidly measure the work function of a SAM-covered substrate and the ionization potential value of a molecule on the surface.

NCO-sP(EO-stat-PO) coatings on gold sensors--a QCM study of hemocompatibility.

PubMed

Sinn, Stefan; Eichler, Mirjam; Müller, Lothar; Bünger, Daniel; Groll, Jürgen; Ziemer, Gerhard; Rupp, Frank; Northoff, Hinnak; Geis-Gerstorfer, Jürgen; Gehring, Frank K; Wendel, Hans P

2011-01-01

The reliability of implantable blood sensors is often hampered by unspecific adsorption of plasma proteins and blood cells. This not only leads to a loss of sensor signal over time, but can also result in undesired host vs. graft reactions. Within this study we evaluated the hemocompatibility of isocyanate conjugated star shaped polytheylene oxide-polypropylene oxide co-polymers NCO-sP(EO-stat-PO) when applied to gold surfaces as an auspicious coating material for gold sputtered blood contacting sensors. Quartz crystal microbalance (QCM) sensors were coated with ultrathin NCO-sP(EO-stat-PO) films and compared with uncoated gold sensors. Protein resistance was assessed by QCM measurements with fibrinogen solution and platelet poor plasma (PPP), followed by quantification of fibrinogen adsorption. Hemocompatibility was tested by incubation with human platelet rich plasma (PRP). Thrombin antithrombin-III complex (TAT), β-thromboglobulin (β-TG) and platelet factor 4 (PF4) were used as coagulation activation markers. Furthermore, scanning electron microscopy (SEM) was used to visualize platelet adhesion to the sensor surfaces. Compared to uncoated gold sensors, NCO-sP(EO-stat-PO) coated sensors revealed significant better resistance against protein adsorption, lower TAT generation and a lower amount of adherent platelets. Moreover, coating with ultrathin NCO-sP(EO-stat-PO) films creates a cell resistant hemocompatible surface on gold that increases the chance of prolonged sensor functionality and can easily be modified with specific receptor molecules.

NCO-sP(EO-stat-PO) Coatings on Gold Sensors—a QCM Study of Hemocompatibility

PubMed Central

Sinn, Stefan; Eichler, Mirjam; Müller, Lothar; Bünger, Daniel; Groll, Jürgen; Ziemer, Gerhard; Rupp, Frank; Northoff, Hinnak; Geis-Gerstorfer, Jürgen; Gehring, Frank K.; Wendel, Hans P.

2011-01-01

The reliability of implantable blood sensors is often hampered by unspecific adsorption of plasma proteins and blood cells. This not only leads to a loss of sensor signal over time, but can also result in undesired host vs. graft reactions. Within this study we evaluated the hemocompatibility of isocyanate conjugated star shaped polytheylene oxide—polypropylene oxide co-polymers NCO-sP(EO-stat-PO) when applied to gold surfaces as an auspicious coating material for gold sputtered blood contacting sensors. Quartz crystal microbalance (QCM) sensors were coated with ultrathin NCO-sP(EO-stat-PO) films and compared with uncoated gold sensors. Protein resistance was assessed by QCM measurements with fibrinogen solution and platelet poor plasma (PPP), followed by quantification of fibrinogen adsorption. Hemocompatibility was tested by incubation with human platelet rich plasma (PRP). Thrombin antithrombin-III complex (TAT), β-thromboglobulin (β-TG) and platelet factor 4 (PF4) were used as coagulation activation markers. Furthermore, scanning electron microscopy (SEM) was used to visualize platelet adhesion to the sensor surfaces. Compared to uncoated gold sensors, NCO-sP(EO-stat-PO) coated sensors revealed significant better resistance against protein adsorption, lower TAT generation and a lower amount of adherent platelets. Moreover, coating with ultrathin NCO-sP(EO-stat-PO) films creates a cell resistant hemocompatible surface on gold that increases the chance of prolonged sensor functionality and can easily be modified with specific receptor molecules. PMID:22163899

Synthesis of gold nanoparticles using silk fibroin and their characterization

NASA Astrophysics Data System (ADS)

Gowda, Mahadeva; Harisha, K. S.; Ranjana, T.; Harish, K. V.; Narayana, B.; Byrappa, K.; Sangappa, Y.

2018-05-01

The synthesis of metal nanoparticales by environmentally friendly processes is an important aspect of nanotechnology today. One such approach that shows immense potential is based on the in situ synthesis of gold nanoparticles (AuNPs) using naturally available materials such as aqueous silk fibroin (SF) obtained from Bombyx mori silk. The UV-visible absorption study revealed the formation of AuNPs by showing characteristic surface plasmon resonance (SPR) band at 525 nm. The X-ray diffraction (XRD) analysis study suggests the synthesized gold nanoparticles are FCC crystal structure. The transmission electron microscopy (TEM) images showed that the formed AuNPs are spherical in shape with smooth edges.

MICROSCOPIC USES OF NANOGOLD.

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

HAINFELD,J.F.POWELL,R.D.FURUYA,F.R.

2003-04-17

Gold has been used for immunocytochemistry since 1971 when Faulk and Taylor discovered adsorption of antibodies to colloidal gold. It is an ideal label for electron microscopy (EM) due to its high atomic number, which scatters electrons efficiently, and the fact that preparative methods have been developed to make uniform particles in the appropriate size range of 5 to 30 nm. Use in light microscopy (LM) generally requires silver enhancement (autometallography; AMG) of these small gold particles. Significant advances in this field since that time have included a better understanding of the conditions for best antibody adsorption, more regular goldmore » size production, adsorption of other useful molecules, like protein A, and advances in silver enhancement. Many studies have also been accomplished showing the usefulness of these techniques to cell biology and biomedical research. A further advance in this field was the development of Nanogold{trademark}, a 1.4 nm gold cluster. A significant difference from colloidal gold is that Nanogold is actually a coordination compound containing a gold core covalently linked to surface organic groups. These in turn may be covalently attached to antibodies. This approach to immunolabeling has several advantages compared to colloidal gold such as vastly better penetration into tissues, generally greater sensitivity, and higher density of labeling. Since Nanogold is covalently coupled to antibodies, it may also be directly coupled to almost any protein, peptide, carbohydrate, or molecule of interest, including molecules which do not adsorb to colloidal gold. This increases the range of probes possible, and expands the applications of gold labeling.« less

The graphene-gold interface and its implications for nanoelectronics.

PubMed

Sundaram, Ravi S; Steiner, Mathias; Chiu, Hsin-Ying; Engel, Michael; Bol, Ageeth A; Krupke, Ralph; Burghard, Marko; Kern, Klaus; Avouris, Phaedon

2011-09-14

We combine optical microspectroscopy and electronic measurements to study how gold deposition affects the physical properties of graphene. We find that the electronic structure, the electron-phonon coupling, and the doping level in gold-plated graphene are largely preserved. The transfer lengths for electrons and holes at the graphene-gold contact have values as high as 1.6 μm. However, the interfacial coupling of graphene and gold causes local temperature drops of up to 500 K in operating electronic devices.

Nanoscale Imaging of Whole Cells Using a Liquid Enclosure and a Scanning Transmission Electron Microscope

PubMed Central

Peckys, Diana B.; Veith, Gabriel M.; Joy, David C.; de Jonge, Niels

2009-01-01

Nanoscale imaging techniques are needed to investigate cellular function at the level of individual proteins and to study the interaction of nanomaterials with biological systems. We imaged whole fixed cells in liquid state with a scanning transmission electron microscope (STEM) using a micrometer-sized liquid enclosure with electron transparent windows providing a wet specimen environment. Wet-STEM images were obtained of fixed E. coli bacteria labeled with gold nanoparticles attached to surface membrane proteins. Mammalian cells (COS7) were incubated with gold-tagged epidermal growth factor and fixed. STEM imaging of these cells resulted in a resolution of 3 nm for the gold nanoparticles. The wet-STEM method has several advantages over conventional imaging techniques. Most important is the capability to image whole fixed cells in a wet environment with nanometer resolution, which can be used, e.g., to map individual protein distributions in/on whole cells. The sample preparation is compatible with that used for fluorescent microscopy on fixed cells for experiments involving nanoparticles. Thirdly, the system is rather simple and involves only minimal new equipment in an electron microscopy (EM) laboratory. PMID:20020038

Shape Effects in Nanoparticle-Based Imaging Agents

NASA Astrophysics Data System (ADS)

Culver, Kayla Shani Brook

At the nanoscale, material properties become highly size and shape dependent. These properties can be manipulated and exploited for a variety of biomedical applications, including sensing, drug delivery, diagnostics, and imaging. In particular, nanoparticles of different materials, sizes and shapes have been developed as high-performance contrast agents for optical, electron, and medical imaging. In this thesis, I focus on gold nanoparticles because they are widely used as contrast agents in multiple types of imaging modalities. Additionally, the surface of gold can be readily functionalized with ligands and the structure of the particles can be manipulated to modulate their performance as imaging agents. The properties of nanoparticles can generate contrast directly. For example, the light scattering properties of gold particles can be visualized in optical microscopy, the high electron density of gold produces contrast in electron microscopy, and the x-ray absorption properties of gold can be detected in medical x-ray and computed tomography imaging. Alternatively, the properties of the nanomaterial can be exploited to modulate the signal produced by other molecules that are bound to the particle surface. The light emission of molecular fluorophores can be quenched or dramatically increased by coupling to the optical field enhancements of gold nanoparticles, and the performance of gadolinium (Gd(III))-based magnetic resonance imaging (MRI) contrast agents can be increased by coupling to the rotational motion of nanoparticles. In this dissertation, I focus specifically on how the structure of star-shaped gold particles (nanostars) can be exploited as single-particle optical probes and to dramatically enhance the relaxivity of Gd(III) bound to the surface. Differential interference contrast (DIC) is a type of wide-field diffraction-limited optical microscopy that is commonly used by biologists to image cells without labels. Here, I demonstrate the DIC can be used to characterize complex nanoscale structural features and spectral properties of gold nanostars. Specifically, by evaluating the DIC contrast and image patterns of single nanostars, I distinguished between flat and 3D geometries, identified nanostars with 4-fold symmetry, and determined nanostar orientation. Additionally, in multi-wavelength DIC imaging, an inversion in the contrast could be used to indicate the localized surface plasmon resonance of nanostars with 1 and 2 branches. Next, I used DIC to track the rotational and translational dynamics of functionalized nanostars interacting with live cell membranes. The DNA aptamer ligand on the nanostars specifically targets the transmembrane receptor HER2. I tracked single nanoconstructs over long time scales (˜ 20 minutes per particle, > 80 minutes total) with high temporal resolution (4 fps) and found that analysis of the DIC contrast fluctuations could be used to identify multiple modes of rotational behavior on the cell membrane. I developed MATLAB programs to track the moving nanoconstructs in a dynamic background environment and set up a customized live-cell perfusion chamber that is compatible with the bulky high numerical aperture optics. The combination of the environmental control in the chamber and the low light levels required to visualize single nanostars make this technique optimal for long-term tracking of single nanoconstructs in viable cells. Although nanoparticle size is well-known to influence the relaxivity of Gd(III)-based MRI contrast agents that are attached to the surface, the role of nanoparticle shape was previously unknown. Recently, we discovered that the relaxivity of Gd(III)-conjugated DNA bound to nanostars was three-fold higher than that of analogous spherical nanoconstructs. The relaxivities reached enhancements that were beyond limits that could be explained theoretically by size effects alone. We found that the extremely large enhancements could be explained by elongated water residence times in the second coordination sphere. Here, we investigated in detail how the complex structure of the nanostars mediates these effects. By sorting the nanostars by shape, we found that relaxivity increases with increasing branch number. Thus, we hypothesize that the confinement of the Gd(III)-DNA in the regions of negative surface curvature between branches creates a dense hydrophilic environment that promotes relaxation of second-sphere water molecules. These results demonstrate that shape is a new parameter that can be tuned in the optimization of nanoparticle-based T1 MRI contrast agents. It is important to characterize the potential toxicity of nanomaterials that are intended for use in biomedical applications. Thus, I evaluated the in vivo biodistribution and acute toxicity in rats of gold nanostars functionalized with DNA. As expected for nanoparticles of this size (˜50 nm) and surface charge (negative), the primary clearance mechanism was through the liver and spleen. Importantly, even at the highest dose, no signs of acute toxicity were observed based on hematology, clinical chemistry, and histology, indicating that DNA-coated gold nanostars are highly biocompatible. Additionally, I exploited the high contrast of gold in electron microscopy to track the fate of the nanoconstructs within organs ex vivo. In the liver, the nanoconstructs were sequestered in lysosomes of Kupffer cells. The electron microscopy analysis also indicated that the branched structure of the nanostars was intact even after 2 weeks in the liver, which is important for shape-dependent applications.

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules.

PubMed

Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

2017-01-26

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans -1,2-bis(4-pyridyl)ethylene (BPE).

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

NASA Astrophysics Data System (ADS)

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-01

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water. Electronic supplementary information (ESI) available: Synthetic protocols, XPS measurements, contact angle measurements, additional cyclic voltammograms and electrochemical impedance spectroscopy. See DOI: 10.1039/c5nr06977g

Oxide mediated liquid-solid growth of high aspect ratio aligned gold silicide nanowires on Si(110) substrates.

PubMed

Bhatta, Umananda M; Rath, Ashutosh; Dash, Jatis K; Ghatak, Jay; Yi-Feng, Lai; Liu, Chuan-Pu; Satyam, P V

2009-11-18

Silicon nanowires grown using the vapor-liquid-solid method are promising candidates for nanoelectronics applications. The nanowires grow from an Au-Si catalyst during silicon chemical vapor deposition. In this paper, the effect of temperature, oxide at the interface and substrate orientation on the nucleation and growth kinetics during formation of nanogold silicide structures is explained using an oxide mediated liquid-solid growth mechanism. Using real time in situ high temperature transmission electron microscopy (with 40 ms time resolution), we show the formation of high aspect ratio ( approximately 15.0) aligned gold silicide nanorods in the presence of native oxide at the interface during in situ annealing of gold thin films on Si(110) substrates. Steps observed in the growth rate and real time electron diffraction show the existence of liquid Au-Si nano-alloy structures on the surface besides the un-reacted gold nanostructures. These results might enable us to engineer the growth of nanowires and similar structures with an Au-Si alloy as a catalyst.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers

NASA Astrophysics Data System (ADS)

Del Rosso, T.; Rey, N. A.; Rosado, T.; Landi, S.; Larrude, D. G.; Romani, E. C.; Freire Junior, F. L.; Quinteiro, S. M.; Cremona, M.; Aucelio, R. Q.; Margheri, G.; Pandoli, O.

2016-06-01

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers.

PubMed

Del Rosso, T; Rey, N A; Rosado, T; Landi, S; Larrude, D G; Romani, E C; Junior, F L Freire; Quinteiro, S M; Cremona, M; Aucelio, R Q; Margheri, G; Pandoli, O

2016-06-24

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Flexible, Cuttable, and Self-Waterproof Bending Strain Sensors Using Microcracked Gold Nanofilms@Paper Substrate.

PubMed

Liao, Xinqin; Zhang, Zheng; Liang, Qijie; Liao, Qingliang; Zhang, Yue

2017-02-01

Rapid advances in functional sensing electronics place tremendous demands on innovation toward creative uses of versatile advanced materials and effective designs of device structures. Here, we first report a feasible and effective fabrication strategy to integrate commercial abrasive papers with microcracked gold (Au) nanofilms to construct cuttable and self-waterproof crack-based resistive bending strain sensors. Via introducing surface microstructures, the sensitivities of the bending strain sensors are greatly enhanced by 27 times than that of the sensors without surface microstructures, putting forward an alternative suggestion for other flexible electronics to improve their performances. Besides, the bending strain sensors also endow rapid response and relaxation time of 20 ms and ultrahigh stability of >18 000 strain loading-unloading cycles in conjunction with flexibility and robustness. In addition, the concepts of cuttability and self-waterproofness (attain and even surpass IPX-7) of the bending strain sensors have been demonstrated. Because of the distinctive sensing properties, flexibility, cuttability, and self-waterproofness, the bending strain sensors are attractive and promising for wearable electronic devices and smart health monitoring system.

In-plane conductance of thin films as a probe of surface chemical environment: Adsorbate effects on film electronic properties of indium tin oxide and gold

NASA Astrophysics Data System (ADS)

Swint, Amy Lynn

Changes in the in-plane conductance of conductive thin films are observed as a result of chemical adsorption at the surface. Reaction of the indium tin oxide (ITO) surface with Bronsted acids (bases) leads to increases (decreases) in its in-plane conductance as measured by a four-point probe configuration. The conductance varies monotonically with pH suggesting that the degree of surface protonation or hydroxylation controls the surface charge density, which in turn affects the width of the n-type depletion layer, and ultimately the in-plane conductance. Measurements at constant pH with a series of tetraalkylammonium hydroxide species of varying cation size indicate that surface dipoles also affect ITO conductance by modulating the magnitude of the surface polarization. Modulating the double layer with varying aqueous salt solutions also affects ITO conductance, though not to the same degree as strong Bronsted acids and bases. Solvents of varying dielectric constant and proton donating ability (ethanol, dimethylformamide) decrease ITO conductance relative to H2O. In addition, changing solvent gives rise to thermally-derived conductance transients, which result from exothermic solvent mixing. The self-assembly of alkanethiols at the surface increases the conductance of ITO films, most likely through carrier population effects. In all cases examined the combined effects of surface charge, adsorbed dipole layer magnitude and carrier injection are responsible for altering the ITO conductance. Besides being directly applicable to the control of electronic properties, these results also point to the use of four-point probe resistance measurements in condensed phase sensing applications. Ultrasensitive conductance-based gas phase sensing of organothiol adsorption to gold nanowires is accomplished with a limit of detection in the 105 molecule range. Further refinement of the inherently low noise resistance measurement may lead to observation of single adsorption events at the gold surface.

Gold atoms and dimers on amorphous SiO(2): calculation of optical properties and cavity ringdown spectroscopy measurements.

PubMed

Del Vitto, Annalisa; Pacchioni, Gianfranco; Lim, Kok Hwa; Rösch, Notker; Antonietti, Jean-Marie; Michalski, Marcin; Heiz, Ulrich; Jones, Harold

2005-10-27

We report on the optical absorption spectra of gold atoms and dimers deposited on amorphous silica in size-selected fashion. Experimental spectra were obtained by cavity ringdown spectroscopy. Issues on soft-landing, fragmentation, and thermal diffusion are discussed on the basis of the experimental results. In parallel, cluster and periodic supercell density functional theory (DFT) calculations were performed to model atoms and dimers trapped on various defect sites of amorphous silica. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [[triple bond]Si(.-)], nonbridging oxygen [[triple bond]Si-O(.-)], and the silanolate group [[triple bond]Si-O(-)] act as trapping centers for the gold particles. The results are not only important for understanding the chemical bonding of atoms and clusters on oxide surfaces, but they will also be of fundamental interest for photochemical studies of size-selected clusters on surfaces.

Green Synthesis, Characterization and Application of Proanthocyanidins-Functionalized Gold Nanoparticles

PubMed Central

Biao, Linhai; Tan, Shengnan; Meng, Qinghuan; Gao, Jing; Zhang, Xuewei; Liu, Zhiguo; Fu, Yujie

2018-01-01

Green synthesis of gold nanoparticles using plant extracts is one of the more promising approaches for obtaining environmentally friendly nanomaterials for biological applications and environmental remediation. In this study, proanthocyanidins-functionalized gold nanoparticles were synthesized via a hydrothermal method. The obtained gold nanoparticles were characterized by ultraviolet and visible spectrophotometry (UV-Vis), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray diffraction (XRD) measurements. UV-Vis and FTIR results indicated that the obtained products were mainly spherical in shape, and that the phenolic hydroxyl of proanthocyanidins had strong interactions with the gold surface. TEM and XRD determination revealed that the synthesized gold nanoparticles had a highly crystalline structure and good monodispersity. The application of proanthocyanidins-functionalized gold nanoparticles for the removal of dyes and heavy metal ions Ni2+, Cu2+, Cd2+ and Pb2+ in an aqueous solution was investigated. The primary results indicate that proanthocyanidins-functionalized gold nanoparticles had high removal rates for the heavy metal ions and dye, which implies that they have potential applications as a new kind of adsorbent for the removal of contaminants in aqueous solution. PMID:29361727

Electrochemical Corrosion of Stainless Steel in Thiosulfate Solutions Relevant to Gold Leaching

NASA Astrophysics Data System (ADS)

Choudhary, Lokesh; Wang, Wei; Alfantazi, Akram

2016-01-01

This study aims to characterize the electrochemical corrosion behavior of stainless steel in the ammoniacal thiosulfate gold leaching solutions. Electrochemical corrosion response was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy, while the semi-conductive properties and the chemical composition of the surface film were characterized using Mott-Schottky analysis and X-ray photoelectron spectroscopy, respectively. The morphology of the corroded specimens was analyzed using scanning electron microscopy. The stainless steel 316L showed no signs of pitting in the ammoniacal thiosulfate solutions.

Cytogenetic evaluation of gold nanorods using Allium cepa test.

PubMed

Rajeshwari, A; Roy, Barsha; Chandrasekaran, Natarajan; Mukherjee, Amitava

2016-12-01

The current study reveals the impact of gold nanorods (NRs) capped with CTAB (cetyltrimethylammonium bromide) or PEG (polyethylene glycol) on Allium cepa. The morphology and surface charge of CTAB- and PEG-capped gold NRs were characterized by electron microscopic and zeta potential analyses. The chromosomal aberrations like clumped chromosome, chromosomal break, chromosomal bridge, diagonal anaphase, disturbed metaphase, laggard chromosome, and sticky chromosome were observed in the root tip cells exposed to different concentrations (0.1, 1, and 10 μg/mL) of CTAB- and PEG-capped gold NRs. We found that both CTAB- and PEG-capped gold NRs were able to induce toxicity in the plant system after 4-h interaction. At a maximum concentration of 10 μg/mL, the mitotic index reduction induced by CTAB-capped gold NRs was 40-fold higher than that induced by PEG-capped gold NRs. The toxicity of gold NRs was further confirmed by lipid peroxidation and oxidative stress analyses. The unbound CTAB also contributed to the toxicity in root tip cells, while PEG alone shows less toxicity to the cells. The vehicle control CTAB contributed to the toxic effects in root tip cells, while PEG alone did not show any toxicity to the cells. The results revealed that even though both the particles have adverse effects on A. cepa, there was a significant difference in the mitotic index and oxidative stress generation in root cells exposed to CTAB-capped gold NRs. Thus, this study concludes that the surface polymerization of gold NRs by PEG can reduce the toxicity of CTAB-capped gold NRs. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Sorption-reduction coupled gold recovery process boosted by Pycnoporus sanguineus biomass: Uptake pattern and performance enhancement via biomass surface modification.

PubMed

Shi, Chaohong; Zhu, Nengwu; Kang, Naixin; Wu, Pingxiao; Zhang, Xiaoping; Zhang, Yanhong

2017-09-01

Biorecovery is emerging as a promising process to retrieve gold from secondary resources. The present study aimed to explore the uptake pattern of Pycnoporus sanguineus biomass for gold, identify the effective functional groups in gold recovery process, and thus further intensify the process via microbial surface modification. Results showed that P. sanguineus biomass could effectively recover gold with the formation of highly crystal AuNPs without any exogeneous electron donor. Under the conditions of various initial gold concentrations (1.0, 2.0, and 3.0 mM), biomass dosage of 2.0 g/L, solution pH value of 4.0, and incubation temperature of 30°C, the uptake equilibrium established after 4, 8, and 12 h, respectively. The uptake process could be well described by pseudo-second order kinetics model (R 2  = 0.9988) and Langmuir isotherm model (R 2  = 0.9958). The maximum uptake capacity of P. sanguineus reached as high as 358.69 mg/g. Further analysis indicated that amino, carboxyl and hydroxyl groups positively contributed to the uptake process. Among them, amino group significantly favored the uptake of gold during recovery process. When P. sanguineus biomass was modified by introduction of amino group, the gold uptake process was successfully intensified by shortening the uptake period and enhancing the uptake capacity. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1314-1322, 2017. © 2017 American Institute of Chemical Engineers.

Reshaping, Fragmentation, and Assembly of Gold Nanoparticles Assisted by Pulse Lasers

PubMed Central

2016-01-01

Conspectus The vast majority of the outstanding applications of metal nanoparticles (NPs) developed during the last two decades have arisen from their unique optical properties. Within this context, rational synthesis and assembly of gold NPs have been the main research focus, aiming at the design of nanoplasmonic devices with tailored optical functionalities. The progress made in this field is thus to be ascribed to the understanding of the origin of the interaction between light and such gold nanostructures, the dynamics of which have been thoroughly investigated with significant contributions from short and ultrashort pulse laser technologies. We focus this Account on the potential of pulse lasers to provide new fundamental insights into the electron dynamics involved in the interaction of light with the free conduction electrons of Au NPs, that is, localized surface plasmon resonances (LSPRs). The excitation of LSPRs with a femtosecond pulse laser is followed by thermalization of the Au NP electrons and the subsequent relaxation of the nanocrystal lattice and the surrounding environment, which generally results in surface melting. By contrast, nanosecond irradiation usually induces AuNP fragmentation and uncontrolled melting due to overlapping excitation and relaxation phenomena. These concepts have been exploited toward the preparation of highly monodisperse gold nanospheres via pulse laser irradiation of polyhedral nanocrystal colloids, or in the fabrication of nanostructures with “written-in” optical properties. The applicability of pulsed coherent light has been extended toward the direct synthesis and manipulation of Au NPs. Through ablation of a gold target in a liquid with pulse lasers, spherical Au NPs can be synthesized with no need of stabilizing ligands, which is a great advantage in terms of reducing toxicity, rendering these NPs particularly suitable for medical applications. In addition, femtosecond laser irradiation has been proven a unique tool for the controlled welding of plasmonic gold nanostructures by electromagnetic field enhancement at the hot spots of assembled Au NPs. The combination of such nanostructures with pulse lasers promises significant chemical and biochemical advances, including the structural determination of organic reaction intermediates, the investigation of phase transitions in inorganic nanomaterials at mild reaction conditions, or the efficient photothermal destruction of cancer cells avoiding damage of surrounding tissue. PMID:27035211

Nucleation and island growth of alkanethiolate ligand domains on gold nanoparticles.

PubMed

Wang, Yifeng; Zeiri, Offer; Neyman, Alevtina; Stellacci, Francesco; Weinstock, Ira A

2012-01-24

The metal oxide cluster α-AlW(11)O(39)(9-) (1), readily imaged by cryogenic transmission electron microscopy (cryo-TEM), is used as a diagnostic protecting anion to investigate the self-assembly of alkanethiolate monolayers on electrostatically stabilized gold nanoparticles in water. Monolayers of 1 on 13.8 ± 0.9 nm diameter gold nanoparticles are displaced from the gold surface by mercaptoundecacarboxylate, HS(CH(2))(10)CO(2)(-) (11-MU). During this process, no aggregation is observed by UV-vis spectroscopy, and the intermediate ligand-shell organizations of 1 in cryo-TEM images indicate the presence of growing hydrophobic domains, or "islands", of alkanethiolates. UV-vis spectroscopic "titrations", based on changes in the surface plasmon resonance upon exchange of 1 by thiol, reveal that the 330 ± 30 molecules of 1 initially present on each gold nanoparticle are eventually replaced by 2800 ± 30 molecules of 11-MU. UV-vis kinetic data for 11-MU-monolayer formation reveal a slow phase, followed by rapid self-assembly. The Johnson, Mehl, Avrami, and Kolmogorov model gives an Avrami parameter of 2.9, indicating continuous nucleation and two-dimensional island growth. During nucleation, incoming 11-MU ligands irreversibly displace 1 from the Au-NP surface via an associative mechanism, with k(nucleation) = (6.1 ± 0.4) × 10(2) M(-1) s(-1), and 19 ± 8 nuclei, each comprised of ca. 8 alkanethiolates, appear on the gold-nanoparticle surface before rapid growth becomes kinetically dominant. Island growth is also first-order in [11-MU], and its larger rate constant, k(growth), (2.3 ± 0.2) × 10(4) M(-1) s(-1), is consistent with destabilization of molecules of 1 at the boundaries between the hydrophobic (alkanethiolate) and the electrostatically stabilized (inorganic) domains. © 2011 American Chemical Society

Seeded Growth of Monodisperse Gold Nanorods Using Bromide-Free Surfactant Mixtures

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

Ye, XC; Gao, YZ; Chen, J

We demonstrate for the first time that monodisperse gold nanorods (NRs) with broadly tunable dimensions and longitudinal surface plasmon resonances can be synthesized using a bromide-free surfactant mixture composed of alkyltrimethylammonium chloride and sodium oleate. It is found that uniform gold NRs can be obtained even with an iodide concentration approaching 100 mu M in the growth solution. In contrast to conventional wisdom, our results provide conclusive evidence that neither bromide as the surfactant counterion nor a high concentration of bromide ions in the growth solution is essential for gold NR formation. Correlated electron microscopy study of three-dimensional structures ofmore » gold NRs reveals a previously unprecedented octagonal prismatic structure enclosed predominantly by high index {310} crystal planes. These findings should have profound implications for a comprehensive mechanistic understanding of seeded growth of anisotropic metal nanocrystals.« less

Femtosecond laser generated gold nanoparticles and their plasmonic properties

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

Das, Rupali, E-mail: phz148121@iitd.ac.in; Navas, M. P.; Soni, R. K.

The pulsed laser ablation in liquid medium is now commonly used to generate stable colloidal nanoparticles (NPs) in absence of any chemical additives or stabilizer with diverse applications. In this paper, we report generation of gold NPs (Au NPs) by ultra-short laser pulses. Femtosecond (fs) laser radiation (λ = 800 nm) has been used to ablate a gold target in pure de-ionized water to produce gold colloids with smallsize distribution. The average size of the particles can be further controlled by subjecting to laser-induced post-irradiation providing a versatile physical method of size-selected gold nanoparticles. The optical extinction and morphological dimensions weremore » investigated with UV-Vis spectroscopy and Transmission Electron Microscopy measurements, respectively. Finite difference time domain (FDTD) method is employed to calculate localized surface plasmon (LSPR) wavelength and the near-field generated by Au NPs and their hybrids.« less

Extracellular biosynthesis of gold and silver nanoparticles using Krishna tulsi ( Ocimum sanctum) leaf

NASA Astrophysics Data System (ADS)

Philip, Daizy; Unni, C.

2011-05-01

Aqueous extract of Ocimum sanctum leaf is used as reducing agent for the environmentally friendly synthesis of gold and silver nanoparticles. The nanoparticles were characterized using UV-vis, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. These methods allow the synthesis of hexagonal gold nanoparticles having size ∼30 nm showing two surface plasmon resonance (SPR) bands by changing the relative concentration of HAuCl 4 and the extract. Broadening of SPR is observed at larger quantities of the extract possibly due to biosorption of gold ions. Silver nanoparticles with size in the range 10-20 nm having symmetric SPR band centered around 409 nm are obtained for the colloid synthesized at room temperature at a pH of 8. Crystallinity of the nanoparticles is confirmed from the XRD pattern. Biomolecules responsible for capping are different in gold and silver nanoparticles as evidenced by the FTIR spectra.

Enzymatic formation of gold nanoparticles by submerged culture of the basidiomycete Lentinus edodes.

PubMed

Vetchinkina, Elena P; Loshchinina, Ekaterina A; Burov, Andrey M; Dykman, Lev A; Nikitina, Valentina E

2014-07-20

We report for the first time that the medicinal basidiomycete Lentinus edodes can reduce Au(III) from chloroauric acid (HAuCl4) to elemental Au [Au(0)], forming nanoparticles. Several methods, including transmission electron microscopy, electron energy loss spectroscopy, X-ray fluorescence, and dynamic light scattering, were used to show that when the fungus was grown submerged, colloidal gold accumulated on the surface of and inside the mycelial hyphae as electron-dense particles mostly spherical in shape, with sizes ranging from 5 to 50nm. Homogeneous proteins (the fungal enzymes laccase, tyrosinase, and Mn-peroxidase) were found for the first time to be involved in the reduction of Au(III) to Au(0) from HAuCl4. A possible mechanism forming Au nanoparticles is discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecule counting with alkanethiol and DNA immobilized on gold microplates for extended gate FET.

PubMed

Cao, Zhong; Xiao, Zhong-Liang; Zhang, Ling; Luo, Dong-Mei; Kamahori, Masao; Shimoda, Maki

2013-04-01

Several molecule counting methods based on electrochemical characterization of alkanethiol and thiolated single-stranded oligonucleotide (HS-ssDNA) immobilized on gold microplates, which were used as extended gates of field effect transistors (FETs), have been investigated in this paper. The surface density of alkanethiol and DNA monolayers on gold microplates were quantitatively evaluated from the reductive desorption charge by using cyclic voltammetry (CV) and fast CV (FCV) methods in strong alkali solution. Typically, the surface density of 6-hydroxy-1-hexanethiol (6-HHT) was evaluated to be 4.639 molecules/nm(2), and the 28 base-pair dsDNA about 1.226-4.849 molecules/100 nm(2) on Au microplates after post-treatment with 6-HHT. The behaviors on surface potential and capacitance of different aminoalkanethiols on Au microplates were measured in 0.1 mol/L Na2SO4 and 10 mmol/L Tris-HCl (pH=7.4) solutions, indicating that the surface potential increases and the double-layer capacitance decreases with the length of carbon chain increased for the thiol monolayers, which obey a physics relationship for a capacitor. Comparably, a simple sensing method based on the electronic signals of biochemical reaction events on DNA immobilization and hybridization at the Au surface of the extended gate FET (EGFET) was developed, with which the surface density of the hybridized dsDNA on the gold surface of the EGFET was evaluated to be 1.36 molecules per 100 nm(2), showing that the EGFET is a promising sensing biochip for DNA molecule counting. Copyright © 2012 Elsevier B.V. All rights reserved.

Magnetic and interface properties of the core-shell Fe3O4/Au nanocomposites

NASA Astrophysics Data System (ADS)

Baskakov, A. O.; Solov'eva, A. Yu.; Ioni, Yu. V.; Starchikov, S. S.; Lyubutin, I. S.; Khodos, I. I.; Avilov, A. S.; Gubin, S. P.

2017-11-01

Core-shell Fe3O4/Au nanostructures were obtained with an advanced method of two step synthesis and several complementary methodics were applied for investigation structural and magnetic properties of the samples. Along with X-ray diffraction and transmission electron microscopy, electron diffraction, optical, Raman and Mössbauer spectroscopy were used for nanoparticle characterization. It was established that the physical and structural properties Fe3O4/Au nanocomposites are specific of intrinsic properties of gold and magnetite. Mössbauer and Raman spectroscopy data indicated that magnetite was in a nonstoichiometric state with an excess of trivalent iron both in the initial Fe3O4 nanoparticles and in the Fe3O4/Au nanocomposites. As follows from the Mössbauer data, magnetic properties of iron ions in the internal area (in core) and in the surface layer of magnetite nanoparticles are different due to the rupture of exchange bonds at the particles surface. This leads to decrease in an effective magnetic moment at the surface. Gold atoms at the interface of the composites interact with dangling bonds of magnetite and stabilize the magnetic properties of the surface layers of magnetite.

Electron beam patterning for writing of positively charged gold colloidal nanoparticles

NASA Astrophysics Data System (ADS)

Zafri, Hadar; Azougi, Jonathan; Girshevitz, Olga; Zalevsky, Zeev; Zitoun, David

2018-02-01

Synthesis at the nanoscale has progressed at a very fast pace during the last decades. The main challenge today lies in precise localization to achieve efficient nanofabrication of devices. In the present work, we report on a novel method for the patterning of gold metallic nanoparticles into nanostructures on a silicon-on-insulator (SOI) wafer. The fabrication makes use of relatively accessible equipment, a scanning electron microscope (SEM), and wet chemical synthesis. The electron beam implants electrons into the insulating material, which further anchors the positively charged Au nanoparticles by electrostatic attraction. The novel fabrication method was applied to several substrates useful in microelectronics to add plasmonic particles. The resolution and surface density of the deposition were tuned, respectively, by the electron energy (acceleration voltage) and the dose of electronic irradiation. We easily achieved the smallest written feature of 68 ± 18 nm on SOI, and the technique can be extended to any positively charged nanoparticles, while the resolution is in principle limited by the particle size distribution and the scattering of the electrons in the substrate. [Figure not available: see fulltext.

Excitation of propagating surface plasmons with a scanning tunnelling microscope.

PubMed

Wang, T; Boer-Duchemin, E; Zhang, Y; Comtet, G; Dujardin, G

2011-04-29

Inelastic electron tunnelling excitation of propagating surface plasmon polaritons (SPPs) on a thin gold film is demonstrated. This is done by combining a scanning tunnelling microscope (STM) with an inverted optical microscope. Analysis of the leakage radiation in both the image and Fourier planes unambiguously shows that the majority (up to 99.5%) of the detected photons originate from propagating SPPs with propagation lengths of the order of 10  µm. The remaining photon emission is localized under the STM tip and is attributed to a tip-gold film coupled plasmon resonance as evidenced by the bimodal spectral distribution and enhanced emission intensity observed using a silver STM tip for excitation.

Simple Fabrication of Gold Nanobelts and Patterns

PubMed Central

Zhang, Renyun; Hummelgård, Magnus; Olin, Håkan

2012-01-01

Gold nanobelts are of interest in several areas; however, there are only few methods available to produce these belts. We report here on a simple evaporation induced self-assembly (EISA) method to produce porous gold nanobelts with dimensions that scale across nanometer (thickness ∼80 nm) and micrometer (width ∼20 µm), to decimeter (length ∼0.15 m). The gold nanobelts are well packed on the beaker wall and can be easily made to float on the surface of the solution for depositing onto other substrates. Microscopy showed that gold nanobelts had a different structure on the two sides of the belt; the density of gold nanowires on one side was greater than on the other side. Electrical measurements showed that these nanobelts were sensitive to compressive or tensile forces, indicating a potential use as a strain sensor. The patterned nanobelts were further used as a template to grow ZnO nanowires for potential use in applications such as piezo-electronics. PMID:22291962

Optical Properties of Plasmonic Nanostructures for Bio-Imaging and Bio-Sensing Applications

NASA Astrophysics Data System (ADS)

Kravets, Vira V.

Kravets, Vira V. (Ph.D., Physics). Optical properties of plasmonic nanostructures for bio-imaging and bio-sensing applications. Dissertation directed by Associate Professor Anatoliy Pinchuk. ABSTRACT. This dissertation explores the physics of free electron excitations in gold nanoparticle chains, silver nanoparticle colloids, and thin gold films. Electron excitations in nanostructures (surface plasmons, SP) are responsible for unique optical properties, which are applied in bio-sensing and bio-imaging applications. For gold nanoparticle chains, the effect of SP on resonance light absorption was studied experimentally and theoretically. Mainly, how the spectral position of the absorption peak depends on inter-particle distances. This dependence is used in “molecular rulers”, providing spatial resolution below the Rayleigh limit. The underlying theory is based on particle interaction via scattered dipole fields. Often in literature only the near-field component of the scattered field is considered. Here, I show that middle and far fields should not be neglected for calculation of extinction by particle chains. In silver nanoparticles, SP excitations produce two independent effects: (a) the intrinsic fluorescence of the particles, and (b) the enhancement of a molecule’s fluorescence by a particle’s surface. The mechanism of (a) is deduced by studying how fluorescence depends on particle size. For (b), I show that fluorescence of a dye molecule on the surface of a nanoparticle is enhanced, when compared to that of the free-standing dye. I demonstrate that the dye’s fluorescent quantum yield is dependent on the particle’s size, making labeled silver nanoparticles attractive candidates as bio-imaging agents. Labeled nanoparticles are applied to cell imaging, and their bio-compatibility with two cell lines is evaluated here. Finally, in gold films under attenuated total internal reflection (ATR) conditions, the SP create a propagating wave (SP-polariton, SPP) when coupled with the incident light. Because of the sensitivity of SPPs to the medium adjacent to the gold film surface, they are widely applied in bio-sensing applications. A toolbox for the description of sputter-deposited gold films is presented here: it employs three experimental techniques (ATR, transmittance and atomic force microscopy) in combination with the effective medium theory for double-layered film model. Our findings have allowed for the avoidance of superficial fitting parameters in our model.

Scattering-Type Surface-Plasmon-Resonance Biosensors

NASA Technical Reports Server (NTRS)

Wang, Yu; Pain, Bedabrata; Cunningham, Thomas; Seshadri, Suresh

2005-01-01

Biosensors of a proposed type would exploit scattering of light by surface plasmon resonance (SPR). Related prior biosensors exploit absorption of light by SPR. Relative to the prior SPR biosensors, the proposed SPR biosensors would offer greater sensitivity in some cases, enough sensitivity to detect bioparticles having dimensions as small as nanometers. A surface plasmon wave can be described as a light-induced collective oscillation in electron density at the interface between a metal and a dielectric. At SPR, most incident photons are either absorbed or scattered at the metal/dielectric interface and, consequently, reflected light is greatly attenuated. The resonance wavelength and angle of incidence depend upon the permittivities of the metal and dielectric. An SPR sensor of the type most widely used heretofore includes a gold film coated with a ligand a substance that binds analyte molecules. The gold film is thin enough to support evanescent-wave coupling through its thickness. The change in the effective index of refraction at the surface, and thus the change in the SPR response, increases with the number of bound analyte molecules. The device is illuminated at a fixed wavelength, and the intensity of light reflected from the gold surface opposite the ligand-coated surface is measured as a function of the angle of incidence. From these measurements, the angle of minimum reflection intensity is determined

TAT and HA2 Facilitate Cellular Uptake of Gold Nanoparticles but Do Not Lead to Cytosolic Localisation

PubMed Central

Free, Paul; Lévy, Raphaël

2015-01-01

The methods currently available to deliver functional labels and drugs to the cell cytosol are inefficient and this constitutes a major obstacle to cell biology (delivery of sensors and imaging probes) and therapy (drug access to the cell internal machinery). As cell membranes are impermeable to most molecular cargos, viral peptides have been used to bolster their internalisation through endocytosis and help their release to the cytosol by bursting the endosomal vesicles. However, conflicting results have been reported on the extent of the cytosolic delivery achieved. To evaluate their potential, we used gold nanoparticles as model cargos and systematically assessed how the functionalisation of their surface by either or both of the viral peptides TAT and HA2 influenced their intracellular delivery. We evaluated the number of gold nanoparticles present in cells after internalisation using photothermal microscopy and their subcellular localisation by electron microscopy. While their uptake increased when the TAT and/or HA2 viral peptides were present on their surface, we did not observe a significant cytosolic delivery of the gold nanoparticles. PMID:25836335

Quintuple-modality (SERS-MRI-CT-TPL-PTT) plasmonic nanoprobe for theranostics

NASA Astrophysics Data System (ADS)

Liu, Yang; Chang, Zheng; Yuan, Hsiangkuo; Fales, Andrew M.; Vo-Dinh, Tuan

2013-11-01

A unique quintuple-modality theranostic nanoprobe (QMT) is developed with gold nanostars for surface-enhanced Raman scattering (SERS), magnetic resonance imaging (MRI), computed tomography (CT), two-photon luminescence (TPL) imaging and photothermal therapy (PTT). The synthesized gold nanostars were tagged with a SERS reporter and linked with an MRI contrast agent Gd3+. In vitro experiments demonstrated the developed QMT nanoprobe to be a potential theranostic agent for future biomedical applications.A unique quintuple-modality theranostic nanoprobe (QMT) is developed with gold nanostars for surface-enhanced Raman scattering (SERS), magnetic resonance imaging (MRI), computed tomography (CT), two-photon luminescence (TPL) imaging and photothermal therapy (PTT). The synthesized gold nanostars were tagged with a SERS reporter and linked with an MRI contrast agent Gd3+. In vitro experiments demonstrated the developed QMT nanoprobe to be a potential theranostic agent for future biomedical applications. Electronic supplementary information (ESI) available: Details of experimental section, characterization details and relaxivity curve of developed QMT nanoprobe in water at 1.5 T magnetic filed strength. See DOI: 10.1039/c3nr03762b

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

PubMed

Aizawa, Masato; Buriak, Jillian M

2006-05-03

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

Highly sensitive immunosensing of prostate specific antigen using poly cysteine caped by graphene quantum dots and gold nanoparticle: A novel signal amplification strategy.

PubMed

Malekzad, Hediyeh; Hasanzadeh, Mohammad; Shadjou, Nasrin; Jouyban, Abolghasem

2017-12-01

A mediator-free electrochemical immunosensor for quantitation of prostate specific antigen (PSA) based on dual signal amplification strategy was fabricated. In this work, PSA-antibody (anti-PSA) was immobilized onto a green and biocompatible nanocomposite containing poly l-cysteine (P-Cys) as conductive matrix and graphene quantum dots (GQDs)/gold nanoparticles (GNPs) as dual signal amplification elements. Therefore, a novel multilayer film based on P-Cys, GQDs, and GNPs was exploited to develop a highly sensitive amperometric immunosensor for detection of PSA. Fully electrochemical methodology was used to prepare a new transducer on a gold surface which provided a high surface area to immobilize a high amount of the anti-PSA. Importantly, GNPs prepared by soft template synthesized method lead to compact morphology was achieved. The surface morphology of electrode surface was characterized by high-resolution field emission scanning electron microscope (FE-SEM) and energy dispersive spectroscopy (EDX). Chemical compositions of the gold nanoparticles were analysed by an EDX. The immunosensor was employed for the detection of PSA in physiological pH. Under optimized condition the calibration curve for PSA concentration was linear up to 2-9pgmL -1 with lower limit of quantification of 1.8pgmL -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

Surface acoustic wave/silicon monolithic sensor/processor

NASA Technical Reports Server (NTRS)

Kowel, S. T.; Kornreich, P. G.; Nouhi, A.; Kilmer, R.; Fathimulla, M. A.; Mehter, E.

1983-01-01

A new technique for sputter deposition of piezoelectric zinc oxide (ZnO) is described. An argon-ion milling system was converted to sputter zinc oxide films in an oxygen atmosphere using a pure zinc oxide target. Piezoelectric films were grown on silicon dioxide and silicon dioxide overlayed with gold. The sputtered films were evaluated using surface acoustic wave measurements, X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and resistivity measurements. The effect of the sputtering conditions on the film quality and the result of post-deposition annealing are discussed. The application of these films to the generation of surface acoustic waves is also discussed.

Graphene Oxide-Promoted Reshaping and Coarsening of Gold Nanorods and Nanoparticles

PubMed Central

Pan, Hanqing; Low, Serena; Weerasuriya, Nisala; Shon, Young-Seok

2015-01-01

This paper describes thermally induced reshaping and coarsening behaviors of gold nanorods and nanoparticles immobilized on the surface of graphene oxide. Cetyltrimethylammonium bromide-stabilized gold nanorods with an aspect ratio of ~3.5 (54:15 nm) and glutathione-capped gold nanoparticles with an average core size of ~3 nm were synthesized and self-assembled onto the surface of graphene oxide. The hybrid materials were then heated at different temperatures ranging from 50 to 300 °C. The effects of heat treatments were monitored using UV–vis spectroscopy and transmission electron microscopy (TEM). These results were directly compared with those of heat-treated free-standing gold nanorods and nanoparticles without graphene oxide to understand the heat-induced morphological changes of the nanohybrids. The obtained results showed that the gold nanorods would undergo a complete reshaping to spherical particles at the temperature of 50 °C when they are assembled on graphene oxide. In comparison, the complete reshaping of free-standing gold nanorods to spherical particles would ultimately require a heating of the samples at 200 °C. In addition, the spherical gold nanoparticles immobilized on graphene oxide would undergo a rapid coarsening at the temperature of 100–150 °C, which was lower than the temperature (150–200 °C) required for visible coarsening of free-standing gold nanoparticles. The results indicated that graphene oxide facilitates the reshaping and coarsening of gold nanorods and nanoparticles, respectively, during the heat treatments. The stripping and spillover of stabilizing ligands promoted by graphene oxide are proposed to be the main mechanism for the enhancements in the heat-induced transformations of nanohybrids. PMID:25611371

The Evolution of Fabricated Gold Thin Films to Nano-Micro Particles Under Thermal Annealing Process

NASA Astrophysics Data System (ADS)

Hajivaliei, Mahdi; Nazari, Saeed

2016-06-01

Gold (Au) thin films with thickness of 35nm were prepared by electron beam deposition onto flat glass substrates under high vacuum (5.3×10-3Pa) condition and they were annealed in the range of 573-873 K for 1 and 2h in atmospheric pressure. The influence of the annealing temperature on the evolution of Au thin film to nano-micro particles was studied. Moreover, the basic properties of the films, namely morphological, structural and optical were investigated. The X-ray diffraction (XRD) analysis revealed that the Au thin films were cubic structure phase with lattice parameter around a=4.0786Å. The most preferential orientation is along (111) planes for all Au films. The lattice parameter and grain size in the films were calculated by X-ray patterns and correlated with annealing temperatures. The obtained results of ultraviolet-visible spectrometry (UV-Vis) indicate that with increasing annealing temperature, the surface plasmon resonance peak of gold nanocrystallite will disappear which implies the size of particles are grown. Field-emission scanning electron microscopy (FE-SEM) results show that the prepared gold thin films have been converted to nano-micro gold particles in different annealing temperatures. These results lead to controlling the size of produced nanocrystallite.

Three-dimensionally ordered macroporous (3DOM) gold-nanoparticle-doped titanium dioxide (GTD) photonic crystals modified electrodes for hydrogen peroxide biosensor.

PubMed

Li, Jianlin; Han, Tao; Wei, Nannan; Du, Jiangyan; Zhao, Xiangwei

2009-12-15

Gold nanoparticles have been introduced into the wall framework of titanium dioxide photonic crystals by the colloidal crystal template technique. The three-dimensionally ordered macroporous gold-nanoparticle-doped titanium dioxide (3DOM GTD) film was modified on the indium-tin oxide (ITO) electrode surface and used for the hydrogen peroxide biosensor. The direct electron transfer and electrocatalysis of horseradish peroxidase (HRP) immobilized on this film have been investigated. The 3DOM GTD film could provide a good microenvironment for retaining the biological bioactivity, large internal area, and superior conductivity. The HRP/3DOM GTD/ITO electrode exhibited two couples of redox peaks corresponding to the HRP intercalated in the mesopores and adsorbed on the external surface of the film with the formal potential of -0.19 and -0.52V in 0.1M PBS (pH 7.4), respectively. The HRP intercalated in the mesopores showed a surface-controlled process with a single proton transfer. The direct electron transfer between the adsorbed HRP and the electrode is achieved without the aid of an electron mediator. The H(2)O(2) biosensor displayed a rapid eletrocatalytic response (less than 3s), a wide linear range from 0.5 microM to 1.4mM with a detection limit of 0.2 microM, high sensitivity (179.9 microAmM(-1)), good stability and reproducibility. Compared with the free-Au doped titanium dioxide photonic crystals modified electrode, the GTD modified electrode could greatly enhance the response current signal, linear detection range and higher sensitivity. The 3DOM GTD provided a new matrix for protein immobilization and direct transfer study and opened a way for low conductivity electrode biosensor.

Heparin Assisted Photochemical Synthesis of Gold Nanoparticles and Their Performance as SERS Substrates

PubMed Central

Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio

2014-01-01

Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319

Direct patterning of a cyclotriveratrylene derivative for directed self-assembly of C60

NASA Astrophysics Data System (ADS)

Osner, Zachary R.; Nyamjav, Dorjderem; Holz, Richard C.; Becker, Daniel P.

2011-07-01

A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials.

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.

Yeast cytochrome c integrated with electronic elements: a nanoscopic and spectroscopic study down to single-molecule level

NASA Astrophysics Data System (ADS)

Delfino, I.; Bonanni, B.; Andolfi, L.; Baldacchini, C.; Bizzarri, A. R.; Cannistraro, S.

2007-06-01

Various aspects of redox protein integration with nano-electronic elements are addressed by a multi-technique investigation of different yeast cytochrome c (YCC)-based hybrid systems. Three different immobilization strategies on gold via organic linkers are explored, involving either covalent bonding or electrostatic interaction. Specifically, Au surfaces are chemically modified by self-assembled monolayers (SAMs) exposing thiol-reactive groups, or by acid-oxidized single-wall carbon nanotubes (SWNTs). Atomic force microscopy and scanning tunnelling microscopy are employed to characterize the morphology and the electronic properties of single YCC molecules adsorbed on the modified gold surfaces. In each hybrid system, the protein molecules are stably assembled, in a native configuration. A standing-up arrangement of YCC on SAMs is suggested, together with an enhancement of the molecular conduction, as compared to YCC directly assembled on gold. The electrostatic interaction with functionalized SWNTs allows several YCC adsorption geometries, with a preferential high-spin haem configuration, as outlined by Raman spectroscopy. Moreover, the conduction properties of YCC, explored in different YCC nanojunctions by conductive atomic force microscopy, indicate the effectiveness of electrical conduction through the molecule and its dependence on the electrode material. The joint employment of several techniques confirms the key role of a well-designed immobilization strategy, for optimizing biorecognition capabilities and electrical coupling with conductive substrates at the single-molecule level, as a starting point for advanced applications in nano-biotechnology.

Mechanically Assisted Self-Healing of Ultrathin Gold Nanowires.

PubMed

Wang, Binjun; Han, Ying; Xu, Shang; Qiu, Lu; Ding, Feng; Lou, Jun; Lu, Yang

2018-04-17

As the critical feature sizes of integrated circuits approaching sub-10 nm, ultrathin gold nanowires (diameter <10 nm) have emerged as one of the most promising candidates for next-generation interconnects in nanoelectronics. Also due to their ultrasmall dimensions, however, the structures and morphologies of ultrathin gold nanowires are more prone to be damaged during practical services, for example, Rayleigh instability can significantly alter their morphologies upon Joule heating, hindering their applications as interconnects. Here, it is shown that upon mechanical perturbations, predamaged, nonuniform ultrathin gold nanowires can quickly recover into uniform diameters and restore their smooth surfaces, via a simple mechanically assisted self-healing process. By examining the local self-healing process through in situ high-resolution transmission electron microscopy, the underlying mechanism is believed to be associated with surface atomic diffusion as evidenced by molecular dynamics simulations. In addition, mechanical manipulation can assist the atoms to overcome the diffusion barriers, as suggested by ab initio calculations, to activate more surface adatoms to diffuse and consequently speed up the self-healing process. This result can provide a facile method to repair ultrathin metallic nanowires directly in functional devices, and quickly restore their microstructures and morphologies by simple global mechanical perturbations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH 3, OH, and CONHCH 3 functionalized self-assembled monolayers

NASA Astrophysics Data System (ADS)

Morales-Cruz, Angel L.; Tremont, Rolando; Martínez, Ramón; Romañach, Rodolfo; Cabrera, Carlos R.

2005-03-01

Chemical and mechanical properties of different compounds can be elucidated by measuring fundamental forces such as adhesion, attraction and repulsion, between modified surfaces by means of atomic force microscopy (AFM) in force mode calibration. This work presents a combination of AFM, self-assembled monolayers (SAMs), and crystallization techniques to study the forces of interaction between excipients and active ingredients used in pharmaceutical formulations. SAMs of 16-mercaptohexadecanoate, which represent magnesium stereate, were used to modify the probe tip, whereas CH3-, OH- and CONHCH3-functional SAMs were formed on a gold-coated mica substrate, and used as examples of the surfaces of lactose and theophylline. The crystals of lactose and theophylline were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modification of gold surfaces with 16-mercaptohexadecanoate, 10-mercapto-1-decanol (OH-functional SAM), 1-decanethiol (CH3-functional) and N-methyl-11-mercaptoundecanamide (CONHCH3-functional SAM) was studied by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Fourier transform-infrared spectroscopy (FT-IR) in specular reflectance mode. XPS and AES results of the modified surfaces showed the presence of sulfur binding, and kinetic energies that correspond to the presence of 10-mercapto-1-decanol, 1-decanethiol, N-methyl-11-mercaptoundecanamide and the salt of 16-mercaptohexadecanoic acid. The absorption bands in the IR spectra further confirm the modification of the gold-coated substrates with these compounds. Force versus distance measurements were performed between the modified tip and the modified gold-coated mica substrates. The mean adhesion forces between the COO-Ca2+ functionalized tip and the CH3-, OH-, and CONHCH3-modified substrates were determined to be 4.5, 8.9 and 6.3 nN, respectively. The magnitude of the adhesion force (ion-dipole) interaction between the modified tip and substrate decreases in the following order: COO-Ca2+/OH > COO-Ca2+/CONHCH3 > COO-Ca2+/CH3.

Graphene–Gold Nanoparticles Hybrid—Synthesis, Functionalization, and Application in a Electrochemical and Surface-Enhanced Raman Scattering Biosensor

PubMed Central

Khalil, Ibrahim; Julkapli, Nurhidayatullaili Muhd; Yehye, Wageeh A.; Basirun, Wan Jefrey; Bhargava, Suresh K.

2016-01-01

Graphene is a single-atom-thick two-dimensional carbon nanosheet with outstanding chemical, electrical, material, optical, and physical properties due to its large surface area, high electron mobility, thermal conductivity, and stability. These extraordinary features of graphene make it a key component for different applications in the biosensing and imaging arena. However, the use of graphene alone is correlated with certain limitations, such as irreversible self-agglomerations, less colloidal stability, poor reliability/repeatability, and non-specificity. The addition of gold nanostructures (AuNS) with graphene produces the graphene–AuNS hybrid nanocomposite which minimizes the limitations as well as providing additional synergistic properties, that is, higher effective surface area, catalytic activity, electrical conductivity, water solubility, and biocompatibility. This review focuses on the fundamental features of graphene, the multidimensional synthesis, and multipurpose applications of graphene–Au nanocomposites. The paper highlights the graphene–gold nanoparticle (AuNP) as the platform substrate for the fabrication of electrochemical and surface-enhanced Raman scattering (SERS)-based biosensors in diverse applications as well as SERS-directed bio-imaging, which is considered as an emerging sector for monitoring stem cell differentiation, and detection and treatment of cancer. PMID:28773528

Graphene-Gold Nanoparticles Hybrid-Synthesis, Functionalization, and Application in a Electrochemical and Surface-Enhanced Raman Scattering Biosensor.

PubMed

Khalil, Ibrahim; Julkapli, Nurhidayatullaili Muhd; Yehye, Wageeh A; Basirun, Wan Jefrey; Bhargava, Suresh K

2016-05-24

Graphene is a single-atom-thick two-dimensional carbon nanosheet with outstanding chemical, electrical, material, optical, and physical properties due to its large surface area, high electron mobility, thermal conductivity, and stability. These extraordinary features of graphene make it a key component for different applications in the biosensing and imaging arena. However, the use of graphene alone is correlated with certain limitations, such as irreversible self-agglomerations, less colloidal stability, poor reliability/repeatability, and non-specificity. The addition of gold nanostructures (AuNS) with graphene produces the graphene-AuNS hybrid nanocomposite which minimizes the limitations as well as providing additional synergistic properties, that is, higher effective surface area, catalytic activity, electrical conductivity, water solubility, and biocompatibility. This review focuses on the fundamental features of graphene, the multidimensional synthesis, and multipurpose applications of graphene-Au nanocomposites. The paper highlights the graphene-gold nanoparticle (AuNP) as the platform substrate for the fabrication of electrochemical and surface-enhanced Raman scattering (SERS)-based biosensors in diverse applications as well as SERS-directed bio-imaging, which is considered as an emerging sector for monitoring stem cell differentiation, and detection and treatment of cancer.

Electrochemical synthesis of nanostructured gold film for the study of carbohydrate–lectin interactions using localized surface plasmon resonance spectroscopy

PubMed Central

Bhattarai, Jay K.; Sharma, Abeera; Fujikawa, Kohki; Demchenko, Alexei V.; Stine, Keith J.

2014-01-01

Localized surface plasmon resonance (LSPR) spectroscopy is a label-free chemical and biological molecular sensing technique whose sensitivity depends upon development of nanostructured transducers. Herein, we report an electrodeposition method for fabricating nanostructured gold films (NGFs) that can be used as transducers in LSPR spectroscopy. The NGF was prepared by electrodepositing gold from potassium dicyanoaurate solution onto a flat gold surface using two sequential controlled potential steps. Imaging by scanning electron microscopy reveals a morphology consisting of randomly configured block-like nanostructures. The bulk refractive index sensitivity of the prepared NGF is 100 ± 2 nm RIU−1 and the initial peak in the reflectance spectrum is at 518 ± 1 nm under N2(g). The figure of merit is 1.7. In addition, we have studied the interaction between carbohydrate (mannose) and lectin (Concanavalin A) on the NGF surface using LSPR spectroscopy by measuring the interaction of 8-mercaptooctyl-α-D-mannopyranoside (αMan-C8-SH) with Concanavalin A by first immobilizing αMan-C8-SH in mixed SAMs with 3,6-dioxa-8-mercaptooctanol (TEG-SH) on the NGF surface. The interaction of Con A with the mixed SAMs is confirmed using electrochemical impedance spectroscopy. Finally, the NGF surface was regenerated to its original sensitivity by removing the SAM and the bound biomolecules. The results from these experiments contribute toward the development of inexpensive LSPR based sensors that could be useful for studying glycan–protein interactions and other bioanalytical purposes. PMID:25442712

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

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

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.more » 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 was found to be Au11L52+ at lower coverage and Au11L5+ at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces.« less

Nanopatterning the electronic properties of gold surfaces with self-organized superlattices of metallic nanostructures.

PubMed

Didiot, Clement; Pons, Stephane; Kierren, Bertrand; Fagot-Revurat, Yannick; Malterre, Daniel

2007-10-01

The self-organized growth of nanostructures on surfaces could offer many advantages in the development of new catalysts, electronic devices and magnetic data-storage media. The local density of electronic states on the surface at the relevant energy scale strongly influences chemical reactivity, as does the shape of the nanoparticles. The electronic properties of surfaces also influence the growth and decay of nanostructures such as dimers, chains and superlattices of atoms or noble metal islands. Controlling these properties on length scales shorter than the diffusion lengths of the electrons and spins (some tens of nanometres for metals) is a major goal in electronics and spintronics. However, to date, there have been few studies of the electronic properties of self-organized nanostructures. Here we report the self-organized growth of macroscopic superlattices of Ag or Cu nanostructures on Au vicinal surfaces, and demonstrate that the electronic properties of these systems depend on the balance between the confinement and the perturbation of the surface states caused by the steps and the nanostructures' superlattice. We also show that the local density of states can be modified in a controlled way by adjusting simple parameters such as the type of metal deposited and the degree of coverage.

Spontaneous grafting: a novel approach to graft diazonium cations on gold nanoparticles in aqueous medium and their self-assembly on electrodes.

PubMed

Kesavan, Srinivasan; John, S Abraham

2014-08-15

The spontaneous grafting of aminophenyl groups on gold nanoparticles (AuNPs) by reaction with in situ generated 4-aminophenyl diazonium cations (APD) in an aqueous medium was described. The spontaneous grafting was likely to proceed by transfer of electrons from AuNPs to the APD cations to form an aminophenyl radical and subsequent attachment with AuNPs. The aminophenyl (AP) functionalized gold nanoparticles (AP-AuNPs) were characterized by UV-visible spectroscopy, high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction, FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and surface-enhanced Raman spectroscopy (SERS). The absence of characteristic vibrational bands corresponding to diazonium group in the FT-IR spectrum confirmed the reduction of the aminophenyl diazonium cations at the surface of AuNPs. The spontaneous attachment of AP on AuNPs was confirmed by XPS from the observed binding energy values for -NH2 at 399.4 eV and -N=N- at 400.2 eV. The SERS spectrum reveals the presence Au-C (437 cm(-1)) bond on AP-AuNPs. Further, the AP-AuNPs were self-assembled on GC/ITO electrode (AP-AuNPs modified electrode) with the aid of free amine groups present on the surface of AP-AuNPs via Michael's nucleophilic addition reaction. The AP-AuNPs modified electrode was characterized by cyclic voltammetry, impedance spectroscopy, UV-visible spectroscopy and scanning electron microscopy. Impedance studies show that the electron transfer reaction of [Fe(CN)6](3-/4-) was higher at the AP-AuNPs modified electrode (1.81×10(-4) cm s(-1)) than at bare (3.77×10(-5) cm s(-1)) GC electrode. Finally, the electrocatalytic activity of the AP-AuNPs modified electrode was demonstrated by studying the oxidation of dopamine (DA). Copyright © 2014 Elsevier Inc. All rights reserved.

Electrosynthesis and characterization of polypyrrole/cashew gum composite grown on gold surface in aqueous medium

USDA-ARS?s Scientific Manuscript database

Electronic systems consisting of renewable, biodegradable materials and minimum amounts of toxic materials are desirable. This study was carried out to investigate the electrosynthesis and evaluation of the electrochemical, morphological, and topographical characteristics of a novel conducting polyp...

Emission dynamics of hybrid plasmonic gold/organic GaN nanorods

NASA Astrophysics Data System (ADS)

Mohammadi, F.; Schmitzer, H.; Kunert, G.; Hommel, D.; Ge, J.; Duscher, G.; Langbein, W.; Wagner, H. P.

2017-12-01

We studied the emission of bare and aluminum quinoline (Alq3)/gold coated wurtzite GaN nanorods by temperature- and intensity-dependent time-integrated and time-resolved photoluminescence (PL). The GaN nanorods of ˜1.5 μm length and ˜250 nm diameter were grown by plasma-assisted molecular beam epitaxy. Gold/Alq3 coated GaN nanorods were synthesized by organic molecular beam deposition. The near band-edge and donor-acceptor pair luminescence was investigated in bare GaN nanorods and compared with multilevel model calculations providing the dynamical parameters for electron-hole pairs, excitons, impurity bound excitons, donors and acceptors. Subsequently, the influence of a 10 nm gold coating without and with an Alq3 spacer layer was studied and the experimental results were analyzed with the multilevel model. Without a spacer layer, a significant PL quenching and lifetime reduction of the near band-edge emission is found. The behavior is attributed to surface band-bending and Förster energy transfer from excitons to surface plasmons in the gold layer. Inserting a 5 nm Alq3 spacer layer reduces the PL quenching and lifetime reduction which is consistent with a reduced band-bending and Förster energy transfer. Increasing the spacer layer to 30 nm results in lifetimes which are similar to uncoated structures, showing a significantly decreased influence of the gold coating on the excitonic dynamics.

Emission dynamics of hybrid plasmonic gold/organic GaN nanorods.

PubMed

Mohammadi, F; Schmitzer, H; Kunert, G; Hommel, D; Ge, J; Duscher, G; Langbein, W; Wagner, H P

2017-12-15

We studied the emission of bare and aluminum quinoline (Alq 3 )/gold coated wurtzite GaN nanorods by temperature- and intensity-dependent time-integrated and time-resolved photoluminescence (PL). The GaN nanorods of ∼1.5 μm length and ∼250 nm diameter were grown by plasma-assisted molecular beam epitaxy. Gold/Alq 3 coated GaN nanorods were synthesized by organic molecular beam deposition. The near band-edge and donor-acceptor pair luminescence was investigated in bare GaN nanorods and compared with multilevel model calculations providing the dynamical parameters for electron-hole pairs, excitons, impurity bound excitons, donors and acceptors. Subsequently, the influence of a 10 nm gold coating without and with an Alq 3 spacer layer was studied and the experimental results were analyzed with the multilevel model. Without a spacer layer, a significant PL quenching and lifetime reduction of the near band-edge emission is found. The behavior is attributed to surface band-bending and Förster energy transfer from excitons to surface plasmons in the gold layer. Inserting a 5 nm Alq 3 spacer layer reduces the PL quenching and lifetime reduction which is consistent with a reduced band-bending and Förster energy transfer. Increasing the spacer layer to 30 nm results in lifetimes which are similar to uncoated structures, showing a significantly decreased influence of the gold coating on the excitonic dynamics.

Ultrafast direct electron transfer at organic semiconductor and metal interfaces.

PubMed

Xiang, Bo; Li, Yingmin; Pham, C Huy; Paesani, Francesco; Xiong, Wei

2017-11-01

The ability to control direct electron transfer can facilitate the development of new molecular electronics, light-harvesting materials, and photocatalysis. However, control of direct electron transfer has been rarely reported, and the molecular conformation-electron dynamics relationships remain unclear. We describe direct electron transfer at buried interfaces between an organic polymer semiconductor film and a gold substrate by observing the first dynamical electric field-induced vibrational sum frequency generation (VSFG). In transient electric field-induced VSFG measurements on this system, we observe dynamical responses (<150 fs) that depend on photon energy and polarization, demonstrating that electrons are directly transferred from the Fermi level of gold to the lowest unoccupied molecular orbital of organic semiconductor. Transient spectra further reveal that, although the interfaces are prepared without deliberate alignment control, a subensemble of surface molecules can adopt conformations for direct electron transfer. Density functional theory calculations support the experimental results and ascribe the observed electron transfer to a flat-lying polymer configuration in which electronic orbitals are found to be delocalized across the interface. The present observation of direct electron transfer at complex interfaces and the insights gained into the relationship between molecular conformations and electron dynamics will have implications for implementing novel direct electron transfer in energy materials.

ATS-6 - Synchronous orbit trapped radiation studies with an electron-proton spectrometer

NASA Technical Reports Server (NTRS)

Walker, R. J.; Swanson, R. L.; Winckler, J. R.; Erickson, K. N.

1975-01-01

The paper discusses the University of Minnesota experiment on ATS-6 designed to study the origin and dynamics of high-energy electrons and protons in the outer radiation belt and in the near-earth plasma sheet. The experiment consists of two nearly identical detector assemblies, each of which is a magnetic spectrometer containing four gold-silicon surface barrier detectors. The instrument provides a clean separation between protons and electrons by the combination of pulse height analysis and magnetic deflection.

Preparation of gold nanoparticles using Salicornia brachiata plant extract and evaluation of catalytic and antibacterial activity

NASA Astrophysics Data System (ADS)

Ayaz Ahmed, Khan Behlol; Subramanian, Swetha; Sivasubramanian, Aravind; Veerappan, Ganapathy; Veerappan, Anbazhagan

2014-09-01

The current study deals with the synthesis of gold nanoparticles (AuNPs) using Salicornia brachiata (Sb) and evaluation of their antibacterial and catalytic activity. The SbAuNPs showed purple color with a characteristic surface plasmon resonance peak at 532 nm. Scanning electron microscopy and transmission electron microscopy revealed polydispersed AuNPs with the size range from 22 to 35 nm. Energy dispersive X-ray and thin layer X-ray diffraction analysis clearly shows that SbAuNPs was pure and crystalline in nature. As prepared gold nanoparticles was used as a catalyst for the sodium borohydride reduction of 4-nitro phenol to 4-amino phenol and methylene blue to leucomethylene blue. The green synthesized nanoparticles exhibited potent antibacterial activity against the pathogenic bacteria, as evidenced by their zone of inhibition. In addition, we showed that the SbAuNPs in combination with the regular antibiotic, ofloxacin, exhibit superior antibacterial activity than the individual.

Three-dimensional locations of gold-labeled proteins in a whole mount eukaryotic cell obtained with 3nm precision using aberration-corrected scanning transmission electron microscopy.

PubMed

Dukes, Madeline J; Ramachandra, Ranjan; Baudoin, Jean-Pierre; Gray Jerome, W; de Jonge, Niels

2011-06-01

Three-dimensional (3D) maps of proteins within the context of whole cells are important for investigating cellular function. However, 3D reconstructions of whole cells are challenging to obtain using conventional transmission electron microscopy (TEM). We describe a methodology to determine the 3D locations of proteins labeled with gold nanoparticles on whole eukaryotic cells. The epidermal growth factor receptors on COS7 cells were labeled with gold nanoparticles, and critical-point dried whole-mount cell samples were prepared. 3D focal series were obtained with aberration-corrected scanning transmission electron microscopy (STEM), without tilting the specimen. The axial resolution was improved with deconvolution. The vertical locations of the nanoparticles in a whole-mount cell were determined with a precision of 3nm. From the analysis of the variation of the axial positions of the labels we concluded that the cellular surface was ruffled. To achieve sufficient stability of the sample under electron beam irradiation during the recording of the focal series, the sample was carbon coated. A quantitative method was developed to analyze the stability of the ultrastructure after electron beam irradiation using TEM. The results of this study demonstrate the feasibility of using aberration-corrected STEM to study the 3D nanoparticle distribution in whole cells. Copyright © 2011 Elsevier Inc. All rights reserved.

Three-dimensional locations of gold-labeled proteins in a whole mount eukaryotic cell obtained with 3 nm precision using aberration-corrected scanning transmission electron microscopy

PubMed Central

Dukes, Madeline J.; Ramachandra, Ranjan; Baudoin, Jean-Pierre; Jerome, W. Gray; de Jonge, Niels

2011-01-01

Three-dimensional (3D) maps of proteins within the context of whole cells are important for investigating cellular function. However, 3D reconstructions of whole cells are challenging to obtain using conventional transmission electron microscopy (TEM). We describe a methodology to determine the 3D locations of proteins labeled with gold nanoparticles on whole eukaryotic cells. The epidermal growth factor receptors on COS7 cells were labeled with gold nanoparticles, and critical-point dried whole-mount cell samples were prepared. 3D focal series were obtained with aberration-corrected scanning transmission electron microscopy (STEM), without tilting the specimen. The axial resolution was improved with deconvolution. The vertical locations of the nanoparticles in a whole-mount cell were determined with a precision of 3 nm. From the analysis of the variation of the axial positions of the labels we concluded that the cellular surface was ruffled. To achieve sufficient stability of the sample under the electron beam irradiation during the recording of the focal series, the sample was carbon coated. A quantitative method was developed to analyze the stability of the ultrastructure after electron beam irradiation using TEM. The results of this study demonstrate the feasibility of using aberration-corrected STEM to study the 3D nanoparticle distribution in whole cells. PMID:21440635

Charge transport with single molecules--an electrochemical approach.

PubMed

Li, Chen; Mishchenko, Artem; Pobelov, Ilya; Wandlowski, Thomas

2010-01-01

After an introduction and brief review of charge transport in nanoscale molecular systems we report on experimental studies in gold / (single) molecule / gold junctions at solid / liquid interfaces employing a scanning tunneling microscopy (STM)-based 'break junction' technique. We demonstrate attempts in developing basic relationships between molecular structure, conductance properties and nanoscale electrochemical concepts based on four case studies from our own work. In experiments with alpha, omega-alkanedithiol and biphenyldithiol molecular junctions we address the role of sulfur-gold couplings and molecular conformation, such as gauche defects in the alkyl chains and the torsion angle between two phenyl rings. Combination with quantum chemistry calculations enabled a detailed molecular-level understanding of the electronic structure and transport characteristics of both systems. Employing the concept of 'electrolyte gating' with redox-active molecules, such as thiol-terminated derivatives of viologens (HS-6V6-SH or (HS-6V6)) we demonstrate the construction of symmetric and asymmetric active molecular junctions with transistor- or diode-like behavior upon polarization in an electrochemical environment. The experimental data could be represented quantitatively by the Kutznetsov/Ulstrup model assuming a two-step electron transfer with partial vibration relaxation. Finally, we show that surface-immobilized gold nanoparticles with a diameter of (2.4 +/- 0.5) nm exhibit features of locally addressable multi-state electronic switching upon electrolyte gating, which appears to be reminiscent of a sequential charging through several 'oxidation/reduction states'.

Bright new world

NASA Astrophysics Data System (ADS)

Kroó, Norbert; Rácz, Péter; Varró, Sándor

2016-02-01

Surface plasmons (SPOs) have been excited by intense femtosecond laser pulses on a gold film at room temperature and their near field has been analyzed by the intensity dependent response of an STM and by studying the spectra of multiplasmon emitted electrons. Around 80 GW/cm2 laser intensity, anomalies have been found in both cases, interpreted as the stepping in of electron pairing, transition to a diamagnetic state, and by anomalous Faraday rotation.

Elucidating the electronic structure of supported gold nanoparticles and its relevance to catalysis by means of hard X-ray photoelectron spectroscopy

DOE PAGES

Reinecke, Benjamin N.; Kuhl, Kendra P.; Ogasawara, Hirohito; ...

2015-12-31

We report on the electronic structure of Au (gold) nanoparticles supported onto TiO 2 with a goal of elucidating the most important effects that contribute to their high catalytic activity. We synthesize and characterize with high resolution transmission electron microscopy (HRTEM) 3.4, 5.3, and 9.5 nm diameter TiO 2-supported Au nanoparticles with nearly spherical shape and measure their valence band using Au 5d subshell sensitive hard X-ray photoelectron spectroscopy (HAXPES) conducted at Spring-8. Based on density functional theory (DFT) calculations of various Au surface structures, we interpret the observed changes in the Au 5d valence band structure as a functionmore » of size in terms of an increasing percentage of Au atoms at corners/edges for decreasing particle size. Finally, this work elucidates how Au coordination number impacts the electronic structure of Au nanoparticles, ultimately giving rise to their well-known catalytic activity.« less

Photoelectron spectroscopic study on the electronic structures of the dental gold alloys and their interaction with L-cysteine

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

Ogawa, Koji; Takahashi, Kazutoshi; Azuma, Junpei

The valence electronic structures of the dental gold alloys, type 1, type 3, and K14, and their interaction with L-cysteine have been studied by ultraviolet photoelectron spectroscopy with synchrotron radiation. It was found that the electronic structures of the type-1 and type-3 dental alloys are similar to that of polycrystalline Au, while that of the K14 dental alloy is much affected by Cu. The peak shift and the change in shape due to alloying are observed in all the dental alloys. It is suggested that the new peak observed around 2 eV for the L-cysteine thin films on all themore » dental alloys may be due to the bonding of S 3sp orbitals with the dental alloy surfaces, and the Cu-S bond, as well as the Au-S and Au-O bonds, may cause the change in the electronic structure of the L-cysteine on the alloys.« less

Magnetic field dependent electronic transport of Mn4 single-molecule magnet.

NASA Astrophysics Data System (ADS)

Haque, F.; Langhirt, M.; Henderson, J. J.; Del Barco, E.; Taguchi, T.; Christou, G.

2010-03-01

We have performed single-electron transport measurements on a Mn4 single-molecule magnet (SMM) in where amino groups were added to electrically protect the magnetic core and to increase the stability of the molecule when deposited on the single-electron transistor (SET) chip. A three-terminal SET with nano-gap electro-migrated gold electrodes and a naturally oxidized Aluminum back gate. Experiments were conducted at temperatures down to 230mK in the presence of high magnetic fields generated by a superconducting vector magnet. Mn4 molecules were deposited from solution to form a mono-layer. The optimum deposition time was determined by AFM analysis on atomically flat gold surfaces. We have observed Coulomb blockade an electronic excitations that curve with the magnetic field and present zero-field splitting, which represents evidence of magnetic anisotropy. Level anticrossings and large excitations slopes are associated with the behavior of molecular states with high spin values (S ˜ 9), as expected from Mn4.

Hybrid metal grid-polymer-carbon nanotube electrodes for high luminance organic light emitting diodes

NASA Astrophysics Data System (ADS)

Sam, F. Laurent M.; Dabera, G. Dinesha M. R.; Lai, Khue T.; Mills, Christopher A.; Rozanski, Lynn J.; Silva, S. Ravi P.

2014-08-01

Organic light emitting diodes (OLEDs) incorporating grid transparent conducting electrodes (TCEs) with wide grid line spacing suffer from an inability to transfer charge carriers across the gaps in the grids to promote light emission in these areas. High luminance OLEDs fabricated using a hybrid TCE composed of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS PH1000) or regioregular poly(3-hexylthiophene)-wrapped semiconducting single-walled carbon nanotubes (rrP3HT-SWCNT) in combination with a nanometre thin gold grid are reported here. OLEDs fabricated using the hybrid gold grid/PH1000 TCE have a luminance of 18 000 cd m-2 at 9 V; the same as the reference indium tin oxide (ITO) OLED. The gold grid/rrP3HT-SWCNT OLEDs have a lower luminance of 8260 cd m-2 at 9 V, which is likely due to a rougher rrP3HT-SWCNT surface. These results demonstrate that the hybrid gold grid/PH1000 TCE is a promising replacement for ITO in future plastic electronics applications including OLEDs and organic photovoltaics. For applications where surface roughness is not critical, e.g. electrochromic devices or discharge of static electricity, the gold grid/rrP3HT-SWCNT hybrid TCE can be employed.

Synthesis of a novel glucose capped gold nanoparticle as a better theranostic candidate

PubMed Central

Suvarna, Saritha; Das, Ujjal; KC, Sunil; Mishra, Snehasis; Sudarshan, Mathummal; Saha, Krishna Das; Dey, Sanjit; Chakraborty, Anindita; Narayana, Y.

2017-01-01

Gold nanoparticles are predominantly used in diagnostics, therapeutics and biomedical applications. The present study has been designed to synthesize differently capped gold nanoparticles (AuNps) by a simple, one-step, room temperature procedure and to evaluate the potential of these AuNps for biomedical applications. The AuNps are capped with glucose, 2-deoxy-D-glucose (2DG) and citrate using different reducing agents. This is the first report of synthesis of 2DG-AuNp by the simple room temperature method. The synthesized gold nanoparticles are characterized with UV-Visible Spectroscopy, Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and selected area electron diffraction (SAED), Dynamic light scattering (DLS), and Energy-dispersive X-ray spectroscopy (SEM-EDS). Surface-enhanced Raman scattering (SERS) study of the synthesized AuNps shows increase in Raman signals up to 50 times using 2DG. 3-(4, 5-dimethylthiozol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay has been performed using all the three differently capped AuNps in different cell lines to assess cytotoxcity if any, of the nanoparticles. The study shows that 2DG-AuNps is a better candidate for theranostic application. PMID:28582426

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

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

Zhang, Yu; Lu, Fang; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

DOE PAGES

Zhang, Yu; Lu, Fang; Liu, Shizhong; ...

2018-04-01

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Luminescence quantum yields of gold nanoparticles varying with excitation wavelength

NASA Astrophysics Data System (ADS)

Cheng, Yuqing; He, Yingbo; Zhao, Jingyi; Shen, Hongming; Xia, Keyu; Lua, Guowei; Gong, Qihuang

2016-11-01

Luminescence quantum yields (QYs) of gold nanoparticles including nanorods, nanobipyramids and nanospheres are measured elaborately at single nanoparticle level with different excitation wavelengths. It is found that the QYs of the nanostructures are essentially dependent on the excitation wavelength. The QY is higher when the excitation wavelength is blue-detuned and close to the nanoparticles' surface plasmon resonant peak. A phenomenological model based on plasmonic resonator concept is proposed to understand the experimental findings. The excitation wavelength dependent of QY is attributed to the wavelength dependent coupling efficiency between the free electrons oscillation and the intrinsic plasmon resonant radiative mode. These studies should contribute to the understanding of one-photon luminescence from metallic nanostructures and plasmonic surface enhanced spectroscopy.

Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit

NASA Astrophysics Data System (ADS)

Gruber, Thomas; Liao, Ke; Tsatsoulis, Theodoros; Hummel, Felix; Grüneis, Andreas

2018-04-01

Modern electronic structure theories can predict and simulate a wealth of phenomena in surface science and solid-state physics. In order to allow for a direct comparison with experiment, such ab initio predictions have to be made in the thermodynamic limit, substantially increasing the computational cost of many-electron wave-function theories. Here, we present a method that achieves thermodynamic limit results for solids and surfaces using the "gold standard" coupled cluster ansatz of quantum chemistry with unprecedented efficiency. We study the energy difference between carbon diamond and graphite crystals, adsorption energies of water on h -BN, as well as the cohesive energy of the Ne solid, demonstrating the increased efficiency and accuracy of coupled cluster theory for solids and surfaces.

Using Graphene Liquid Cell Transmission Electron Microscopy to Study in Situ Nanocrystal Etching.

PubMed

Hauwiller, Matthew R; Ondry, Justin C; Alivisatos, A Paul

2018-05-17

Graphene liquid cell electron microscopy provides the ability to observe nanoscale chemical transformations and dynamics as the reactions are occurring in liquid environments. This manuscript describes the process for making graphene liquid cells through the example of graphene liquid cell transmission electron microscopy (TEM) experiments of gold nanocrystal etching. The protocol for making graphene liquid cells involves coating gold, holey-carbon TEM grids with chemical vapor deposition graphene and then using those graphene-coated grids to encapsulate liquid between two graphene surfaces. These pockets of liquid, with the nanomaterial of interest, are imaged in the electron microscope to see the dynamics of the nanoscale process, in this case the oxidative etching of gold nanorods. By controlling the electron beam dose rate, which modulates the etching species in the liquid cell, the underlying mechanisms of how atoms are removed from nanocrystals to form different facets and shapes can be better understood. Graphene liquid cell TEM has the advantages of high spatial resolution, compatibility with traditional TEM holders, and low start-up costs for research groups. Current limitations include delicate sample preparation, lack of flow capability, and reliance on electron beam-generated radiolysis products to induce reactions. With further development and control, graphene liquid cell may become a ubiquitous technique in nanomaterials and biology, and is already being used to study mechanisms governing growth, etching, and self-assembly processes of nanomaterials in liquid on the single particle level.

Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

PubMed

Mongin, Denis; Shaviv, Ehud; Maioli, Paolo; Crut, Aurélien; Banin, Uri; Del Fatti, Natalia; Vallée, Fabrice

2012-08-28

Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture. Experiments are performed using an optical time-resolved pump-probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron-hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron-hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal-semiconductor nanohybrids in light-harvesting applications and in photocatalysis.

Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods.

PubMed

Lien, Miao-Bin; Kim, Ji-Young; Han, Myung-Geun; Chang, You-Chia; Chang, Yu-Chung; Ferguson, Heather J; Zhu, Yimei; Herzing, Andrew A; Schotland, John C; Kotov, Nicholas A; Norris, Theodore B

2017-06-27

A systematic study is presented of the intensity-dependent nonlinear light scattering spectra of gold nanorods under resonant excitation of the longitudinal surface plasmon resonance (SPR). The spectra exhibit features due to coherent second and third harmonic generation as well as a broadband feature that has been previously attributed to multiphoton photoluminescence arising primarily from interband optical transitions in the gold. A detailed study of the spectral dependence of the scaling of the scattered light with excitation intensity shows unexpected scaling behavior of the coherent signals, which is quantitatively accounted for by optically induced damping of the SPR mode through a Fermi liquid model of the electronic scattering. The broadband feature is shown to arise not from luminescence, but from scattering of the second-order longitudinal SPR mode with the electron gas, where efficient excitation of the second order mode arises from an optical asymmetry of the nanorod. The electronic-temperature-dependent plasmon damping and the Fermi-Dirac distribution together determine the intensity dependence of the broadband emission, and the structure-dependent absorption spectrum determines the spectral shape through the fluctuation-dissipation theorem. Hence a complete self-consistent picture of both coherent and incoherent light scattering is obtained with a single set of physical parameters.

Size-dependent Hamaker constants for silver and gold nanoparticles

NASA Astrophysics Data System (ADS)

Pinchuk, Pavlo; Jiang, Ke

2015-08-01

Hamaker-Lifshitz constants are material specific constants that are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the Drude model, which is based on the assumption of motion of free conducting electrons. For bulk metals, the Drude model does not predict any sizedependence of the dielectric permittivity. However, the conducting electrons in small noble metal nanoparticles (R ~ 10nm) exhibit surface scattering, which changes the complex permittivity function. In this work, we show theoretically that scattering of the free conducting electrons inside silver and gold nanoparticles with the size of 1 - 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. We calculate numerically the Hamaker-Lifshitz constants for silver and gold nanoparticles with different diameters. The results of the study might be of interests for understanding colloidal stability of metal nanoparticles.

Self-assembly of gibberellic amide assemblies and their applications in the growth and fabrication of ordered gold nanoparticles

NASA Astrophysics Data System (ADS)

Smoak, Evan M.; Carlo, Andrew D.; Fowles, Catherine C.; Banerjee, Ipsita A.

2010-01-01

Gibberellins are a group of naturally occurring diterpenoid based phytohormones that play a vital role in plant growth and development. In this work, we have studied the self-assembly of gibberellic acid, a phytohormone, which belongs to the family of gibberellins, and designed amide derivatives of gibberellic acid (GA3) for the facile, green synthesis of gold nanoparticles. It was found that the derivatives self-assembled into nanofibers and nanoribbons in aqueous solutions at varying pH. Further, upon incubation with tetrachloroaurate, the self-assembled GA3-amide derivatives efficiently nucleated and formed gold nanoparticles when heated to 60 °C. Energy dispersive x-ray spectroscopy, transmission electron microscopy and scanning electron microscopy analyses revealed that uniform coatings of gold nanoparticles in the 10-20 nm range were obtained at low pH on the nanowire surfaces without the assistance of additional reducing agents. This simple method for the development of morphology controlled gold nanoparticles using a plant hormone derivative opens doors for a new class of plant biomaterials which can efficiently yield gold nanoparticles in an environmentally friendly manner. The gold encrusted nanowires formed using biomimetic methods may lead on to the formation of conductive nanowires, which may be useful for a wide range of applications such as in optoelectronics and sensors. Further, the spontaneous formation of highly organized nanostructures obtained from plant phytohormone derivatives such as gibberellic acid is of particular interest as it might help in further understanding the supramolecular assembly mechanism of more highly organized biological structures.

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) Detection of Adsorbed (Bio)molecules

PubMed Central

Ionescu, Rodica Elena; Aybeke, Ece Neslihan; Bourillot, Eric; Lacroute, Yvon; Lesniewska, Eric; Adam, Pierre-Michel; Bijeon, Jean-Louis

2017-01-01

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE). PMID:28134754

Calculation of Quasi-Particle Energies of Aromatic Self-Assembled Monolayers on Au(111).

PubMed

Li, Yan; Lu, Deyu; Galli, Giulia

2009-04-14

We present many-body perturbation theory calculations of the electronic properties of phenylene diisocyanide self-assembled monolayers (SAMs) on a gold surface. Using structural models obtained within density functional theory (DFT), we have investigated how the SAM molecular energies are modified by self-energy corrections and how they are affected by the presence of the surface. We have employed a combination of GW (G = Green's function; W = screened Coulomb interaction) calculations of the SAM quasi-particle energies and a semiclassical image potential model to account for surface polarization effects. We find that it is essential to include both quasi-particle corrections and surface screening in order to provide a reasonable estimate of the energy level alignment at a SAM-metal interface. In particular, our results show that within the GW approximation the energy distance between phenylene diisocyanide SAM energy levels and the gold surface Fermi level is much larger than that found within DFT, e.g., more than double in the case of low packing densities of the SAM.

Electron transfer of plurimodified DNA SAMs.

PubMed

Rospigliosi, Alessandro; Ehlich, Rudolf; Hoerber, Heinrich; Middelberg, Anton; Moggridge, Geoff

2007-07-17

An STM-based current-voltage (I/V) investigation of deoxyribonucleic acid (DNA) 18 base pair (bp) oligonucleotide monolayers on gold is presented. Three bases of each of the immobilized and complementary strands were modified with either iodine or phenylethylene moieties. The oligonucleotides were immobilized on template stripped gold (tsg) surfaces and characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM). AFM imaging showed that monolayers of the expected height were formed. A comparative study of normal, halogenated, and phenyl-modified DNA was made with the STM in tunneling spectroscopy (TS) mode. I/V spectroscopic measurements in the range +/-250 mV on both single- and double-stranded (ds) DNA monolayers (modified and unmodified) showed that for negative substrate bias (U(sub)) electron transfer is more efficient through a phenyl-modified monolayer than through normal or halogenated DNA. This effect was particularly clear below a threshold bias of -100 mV. For positive U(sub), unmodified ds DNA was found to conduct slightly better than the modified strands. This is presumably caused by greater order in the unmodified versus modified DNA monolayers. Modifications on the immobilized (thiolated) strand seem to improve electron transport through the DNA monolayer more than modifications on the complementary (not surface-bound) strand.

Green synthesis, characterization and catalytic degradation studies of gold nanoparticles against congo red and methyl orange.

PubMed

Umamaheswari, C; Lakshmanan, A; Nagarajan, N S

2018-01-01

The present study reports, novel and greener method for synthesis of gold nanoparticles (AuNPs) using 5,7-dihydroxy-6-metoxy-3 ' ,4 ' methylenedioxyisoflavone (Dalspinin), isolated from the roots of Dalbergia coromandeliana was carried out for the first time. The synthesized gold nanoparticles were characterized by UV-Vis spectroscopy, high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The observed surface plasmon resonance (SPR) at 532nm in the UV-Vis absorption spectrum indicates the formation of gold nanoparticles. The powder XRD and SAED pattern for synthesized gold nanoparticles confirms crystalline nature. The HR-TEM images showed that the AuNPs formed were small in size, highly monodispersed and spherical in shape. The average particle sizes of the AuNPs are found to be ~10.5nm. The prepared AuNPs were found to be stable for more than 5months without any aggregation. The catalytic degradation studies of the synthesized AuNPs towards degradation of congo red and methyl orange, showed good catalytic in the complete degradation of both the dyes. The reduction catalyzed by gold nanoparticles followed the pseudo-first order kinetics, with a rate constant of 4.5×10 -3 s -1 (R 2 =0.9959) and 1.7×10 -3 s -1 (R 2 =0.9918) for congo red (CR) and methyl orange (MO), respectively. Copyright © 2017. Published by Elsevier B.V.

Redox properties of undoped 5 nm diamond nanoparticles.

PubMed

Holt, Katherine B; Ziegler, Christoph; Caruana, Daren J; Zang, Jianbing; Millán-Barrios, Enrique J; Hu, Jingping; Foord, John S

2008-01-14

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

PubMed Central

Wang, Deli; Liu, Sufen; Wang, Jie; Lin, Ruoqian; Kawasaki, Masahiro; Rus, Eric; Silberstein, Katharine E.; Lowe, Michael A.; Lin, Feng; Nordlund, Dennis; Liu, Hongfang; Muller, David A.; Xin, Huolin L.; Abruña, Héctor D.

2016-01-01

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. The uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications. PMID:27336795

Synthesis of mono-dispersed nanofluids using solution plasma

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

Heo, Yong Kang, E-mail: yk@rd.numse.nagoya-u.ac.jp; Bratescu, Maria Antoaneta, E-mail: maria@rd.numse.nagoya-u.ac.jp; Knowledge Hub Aichi, Yakusa-cho, Nagakute-ku, Toyota

2014-07-14

Small-sized and well-dispersed gold nanoparticles (NPs) for nanofluidics have been synthesized by electrical discharge in liquid environment using termed solution plasma processing (SPP). Electrons and the hydrogen radicals are reducing the gold ions to the neutral form in plasma gas phase and liquid phase, respectively. The gold NPs have the smallest diameter of 4.9 nm when the solution temperature was kept at 20 °C. Nucleation and growth theory describe the evolution of the NP diameter right after the reduction reaction in function of the system temperature, NP surface energy, dispersion energy barrier, and nucleation rate. Negative charges on the NPs surface duringmore » and after SPP generate repulsive forces among the NPs avoiding their agglomeration in solution. Increasing the average energy in the SPP determines a decrease of the zeta potential and an increase of the NPs diameter. An important enhancement of the thermal conductivity of 9.4% was measured for the synthesized nanofluids containing NPs with the smallest size.« less

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

DOE PAGES

Wang, Deli; Liu, Sufen; Wang, Jie; ...

2016-06-23

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. Themore » uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications.« less

Sensitive Adsorptive Voltammetric Method for Determination of Bisphenol A by Gold Nanoparticle/Polyvinylpyrrolidone-Modified Pencil Graphite Electrode

PubMed Central

Yaman, Yesim Tugce; Abaci, Serdar

2016-01-01

A novel electrochemical sensor gold nanoparticle (AuNP)/polyvinylpyrrolidone (PVP) modified pencil graphite electrode (PGE) was developed for the ultrasensitive determination of Bisphenol A (BPA). The gold nanoparticles were electrodeposited by constant potential electrolysis and PVP was attached by passive adsorption onto the electrode surface. The electrode surfaces were characterized by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The parameters that affected the experimental conditions were researched and optimized. The AuNP/PVP/PGE sensor provided high sensitivity and selectivity for BPA recognition by using square wave adsorptive stripping voltammetry (SWAdSV). Under optimized conditions, the detection limit was found to be 1.0 nM. This new sensor system offered the advantages of simple fabrication which aided the expeditious replication, low cost, fast response, high sensitivity and low background current for BPA. This new sensor system was successfully tested for the detection of the amount of BPA in bottled drinking water with high reliability. PMID:27231912

The synthesis of biocompatible and SERS-active gold nanoparticles using chitosan.

PubMed

Potara, Monica; Maniu, Dana; Astilean, Simion

2009-08-05

In this study we present a clean, nontoxic, environmentally friendly synthesis procedure to generate a large variety of gold nanoparticles (GNPs) by using chitosan, a biocompatible, biodegradable, natural polymer, as reducing and stabilizing agent. The formation of gold-chitosan nanocomposites was characterized by UV-vis absorption spectroscopy, transmission electron microscopy (TEM), x-ray diffraction (XRD) and Raman spectroscopy. The results show that the reaction temperature plays a crucial role in controlling the size, shape and crystalline structure of GNPs. In addition, it is demonstrated that chitosan can perform as a scaffold for the assembly of GNPs, which were successfully applied as substrate for surface-enhanced Raman scattering (SERS). To test the SERS activity, a relevant biological molecule--tryptophan--was adopted as the analyte.

The structure of small, vapor-deposited particles. II - Experimental study of particles with hexagonal profile

NASA Technical Reports Server (NTRS)

Yacaman, M. J.; Heinemann, K.; Yang, C. Y.; Poppa, H.

1979-01-01

'Multiply-twinned' gold particles with hexagonal bright field TEM profile were determined to be icosahedra composed of 20 identical and twin-related tetrahedral building units that do not have an fcc structure. The crystal structure of these slightly deformed tetrahedra is rhombohedral. Experimental evidence supporting this particle model was obtained by selected-zone dark field and weak beam dark field electron microscopy. In conjunction with the results of part I, it has been concluded that multiply-twinned gold particles of pentagonal or hexagonal profile that are found during the early stages of the vapor deposition growth process on alkali halide surfaces do not have an fcc crystal structure, which is in obvious contrast to the structure of bulk gold.

Nanophotonic switch: gold-in-Ga2O3 peapod nanowires.

PubMed

Hsieh, Chin-Hua; Chou, Li-Jen; Lin, Gong-Ru; Bando, Yoshio; Golberg, Dimitri

2008-10-01

A novel metal-insulator heterostructure made of twinned Ga2O3 nanowires embedding discrete gold particles along the twin boundary was formed through a reaction between gold, gallium, and silica at 800 degrees C during simple thermal annealing. The Au-in-Ga2O3 peapods spontaneously crystallized under phase separation induced by the formation of twin boundaries. The nanostructures were analyzed by field emission scanning (FESEM) and transmission electron microscopes (FETEM), and their photoresponse was investigated using a double-frequency Nd:YAG laser with a wavelength of 532 nm on a designed single-nanowire device. The surface plasmon resonance (SPR) effects of embedded Au nanoparticles are proposed to be responsible for the remarkable photoresponse of these novel structures.

Surface plasmon resonance-induced photoactivation of gold nanoparticles as bactericidal agents against methicillin-resistant Staphylococcus aureus

PubMed Central

Mocan, Lucian; Ilie, Ioana; Matea, Cristian; Tabaran, Flaviu; Kalman, Ersjebet; Iancu, Cornel; Mocan, Teodora

2014-01-01

Systemic infections caused by methicillin-resistant Staphylococcus aureus (MRSA) and other bacteria are responsible for millions of deaths worldwide, and much of this mortality is due to the rise of antibiotic-resistant organisms as a result of natural selection. Gold nanoparticles synthesized using the standard wet chemical procedure were photoexcited using an 808 nm 2 W laser diode and further administered to MRSA bacteria. Flow cytometry, transmission electron microscopy, contrast phase microscopy, and fluorescence microscopy combined with immunochemical staining were used to examine the interaction of the photoexcited gold nano-particles with MRSA bacteria. We show here that phonon–phonon interactions following laser photoexcitation of gold nanoparticles exhibit increased MRSA necrotic rates at low concentrations and short incubation times compared with MRSA treated with gold nanoparticles alone. These unique data may represent a step forward in the study of bactericidal effects of various nanomaterials, with applications in biology and medicine. PMID:24711697

Preparation of lisinopril-capped gold nanoparticles for molecular imaging of angiotensin-converting enzyme

NASA Astrophysics Data System (ADS)

Li, Yuan; Baeta, Cesar; Aras, Omer; Daniel, Marie-Christine

2009-05-01

Overexpression of angiotensin-converting enzyme (ACE) has been associated with the pathophysiology of cardiac and pulmonary fibrosis. Moreover, the prescription of ACE inhibitors, such as lisinopril, has shown a favorable effect on patient outcome for patients with heart failure or systemic hypertension. Thus targeted imaging of the ACE would be of crucial importance for monitoring tissue ACE activity as well as the treatment efficacy in heart failure. In this respect, lisinopril-coated gold nanoparticles were prepared to provide a new type of probe for targeted molecular imaging of ACE by tuned K-edge computed tomography (CT) imaging. The preparation involved non-modified lisinopril, using its primary amine group as the anchoring function on the gold nanoparticles surface. The stable lisinopril-coated gold nanoparticles obtained were characterized by UV-vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM). Their zeta potential was also measured in order to assess the charge density on the modified gold nanoparticles (GNPs).

The detection of HBV DNA with gold-coated iron oxide nanoparticle gene probes

NASA Astrophysics Data System (ADS)

Xi, Dong; Luo, XiaoPing; Lu, QiangHua; Yao, KaiLun; Liu, ZuLi; Ning, Qin

2008-03-01

Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.

Synthesis of gold and silver nanoparticles using leaf extract of Perilla frutescens--a biogenic approach.

PubMed

Basavegowda, Nagaraj; Lee, Yong Rok

2014-06-01

The present investigation demonstrates a rapid biogenic approach for the synthesis of gold and silver nanoparticles using biologically active and medicinal important Perilla frutescens leaf extract as a reducing and stabilizing agent under ambient conditions. Gold and silver nanoparticles were first synthesized from Perilla frutescens leaf extract which was used as a vegetable and in traditional medicines for a long time in Korea, Japan, and China. The nanoparticles obtained were characterized by UV-vis spectroscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. Surface plasmon resonance spectra of gold and silver nanoparticles were obtained at 540 and 430 nm and triangular and spherical shape respectively. TEM studies showed that the particle sizes of gold and silver nanoparticles ranges -50 nm and -40 nm respectively. X-ray diffraction studies confirm that the biosynthesized nanoparticles were crystalline gold and silver. Fourier transform infra-red spectroscopy revealed that biomolecules were involved in the synthesis and capping of the nanoparticles produced. XRD and EDX confirmed the formation of gold and silver nanoparticles. This is a simple, efficient and rapid method to synthesize gold and silver nanoparticles at room temperature without use of toxic chemicals. Obtained gold and silver nanoparticles can be used in various biomedical and biotechnological applications.

Platinum nanoparticles decorated dendrite-like gold nanostructure on glassy carbon electrodes for enhancing electrocatalysis performance to glucose oxidation

NASA Astrophysics Data System (ADS)

Jia, Hongmei; Chang, Gang; Lei, Ming; He, Hanping; Liu, Xiong; Shu, Honghui; Xia, Tiantian; Su, Jie; He, Yunbin

2016-10-01

Platinum nanoparticles decorated dendrite-like gold nanostructure, bimetal composite materials on glassy carbon electrode (Pt/DGNs/GC) for enhancing electrocatalysis to glucose oxidation was designed and successfully fabricated by a facile two-step deposition method without any templates, surfactants, or stabilizers. Dendrite-like gold nanostructure was firstly deposited on the GC electrode via the potentiostatic method, and then platinum nanoparticles were decorated on the surface of gold substrate through chemical reduction deposition. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) were applied to characterize the evolution of morphology and structure of the as-prepared Pt/DGNs/GC. Based on electrochemical measurements such as cyclic voltammetry, linear voltammetry and chronoamperometry, Pt/DGNs/GC exhibited significantly enhanced electrocatalytic performance to glucose oxidation compared those of pure dendrite-like Au nanoparticles in our previous report. Controlling chemical reduction deposition time, the amount of platinum nanoparticles on Au surface could be regulated, which further tuned electrocatalytic properties toward glucose oxidation. The dendrite-like gold surface partially covered by platinum nanoparticles dramatically enhanced the electrocatalytic performance for the oxidation of glucose because of excellent synergetic effects between gold and platinum species and the increased electrochemical active area from Pt nanoparticles loading. The non-enzymatic glucose biosensor based on Pt/DGNs/GC showed a rapid respond time (within 2 s), wide linear range (from 0.1 mM to 14 mM), low detection limit (0.01 mM), supernal sensitivity (275.44 μA cm-2 mM-1, R = 0.993), satisfactory reproducibility and good stability for glucose sensing. It was demonstrated that Pt/DGNs/GC could work as promising candidate for factual non-enzymatic glucose detection.

Rich variety of substrates for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Nguyen, Bich Ha; Hieu Nguyen, Van; Nhung Tran, Hong

2016-09-01

The efficiency of the application of surface enhanced Raman spectroscopy (SERS) technique to each specified purpose significantly depends on the choice of the SERS substrate with an appropriate structure as well as on its performance. Until the present time a rich variety of SERS substrates was fabricated. They can be classified according to their structures. The present work is a review of main types of SERS substrates for using in the trace analysis application. They can be classified into 4 groups: (1) Substrates using gold nanoparticles (AuNPs) with spherical shape such as colloidal AuNPs, AuNPs fabricated by pulsed laser deposition, by sputtering or by capillary force assembly (CFA), substrates fabricated by electrospinning technique, substrates using metallic nanoparticle arrays fabricated by electron beam lithography combined with CFA method, substrates using silver nanoparticle (AgNP) arrays grain by chemical seeded method, substrates with tunable surface plasmon resonance, substrates based on precies subnanometer plasmonic junctions within AuNP assemblies, substrates fabricated by simultaneously immobilizing both AuNPs and AgNPs on the same glass sides etc. (2) Substrates using nanostructures with non-spherical shapes such as gold nanowire (NW), or highly anisotropic nickel NW together with large area, free-standing carpets, substrates with obviously angular, quasi-vertically aligned cuboid-shaped TiO2 NW arrays decorated with AgNPs, substrates using gold nanoprism monolayer films, substrates using silver nanocube dimmers or monodisperse close-packed gold nanotriangle monolayers. (3) Substrates using multiparticle complex nanostructure such as nanoparticle cluster arrays, gold nanoflowers and nanodendrites. (4) Flexible substrate such as paper-based swab with gold nanorods, adhesive polymer tapes fabricated by inkjet printing method and flexible and adhesive SERS tapes fabricated by decorating AuNPs via the conventional drop-dry method.

Gas-Phase Synthesis of Gold- and Silica-Coated Nanoparticles

NASA Astrophysics Data System (ADS)

Boies, Adam Meyer

2011-12-01

Composite nanoparticles consisting of separate core-shell materials are of interest for a variety of biomedical and industrial applications. By combining different materials at the nanoscale, particles can exhibit enhanced or multi-functional behavior such as plasmon resonance combined with superparamagnetism. Gas-phase nanoparticle synthesis processes are promising because they can continuously produce particles with high mass-yield rates. In this dissertation, new methods are investigated for producing gas-phase coatings of nanoparticles in an "assembly-line" fashion. Separate processes are developed to create coatings from silica and gold that can be used with a variety of core-particle chemistries. A photoinduced chemical vapor deposition (photo-CVD) method is used to produce silica coatings from tetraethyl orthosilicate (TEOS) on the surface of nanoparticles (diameter ˜5--70 nm). Tandem differential mobility analysis (TDMA) of the process demonstrates that particle coatings can be produced with controllable thicknesses (˜1--10 nm) by varying system parameters such as precursor flow rate. Electron microscopy and infrared spectroscopy confirm that the photo-CVD films uniformly coat the particles and that the coatings are silica. In order to describe the coating process a chemical mechanism is proposed that includes gas-phase, surface and photochemical reactions. A chemical kinetics model of the mechanism indicates that photo-CVD coating proceeds primarily through the photodecomposition of TEOS which removes ethyl groups, thus creating activated TEOS species. The activated TEOS then adsorbs onto the surface of the particle where a series of subsequent reactions remove the remaining ethyl groups to produce a silica film with an open site for further attachment. The model results show good agreement with the experimentally measured coating trends, where increased TEOS flow increases coating thickness and increased nitrogen flow decreases coating thickness. Gold decoration of nanoparticles is accomplished by evaporation of solid gold in the presence of an aerosol flow. A hot-wire generation method is developed where gold particles are produced from a composite gold-platinum wire. Investigations of the hot-wire generator show that it can produce particles with a range of sizes and that more uniform, non-agglomerated particles are produced when using smaller diameter tubes where gas velocities across the wire are higher and recirculation zones are diminished. When gold is evaporated in the presence of silica nanoparticles, the silica aerosol is decorated by gold through either homogeneous gold nucleation and subsequent scavenging by the silica nanoparticles, or by heterogeneous nucleation on the silica surface in which the gold "balls up" due to the high surface tension of gold on silica. In both cases the resulting particles exhibit a plasmon absorbance resonance typical of gold nanoparticles (lambda˜550 nm). Finally, the silica coating and gold decoration processes are combined with a thermal plasma technique for synthesizing iron-oxide to produce tri-layer nanoparticles.

Preparation of gold nanoparticles by microwave heating and application of spectroscopy to study conjugate of gold nanoparticles with antibody E. coli O157:H7

NASA Astrophysics Data System (ADS)

Thanh Ngo, Vo Ke; Phuong Uyen Nguyen, Hoang; Phat Huynh, Trong; Nguyen Pham Tran, Nguyen; Lam, Quang Vinh; Dat Huynh, Thanh

2015-09-01

Gold nanoparticles (AuNPs) of 15-20 nm size range have attracted attention for producing smart sensing devices as diagnostic tools in biomedical sciences. Citrate capped AuNPs are negatively charged, which can be exploited for electrostatic interactions with some positively charged biomolecules like antibodies. In this paper we describe a method for the low cost synthesis of gold nanoparticles using sodium citrate (Na3Ct) reduction in chloroauric acid (HAuCl4.3H2O) by microwave heating (diameter about 13-15 nm). Gold nanoparticles were functionalized with surface activation by 3-mercaptopropionic acid for attaching antibody. These nanoparticles were then reacted with anti-E. coli O157:H7, using N-hydroxy succinimide (NHS) and carbondimide hydrochloride (EDC) coupling chemistry. The product was characterized with UV-visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy and zeta potential. In addition, the binding of antibody-gold nanoparticles conjugates to E. coli O157:H7 was demonstrated using transmission electron microscopy (TEM).

Interface effects in the dissolution of silicon into thin gold films

NASA Technical Reports Server (NTRS)

Sankur, H.; Mccaldin, J. O.

1975-01-01

The dissolution of crystalline Si and amorphous Si substrates into thin films of evaporated Au was studied with an electron microprobe and scanning electron microscopy. The dissolution pattern was found to be nonuniform along the plane of the surface and dependent on the crystalline orientation of the Si substrate. The dissolution is greatly facilitated when a very thin layer of Pd is evaporated between the Si substrate and the Au film.

Required Equipment for Photo-Switchable Donor-Acceptor (D-A) Dyad Interfacial Self-Assembled Monolayers for Organic Photovoltaic Cells

DTIC Science & Technology

2014-01-24

Interfacial Tuning via Electron-Blocking/Hole-Transport Layers and Indium Tin Oxide Surface Treatment in Bulk- Heterojunction Organic Photovoltaic Cells...devices Figure 3 shows the compounds we prepared to assemble on gold (Au) surfaces. Results of TPA-C60 dyads (1 and 2) self-assembled on Au electrodes...surface hydroxyl groups, respectively, we decided to prepare compounds 5-7 to attach as SAMs, see Figure 5. Difficulties and unexpected problems

Dielectric function of two-phase colloid-polymer nanocomposite.

PubMed

Mitzscherling, S; Cui, Q; Koopman, W; Bargheer, M

2015-11-28

The plasmon resonance of metal nanoparticles determines their optical response in the visible spectral range. Many details such as the electronic properties of gold near the particle surface and the local environment of the particles influence the spectra. We show how the cheap but highly precise fabrication of composite nanolayers by spin-assisted layer-by-layer deposition of polyelectrolytes can be used to investigate the spectral response of gold nanospheres (GNS) and gold nanorods (GNR) in a self-consistent way, using the established Maxwell-Garnett effective medium (MGEM) theory beyond the limit of homogeneous media. We show that the dielectric function of gold nanoparticles differs from the bulk value and experimentally characterize the shape and the surrounding of the particles thoroughly by SEM, AFM and ellipsometry. Averaging the dielectric functions of the layered surrounding by an appropriate weighting with the electric field intensity yields excellent agreement for the spectra of several nanoparticles and nanorods with various cover-layer thicknesses.

Gold-on-Polymer-Based Sensing Films for Detection of Organic and Inorganic Analytes in the Air

NASA Technical Reports Server (NTRS)

Manatt, Kenneth; Homer, Margie; Ryan, Margaret; Kisor, Adam; Shevade, Abhijit; Jewell, April; Zhou, Hanying

2008-01-01

A document discusses gold-on-polymer as one of the novel sensor types developed for part of the sensor development task. Standard polymer-carbon composite sensors used in the JPL Electronic Nose (ENose) have been modified by evaporating 15 nm of metallic gold on the surface. These sensors have been shown to respond to alcohols, aromatics, ammonia, sulfur dioxide, and elemental mercury in the parts-per-million and parts-per-billion concentration ranges in humidified air. The results have shown good sensitivity of these films operating under mild conditions (operating temperatures 23-28 C and regeneration temperature up to 40 C). This unique sensor combines the diversity of polymer sensors for chemical sensing with their response to a wide variety of analytes with the specificity of a gold sensor that shows strong reaction/binding with selected analyte types, such as mercury or sulfur.

Gold nanowire assembling architecture for H2O2 electrochemical sensor.

PubMed

Guo, Shaojun; Wen, Dan; Dong, Shaojun; Wang, Erkang

2009-02-15

Morphological control of nanomaterials is of great interest due to their size and shape-dependent chemical and physical properties and very important applications in many fields such as biomedicine, sensors, electronics and others. In this paper, we reported a simple strategy for synthesizing gold nanowire assembling architecture at room temperature. It is found that two important factors, the proper volume ratio of ethanol to water and poly(vinyl pyrrolidone) (PVP), will play important roles in synthesizing flower-like short gold nanowire assembling spheres. Furthermore, the obtained flower-like gold assembling spheres with high surface-to-volume ratio have been employed as enhancing materials for electrochemical sensing H(2)O(2). The present electrochemical sensing platform exhibited good electrocatalytic activity towards the reduction of H(2)O(2). The detection limit for H(2)O(2) was found to be 1.2 microM, which was lower than certain enzyme-based biosensors.

Lantana camara Linn leaf extract mediated green synthesis of gold nanoparticles and study of its catalytic activity

NASA Astrophysics Data System (ADS)

Dash, Shib Shankar; Bag, Braja Gopal; Hota, Poulami

2015-03-01

A facile one-step green synthesis of stable gold nanoparticles (AuNPs) has been described using chloroauric acid (HAuCl4) and the leaf extract of Lantana camara Linn (Verbenaceae family) at room temperature. The leaf extract enriched in various types of plant secondary metabolites is highly efficient for the reduction of chloroaurate ions into metallic gold and stabilizes the synthesized AuNPs without any additional stabilizing or capping agents. Detailed characterizations of the synthesized gold nanoparticles were carried out by surface plasmon resonance spectroscopy, transmission electron microscopy, dynamic light scattering, Zeta potential, X-ray diffraction and Fourier transform-infrared spectroscopy studies. The synthesized AuNPs have been utilized as a catalyst for the sodium borohydride reduction of 4-nitrophenol to 4-aminophenol in water at room temperature under mild reaction condition. The kinetics of the reduction reaction has been studied spectrophotometrically.

Exciton emission from bare and hybrid plasmonic GaN nanorods

NASA Astrophysics Data System (ADS)

Mohammadi, Fatemesadat; Kunert, Gerd; Hommel, Detlef; Ge, Jingxuan; Duscher, Gerd; Schmitzer, Heidrun; Wagner, Hans Peter

We study the exciton emission of hybrid gold nanoparticle/Alq3 (aluminiumquinoline)/wurtzite GaN nanorods. GaN nanorods of 1.5 μm length and 250 nm diameter were grown by plasma assisted MBE. Hybrid GaN nanorods were synthesized by organic molecular beam deposition. Temperature and power dependent time integrated (TI) and time resolved (TR) photoluminescence (PL) measurements were performed on bare and hybrid structures. Bare nanorods show donor (D0,X) and acceptor bound (A0,X) exciton emission at 3.473 eV and at 3.463 eV, respectively. TR-PL trace modeling reveal lifetimes of 240 ps and 1.4 ns for the (D0,X) and (A0,X) transition. 10 nm gold coated GaN nanorods show a significant PL quenching and (D0,X) lifetime shortening which is tentatively attributed to impact ionization of (D0,X) due to hot electron injection from the gold nanoparticles. This is supported by electron energy loss spectroscopy that shows a redshift of a midgap state transition indicating a reduction of a preexisting band-bending at the nanorod surface due to positive charging of the gold nanoparticles. Inserting a nominally 5 nm thick Alq3 spacer between the nanorod and the gold reduces the PL quenching and lifetime shortening. Plasmonic nanorods with a 30 nm thick Alq3 spacer reveal lifetimes which are nearly identical to uncoated GaN nanorods.

Production of a Novel Fucoidanase for the Green Synthesis of Gold Nanoparticles by Streptomyces sp. and Its Cytotoxic Effect on HeLa Cells

PubMed Central

Manivasagan, Panchanathan; Oh, Junghwan

2015-01-01

Marine actinobacteria-produced fucoidanases have received considerable attention as one of the major research topics in recent years, particularly for the medical exploitation of fucoidans and their degradation products. The present study describes the optimization and production of a novel fucoidanase for the green synthesis of gold nanoparticles and its biological applications. The production of fucoidanase was optimized using Streptomyces sp. The medium components were selected in accordance with the Plackett-Burman design and were further optimized via response surface methodology. The fucoidanase was statistically optimized with the most significant factors, namely wheat bran 3.3441 g/L, kelp powder 0.7041 g/L, and NaCl 0.8807 g/L, respectively. The biosynthesized gold nanoparticles were determined by UV-vis spectroscopy and were further characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray analysis, and high-resolution transmission electron microscopy. Furthermore, the biosynthesized gold nanoparticles exhibited a dose-dependent cytotoxicity against HeLa cells and the inhibitory concentration (IC50) was found to be 350 µg/mL at 24 h and 250 µg/mL at 48 h. Therefore, the production of novel fucoidanase for the green synthesis of gold nanoparticles has comparatively rapid, less expensive and wide application to anticancer therapy in modern medicine. PMID:26569267

Development of Millimeter Wave Fabry-Pérot Resonator for Simultaneous Electron-Spin and Nuclear Magnetic Resonance Measurement

NASA Astrophysics Data System (ADS)

Ishikawa, Yuya; Ohya, Kenta; Fujii, Yutaka; Fukuda, Akira; Miura, Shunsuke; Mitsudo, Seitaro; Yamamori, Hidetomo; Kikuchi, Hikomitsu

2018-04-01

We report a Fabry-Pérot resonator with spherical and flat mirrors to allow simultaneous electron-spin resonance (ESR) and nuclear magnetic resonance (NMR) measurements that could be used for double magnetic resonance (DoMR). In order to perform simultaneous ESR and NMR measurements, the flat mirror must reflect millimeter wavelength electromagnetic waves and the resonator must have a high Q value ( Q > 3000) for ESR frequencies, while the mirror must simultaneously let NMR frequencies pass through. This requirement can be achieved by exploiting the difference of skin depth for the two frequencies, since skin depth is inversely proportional to the square root of the frequency. In consideration of the skin depth, the optimum conditions for conducting ESR and NMR using a gold thin film are explored by examining the relation between the Q value and the film thickness. A flat mirror with a gold thin film was fabricated by sputtering gold on an epoxy plate. We also installed a Helmholtz radio frequency coil for NMR and tested the system both at room and low temperatures with an optimally thick gold film. As a result, signals were obtained at 0.18 K for ESR and at 1.3 K for NMR. A flat-mirrored resonator with a thin gold film surface is an effective way to locate NMR coils closer to the sample being examined with DoMR.

Production of a Novel Fucoidanase for the Green Synthesis of Gold Nanoparticles by Streptomyces sp. and Its Cytotoxic Effect on HeLa Cells.

PubMed

Manivasagan, Panchanathan; Oh, Junghwan

2015-11-12

Marine actinobacteria-produced fucoidanases have received considerable attention as one of the major research topics in recent years, particularly for the medical exploitation of fucoidans and their degradation products. The present study describes the optimization and production of a novel fucoidanase for the green synthesis of gold nanoparticles and its biological applications. The production of fucoidanase was optimized using Streptomyces sp. The medium components were selected in accordance with the Plackett-Burman design and were further optimized via response surface methodology. The fucoidanase was statistically optimized with the most significant factors, namely wheat bran 3.3441 g/L, kelp powder 0.7041 g/L, and NaCl 0.8807 g/L, respectively. The biosynthesized gold nanoparticles were determined by UV-vis spectroscopy and were further characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray analysis, and high-resolution transmission electron microscopy. Furthermore, the biosynthesized gold nanoparticles exhibited a dose-dependent cytotoxicity against HeLa cells and the inhibitory concentration (IC50) was found to be 350 µg/mL at 24 h and 250 µg/mL at 48 h. Therefore, the production of novel fucoidanase for the green synthesis of gold nanoparticles has comparatively rapid, less expensive and wide application to anticancer therapy in modern medicine.

In Vivo Neural Recording and Electrochemical Performance of Microelectrode Arrays Modified by Rough-Surfaced AuPt Alloy Nanoparticles with Nanoporosity

PubMed Central

Zhao, Zongya; Gong, Ruxue; Zheng, Liang; Wang, Jue

2016-01-01

In order to reduce the impedance and improve in vivo neural recording performance of our developed Michigan type silicon electrodes, rough-surfaced AuPt alloy nanoparticles with nanoporosity were deposited on gold microelectrode sites through electro-co-deposition of Au-Pt-Cu alloy nanoparticles, followed by chemical dealloying Cu. The AuPt alloy nanoparticles modified gold microelectrode sites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and in vivo neural recording experiment. The SEM images showed that the prepared AuPt alloy nanoparticles exhibited cauliflower-like shapes and possessed very rough surfaces with many different sizes of pores. Average impedance of rough-surfaced AuPt alloy nanoparticles modified sites was 0.23 MΩ at 1 kHz, which was only 4.7% of that of bare gold microelectrode sites (4.9 MΩ), and corresponding in vitro background noise in the range of 1 Hz to 7500 Hz decreased to 7.5 μVrms from 34.1 μVrms at bare gold microelectrode sites. Spontaneous spike signal recording was used to evaluate in vivo neural recording performance of modified microelectrode sites, and results showed that rough-surfaced AuPt alloy nanoparticles modified microelectrode sites exhibited higher average spike signal-to-noise ratio (SNR) of 4.8 in lateral globus pallidus (GPe) due to lower background noise compared to control microelectrodes. Electro-co-deposition of Au-Pt-Cu alloy nanoparticles combined with chemical dealloying Cu was a convenient way for increasing the effective surface area of microelectrode sites, which could reduce electrode impedance and improve the quality of in vivo spike signal recording. PMID:27827893

Synthesis of gold nanoparticles on multi-walled carbon nanotubes (Au-MWCNTs) via deposition precipitation method

NASA Astrophysics Data System (ADS)

Zulikifli, Farah Wahida Ahmad; Yazid, Hanani; Halim, Muhammad Zikri Budiman Abdul; Jani, Abdul Mutalib Md

2017-09-01

Carbon nanotubes (CNTs) have received impressive consideration as support materials of noble metal catalysts in heterogeneous catalysis due to their good mechanical strength, large surface area and good durability under harsh conditions. The interaction between CNTs and noble metal nanoparticles (NPs) gives an unusual unique microstructure properties and or modification of the electron density of the noble metal clusters, and enhances the catalytic activity. In this study, the MWCNTs were first treated with a mixture of concentrated sulfuric and nitric acid by sonication to improve its dispersibility and to introduce the carboxylic (-COOH) groups on CNTs surfaces. Gold nanoparticles (Au NPs) on multiwalled carbon nanotubes (MWCNTs) were synthesized by the deposition precipitation (DP) method as this method is simpler, low cost, and excellent method. Then, the effect of reducing agent (NaBH4) on gold distribution on the support of MWCNTs was also studied. Dispersion test, Fourier Transform Infrared spectroscopy (FTIR) and Field Emission Scanning Electron Microscope (FESEM) are all used to characterize the functionalized MWCNTs (fCNTs) and the Au NPs-fCNTs catalyst. There are three important peaks in functionalized MWCNTs which correspond to C=O, O-H, and C-O absorption peaks, as a result of the oxidation of COOH groups on the surface of CNTs. The absorption band at 1717 cm-1 is corresponded to C=O stretching of COOH, while the absorption bands at 3384 cm-1 and 1011cm-1 are associated with O-H bending and C-O stretching, respectively. Surface morphology of Au NPs-fCNTs R4 and Au NPs- fCNTs WR catalyst by FESEM showed that the Au NPs of 19.22 ± 2.33 nm and 23.05 ± 2.57 nm size were successfully deposited on CNTs, respectively.

Guided selective deposition of nanoparticles by tuning of the surface potential

NASA Astrophysics Data System (ADS)

Eklöf, J.; Stolaś, A.; Herzberg, M.; Pekkari, A.; Tebikachew, B.; Gschneidtner, T.; Lara-Avila, S.; Hassenkam, T.; Moth-Poulsen, K.

2017-07-01

Guided deposition of nanoparticles onto different substrates is of great importance for a variety of applications such as biosensing, targeted cancer therapy, anti-bacterial coatings and single molecular electronics. It is therefore important to gain an understanding of what parameters are involved in the deposition of nanoparticles. In this work we have deposited 60 nm, negatively charged, citrate stabilized gold nanoparticles onto microstructures consisting of six different materials, (vanadium (V), silicon dioxide (SiO2), gold (Au), aluminum (Al), copper (Cu) and nickel (Ni)). The samples have then been investigated by scanning electron microscopy to extract the particle density. The surface potential was calculated from the measured surface charge density maps measured by atomic force microscopy while the samples were submerged in a KCl water solution. These values were compared with literature values of the isoelectric points (IEP) of different oxides formed on the metals in an ambient environment. According to measurements, Al had the highest surface potential followed by Ni and Cu. The same trend was observed for the nanoparticle densities. No particles were found on V, SiO2 and Au. The literature values of the IEP showed a different trend compared to the surface potential measurements concluding that IEP is not a reliable parameter for the prediction of NP deposition. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

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

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

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

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 H{sub 2}O{sub 2} as an oxidizer. The reshaping of these nanostructures has been demonstrated as a consequence of an oxidation process in which HGNSs are dissolved by H{sub 2}O{sub 2} under the acidic conditions provided by HCl. Wemore » 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.« less

Electrodeposition of gold particles on aluminum substrates containing copper.

PubMed

Olson, Tim S; Atanassov, Plamen; Brevnov, Dmitri A

2005-01-27

Electrodeposition of adhesive metal films on aluminum is traditionally preceded by the zincate process, which activates the aluminum surface. This paper presents an alternative approach for activation of aluminum by using films containing 99.5% aluminum and 0.5% copper. Aluminum/copper films are made amenable for subsequent electrodeposition by anodization followed by chemical etching of aluminum oxide. The electrodeposition of gold is monitored with electrochemical impedance spectroscopy (EIS). Analysis of EIS data suggests that electrodeposition of gold increases the interfacial capacitance from values typical for electrodes with thin oxide layers to values typical for metal electrodes. Scanning electron microscopy examination of aluminum/copper films following gold electrodeposition shows the presence of gold particles with densities of 10(5)-10(7) particles cm(-2). The relative standard deviation of mean particle diameters is approximately 25%. Evaluation of the micrographs suggests that the electrodeposition occurs by instantaneous nucleation followed by growth of three-dimensional semispherical particles. The gold particles, which are electrically connected to the conductive aluminum/copper film, support a reversible faradaic process for a soluble redox couple. The deposited gold particles are suitable for subsequent metallization of aluminum and fabrication of particle-type films with interesting catalytic, electrical, and optical properties.

Diameter-dependent optical constants of gold mesoparticles electrodeposited on aluminum films containing copper.

PubMed

Brevnov, Dmitri A; Bungay, Corey

2005-08-04

Electrodeposition of gold mesoparticles on anodized and chemically etched aluminum/copper films deposited on silicon wafers proceeds by instantaneous nucleation and with no diffusion limitations. Both of these phenomena favor the formation of relatively monodispersed gold particles. Under the reported electrodeposition conditions, the relative standard deviation of the particle diameter is 25%. The particle coverage is 7 x 10(8) particles cm(-2). The mean particle diameter varies as a function of electrodeposition time in the range of 40-80 nm. Optical constants of gold mesoparticles are resolved by spectroscopic ellipsometry. A two-layer optical model is constructed to determine both extinction coefficients and refractive indexes of gold mesoparticles as a function of the mean particle diameter. The absorption peak, associated with surface plasmons, is modeled with two Lorentz oscillators. Absorption peak maximums shift from 610 to 675 nm as the mean particle diameter increases from 42 to 74 nm. Electrodeposition of gold particles on technologically relevant substrates, such as aluminum/copper films, is expected to increase the utility of gold particles and facilitate their incorporation in nanostructured materials and a variety of electronic and optical devices.

The electrokinetic characterization of gold nanoparticles, functionalized with cationic functional groups, and its' interaction with DNA.

PubMed

Lazarus, Geraldine Genevive; Revaprasadu, Neerish; López-Viota, Julián; Singh, Moganavelli

2014-09-01

Gold nanoparticles have attracted strong biomedical interest for drug delivery due to their low toxic nature, surface plasmon resonance and capability of increasing the stability of the payload. However, gene transfection represents another important biological application. Considering that cellular barriers keep enclosed their secret to deliver genes using nanoparticles, an important step can be achieved by studying the functionalization of nanoparticles with DNA. In the present contribution the synthesis of nanoparticles consisting of a gold core coated with one or more layers of amino acid (l-lysine), and cationic polyelectrolytes (poly-ethyleneimine and poly-l-lysine) is reported. All nanoparticles were subjected to dynamic light scattering, electrophoretic mobility measurements, UV-vis optical spectrophotometry analysis and transmission electron microscopy imaging. In addition, the adsorption of DNA plasmid (pSGS) with linear and supercoiled configurations was studied for those gold nanoparticles under the most suitable surface modifications. Preliminary results showed that the gold nanoparticles functionalized with poly-ethyleneimine and poly-l-lysine, respectively, and bound to linear DNA configurations, present in absolute value a higher electrophoretic mobility irrespective of the pH of the media, compared to the supercoiled and nicked configuration. The findings from this study suggest that poly-ethyleneimine and poly-l-lysine functionalized gold nanoparticles are biocompatible and may be promising in the chemical design and future optimization of nanostructures for biomedical applications such as gene and drug delivery. Copyright © 2014 Elsevier B.V. All rights reserved.

Gold-Based Nanostructures for Ultrafast Dynamic Nanothermometer

NASA Astrophysics Data System (ADS)

Sun, Hongtao

Nano-scale temperature measurements are of significance for fundamental understanding of functional applications and nanosystems, requiring ultimate miniaturization of thermometers with reduced size, maintained sensitivity, simplicity and accuracy of temperature reading. Particularly, grand challenges exist for scenarios of combustion or thermal shock where materials may be subjected to drastic temperature variations and extreme thermal flux, and dynamic thermal sensors with an ultrafast response (seconds to milliseconds) are yet to be developed. Targeting the developments of advanced nano-scale thermal sensors with a fast time response and rapid readout, this thesis reports innovative designs of high surface-to-volume ratio gold nanostructures including ultrathin gold island films on transparent quartz substrates and silica-gold core-shell (SiO2 Au) nanospheres as potential dynamic thermal sensors for accurate temperature determination. The sensing mechanism is based on strong temperature dependences of the thermally-dewetting-induced morphological self-reorganization and characteristic surface plasmon (SP) absorption of the gold nanostructures. The irreversible thermally-induced morphological and optical signatures behave as characteristic "fingerprints" for temperature recording, allowing the retrieval of thermal history ex-situ. The fundamental studies of thermal-induced dewetting process and its corresponding unique optical properties were extensively investigated by high resolution scanning electron microscopy (HR-SEM), atomic force microscopy (AFM), and UV-vis-NIR spectroscopy, which illustrate temperature and time dependent variations. As compared with current nanothermometer technologies such as metal-filled nanotubes, our thermo-sensor offers positively synergistic advantages of ultrafast time response, permanent recording and fast readout of thermal history, and ex-situ capability for effective temperature measurements. In addition, SiO2 Au nanospheres display simultaneously enhanced near bandgap edge (NBE) emissions and suppress defect level emission (DLE) of poly(vinyl alcohol) (PVA) zinc oxide nanoparticles (ZnO NPs), significantly improving the UV emission of the ZnO. Maximum emission enhancement by nearly 4 times was observed using SiO2 Au nanospheres with SP band at 554 nm. The enhanced UV emission is ascribed to the transfer of the energetic electrons excited by SP from gold nanoshells to the conduction band of ZnO. As a result of their superior tunability of surface plasmon resonance (SPR), the SiO2 Au core/shell nanospheres may be very useful in tuning the photoluminescence for a wide range of optoelectronic applications.

Proof-of-principle for SERS imaging of Aspergillus nidulans hyphae using in vivo synthesis of gold nanoparticles.

PubMed

Prusinkiewicz, Martin A; Farazkhorasani, Fatemeh; Dynes, James J; Wang, Jian; Gough, Kathleen M; Kaminskyj, Susan G W

2012-11-07

High spatial resolution methods to assess the physiology of growing cells should permit analysis of fungal biochemical composition. Whole colony methods cannot capture the details of physiology and organism-environment interaction, in part because the structure, function and composition of fungal hyphae vary within individual cells depending on their distance from the growing apex. Surface Enhanced Raman Scattering (SERS) can provide chemical information on materials that are in close contact with appropriate metal substrates, such as nanopatterned gold surfaces and gold nanoparticles (AuNPs). Since nanoparticles can be generated by living cells, we have created conditions for AuNP formation within and on the surface of Aspergillus nidulans hyphae in order to explore their potential for SERS analysis. AuNP distribution and composition have been assessed by UV-Vis spectroscopy, fluorescence light microscopy, transmission electron microscopy, and scanning transmission X-ray microscopy. AuNPs were often associated with hyphal walls, both in the peripheral cytoplasm and on the outer wall surface. Interpretation of SERS spectra is challenging, and will require validation for the diversity of organic molecules present. Here, we show proof-of-principle that it is possible to generate SERS spectra from nanoparticles grown in situ by living hyphae.

Self-assembled organic radicals on Au(111) surfaces: a combined ToF-SIMS, STM, and ESR study.

PubMed

Mannini, Matteo; Sorace, Lorenzo; Gorini, Lapo; Piras, Federica M; Caneschi, Andrea; Magnani, Agnese; Menichetti, Stefano; Gatteschi, Dante

2007-02-27

Electron spin resonance (ESR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning tunneling microscopy (STM) have been used in parallel to characterize the deposition on gold surface of a series of nitronyl nitroxide radicals. These compounds have been specifically synthesized with methyl-thio linking groups suitable to interact with the gold surface to form self-assembled monolayers (SAMs), which can be considered relevant in the research for molecular-based spintronics devices, as suggested in recent papers. The degree of the expected ordering on the surface of these SAMs has been tuned by varying the chemical structure of synthesized radicals. ToF-SIMS has been used to support the evidence of the occurrence of the deposition process. STM has shown the different qualities of the obtained SAMs, with the degree of local order increasing as the degree of freedom of the molecules on the surface is decreased. Finally, ESR has confirmed that the deposition process does not affect the paramagnetic characteristics of radicals and that it affords a complete single-layered coverage of the surface. Further, the absence of angular dependence in the spectra indicates that the small regions of local ordering do not give rise to a long-range order and suggests a quite large mobility of the radical on the surface, probably due to the weak interaction with gold provided by the methyl-thio linking group.

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 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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33776b

Stability, cytotoxicity and cell uptake of water-soluble dendron–conjugated gold nanoparticles with 3, 12 and 17 nm cores† †Electronic supplementary information (ESI) available: Additional characterization methods and procedures in addition to the data for the characterization of glutathione-capped gold nanoparticles and dendron-conjugated gold nanoparticles including FT-IR spectra (Fig. S1 and S2), UV-vis spectra (Fig. S3 and S6), TEM images (Fig. S4), MALDI-TOF/TOF spectra (Fig. S5), fluorescence spectra (Fig. S6 and S7), In vitro cytotoxic assay results (Fig. S9) and ICP-MS results (Tables 1 and 2). DOI: 10.1039/c5tb00608b Click here for additional data file.

PubMed Central

Deol, Suprit; Weerasuriya, Nisala

2015-01-01

This article describes the synthesis of water-soluble dendron–conjugated gold nanoparticles (Den–AuNPs) with various average core sizes and the evaluation of stability, cytotoxicity, cell permeability and uptake of these materials. The characterization of Den–AuNPs using various techniques including transmission electron microscopy (TEM), matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS), 1H NMR, FT-IR, and UV-vis spectroscopy confirms the dendron conjugation to the glutathione-capped gold nanoparticles (AuNPs). The stability of AuNPs and Den–AuNPs in solutions of different pH and salt concentration is determined by monitoring the changes in surface plasmon bands of gold using UV-vis spectroscopy. The stability of Den–AuNPs at different pH remained about the same compared to that of AuNPs. In comparison, the Den–AuNPs are found to be more stable than the precursor AuNPs maintaining their solubility in the aqueous solution with the salt concentration of up to 100 mM. The improved stability of Den–AuNPs suggests that the post-functionalization of thiol-capped gold nanoparticle surfaces with dendrons can further improve the physiological stability and biocompatibility of gold nanoparticle-based materials. Cytotoxicity studies of AuNPs and Den–AuNPs with and without fluorophores are also performed by examining cell viability for 3T3 fibroblasts using a MTT cell proliferation assay. The conjugation of dendrons to the AuNPs with a fluorophore is able to decrease the cytotoxicity brought about by the fluorophore. The successful uptake of Den–AuNPs in mouse fibroblast 3T3 cells shows the physiological viability of the hybrid materials. PMID:26366289

Frequency-doubled Alexandrite laser for use in periodontology: a scanning electron microscopic investigation

NASA Astrophysics Data System (ADS)

Rechmann, Peter; Hennig, Thomas

1996-12-01

During prior studies it could be demonstrated that engaging a frequency double Alexandrite-laser allows a fast and strictly selective ablation of supra- and subgingival calculus. Furthermore, the removal of unstained microbial plaque was observed. First conclusions were drawn following light microscopic investigations on undecalcified sections of irradiated teeth. In the present study the cementum surface after irradiation with a frequency doubled Alexandrite-laser was observed by means of a scanning electron microscope. After irradiation sections of teeth were dried in alcohol and sputtered with gold. In comparison irradiated cementum surfaces of unerupted operatively removed wisdom teeth and tooth surfaces after the selective removal of calculus were investigated. A complete removal of calculus was observed as well as a remaining smooth surface of irradiated cementum.

Corrosion of RoHS-Compliant Surface Finishes in Corrosive Mixed Flowing Gas Environments

NASA Astrophysics Data System (ADS)

Hannigan, K.; Reid, M.; Collins, M. N.; Dalton, E.; Xu, C.; Wright, B.; Demirkan, K.; Opila, R. L.; Reents, W. D.; Franey, J. P.; Fleming, D. A.; Punch, J.

2012-03-01

Recently, the corrosion resistance of printed wiring board (PWB) finishes has generated considerable interest due to field failures observed in various parts of the world. This study investigates the corrosion issues associated with the different lead-free PWB surface finishes. Corrosion products on various PWB surface finishes generated in mixed flowing gas (MFG) environments were studied, and analysis techniques such as scanning electron microscopy, energy-dispersive x-ray, x-ray diffraction, focused ion beam, and scanning Auger microscopy were used to quantify the corrosion layer thickness and determine the composition of corrosion products. The corrosion on organic solderability preservative samples shows similar corrosion products to bare copper and is mainly due to direct attack of copper traces by corrosive gases. The corrosion on electroless nickel immersion gold occurs primarily through the porosity in the film and is accelerated by the galvanic potential between gold and copper; similar results were observed on immersion silver. Immersion tin shows excellent corrosion resistance due to its inherent corrosion resistance in the MFG environment as well as the opposite galvanic potential between tin and copper compared with gold or silver and copper.

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

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

Han, Chang Wan; Choksi, Tej; Milligan, Cory

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

PubMed

Han, Chang Wan; Choksi, Tej; Milligan, Cory; Majumdar, Paulami; Manto, Michael; Cui, Yanran; Sang, Xiahan; Unocic, Raymond R; Zemlyanov, Dmitry; Wang, Chao; Ribeiro, Fabio H; Greeley, Jeffrey; Ortalan, Volkan

2017-08-09

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe 3 O 4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe 3 O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3 O 4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe 3 O 4 , as the surface reduction of nano-Fe 3 O 4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3 O 4 and the extremely strong adhesion between Au and the reduced Fe 3 O 4 . This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

XAS and XMCD investigation of Mn12 monolayers on gold.

PubMed

Mannini, Matteo; Sainctavit, Philippe; Sessoli, Roberta; Cartier dit Moulin, Christophe; Pineider, Francesco; Arrio, Marie-Anne; Cornia, Andrea; Gatteschi, Dante

2008-01-01

The deposition of Mn(12) single molecule magnets on gold surfaces was studied for the first time using combined X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) methods at low temperature. The ability of the proposed approach to probe the electronic structure and magnetism of Mn(12) complexes without significant sample damage was successfully checked on bulk samples. Detailed information on the oxidation state and magnetic polarization of manganese ions in the adsorbates was obtained from XAS and XMCD spectra, respectively. Partial reduction of metal ions to Mn(II) was clearly observed upon deposition on Au(111) of two different Mn(12) derivatives bearing 16-acetylthio-hexadecanoate and 4-(methylthio)benzoate ligands. The average oxidation state, as well as the relative proportions of Mn(II), Mn(III) and Mn(IV) species, are strongly influenced by the deposition protocol. Furthermore, the local magnetic polarizations are significantly decreased as compared with bulk Mn(12) samples. The results highlight an utmost redox instability of Mn(12) complexes at gold surfaces, presumably accompanied by structural rearrangements, which cannot be easily revealed by standard surface analysis based on X-ray photoelectron spectroscopy and scanning tunnelling microscopy.

Potential drug - nanosensor conjugates: Raman, infrared absorption, surface - enhanced Raman, and density functional theory investigations of indolic molecules

NASA Astrophysics Data System (ADS)

Pięta, Ewa; Paluszkiewicz, Czesława; Oćwieja, Magdalena; Kwiatek, Wojciech M.

2017-05-01

An extremely important aspect of planning cancer treatment is not only the drug efficiency but also a number of challenges associated with the side effects and control of this process. That is why it is worth paying attention to the promising potential of the gold nanoparticles combined with a compound treated as a potential drug. This work presents Raman (RS), infrared absorption (IR) and surface-enhanced Raman scattering (SERS) spectroscopic investigations of N-acetyl-5-methoxytryptamine (melatonin) and α-methyl-DL-tryptophan, regarding as anti breast cancer agents. The experimental spectroscopic analysis was supported by the quantum-chemical calculations based on the B3LYP hybrid density functional theory (DFT) at the B3LYP 6-311G(d,p) level of theory. The studied compounds were adsorbed onto two colloidal gold nanosensors synthesized by a chemical reduction method using sodium borohydride (SB) and trisodium citrate (TC), respectively. Its morphology characteristics were obtained using transmission electron microscopy (TEM). It has been suggested that the NH moiety from the aromatic ring, a well-known proton donor, causes the formation of hydrogen bonds with the negatively charged gold surface.

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

DOE PAGES

Han, Chang Wan; Choksi, Tej; Milligan, Cory; ...

2017-06-26

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

Visualization of nanoconstructions with DNA-Aptamers for targeted molecules binding on the surface of screen-printed electrodes

NASA Astrophysics Data System (ADS)

Lapin, Ivan N.; Shabalina, Anastasiia V.; Svetlichyi, Valery A.; Kolovskaya, Olga S.

2018-04-01

Nanoconstructions of gold nanoparticles (NPs) obtained via pulsed laser ablation in liquid with DNA-aptamer specific to protein tumor marker were visualized on the surface of screen-printed electrode using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). AuNPs/aptamer nanoconstuctions distribution on the solid surface was studied. More uniform coverage of the carbon electrode surface with the nanoconstuctions was showed in comparison with DNA-aptamer alone on the golden electrode surface. Targeted binding of the tumor marker molecules with the AuNPs/DNA-aptamer nanoconstuctions was approved.

A DFT study on surface-enhanced Raman spectroscopy of aromatic dithiol derivatives adsorbed on gold nanojunctions

NASA Astrophysics Data System (ADS)

You, Tingting; Lang, Xiufeng; Huang, Anping; Yin, Penggang

2018-01-01

A computational study on aromatic dithiol derivatives (HS-Ar-X-Ar-SH, X = O, S, Se, NH, CH2, Ndbnd N, CHdbnd CH, Ctbnd C) interacting with gold cluster(s) was presented to investigate the chemical enhancement mechanism related to surface-enhanced Raman spectroscopy (SERS) for molecular junctions. Density functional theory (DFT) were performed on derivatives molecules as well as their single-end-linked (SEL) or double-end-linked (DEL) complexes for geometric, spectra, electronic and excitation properties, leading to discussions on dominant factor during SERS process. The resulted enhancement factors of SEL and DEL complexes exhibited specific dependency on linking atom or functional group between two phenyls, which was in accordance with the variation of polarizabilities and molecule-cluster transition energy.

Electrocatalytic oxidation of cellulose at a gold electrode.

PubMed

Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

2014-08-01

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-shot femtosecond laser ablation of gold surface in air and isopropyl alcohol

NASA Astrophysics Data System (ADS)

Kudryashov, S. I.; Saraeva, I. N.; Lednev, V. N.; Pershin, S. M.; Rudenko, A. A.; Ionin, A. A.

2018-05-01

Single-shot IR femtosecond-laser ablation of gold surfaces in ambient air and liquid isopropyl alcohol was studied by scanning electron microscopy characterization of crater topographies and time-resolved optical emission spectroscopy of ablative plumes in regimes, typical for non-filamentary and non-fragmentation laser production of nanoparticle sols. Despite one order of magnitude shorter (few nanoseconds) lifetimes and almost two orders of magnitude lower intensities of the quenched ablative plume emission in the alcohol ambient at the same peak laser fluence, craters for the dry and wet conditions appeared with rather similar nanofoam-like spallative topographies and the same thresholds. These facts envision the underlying surface spallation as one of the basic ablation mechanisms relevant for both dry and wet advanced femtosecond laser surface nano/micro-machining and texturing, as well as for high-throughput femtosecond laser ablative production of colloidal nanoparticles by MHz laser-pulse trains via their direct nanoscale jetting from the nanofoam in air and fluid environments.

Dual emission behavior of phenyleneethynylene gold(I) complexes dictated by intersystem crossing: a theoretical perspective.

PubMed

Wang, Li; Li, Yuanyuan; Zhang, Yanxin; He, Hongqing; Zhang, Jinglai

2015-02-25

In commonly studied gold(I) complexes with oligo (o-, p-, or m-phenyleneethynylene) (PE) ligands, an intriguing photophysical behavior is dual emission composed of fluorescence from S1 and phosphorescence from T1 which is dictated by effective intersystem crossing (ISC) process. In order to explore the salient photodynamics of such oligo-PE gold(I) complexes effectively, we have deliberately chosen three model complexes, namely, Ph-C≡C-Au(PMe3) (1a') and Ph-C≡C-(1,m)C6H4-C≡C-Au(PMe3) (m=4, 2a'; m=3, 3a') in place of the real system. Firstly, electronic structure methods based on DFT and TD-DFT are utilized to perform optimization calculations for the ground- and lowest-lying excited states, respectively. Next, basic photophysical properties including absorption and emission spectra are investigated by TD-DFT under the optimized geometries. Besides, on the basis of the electronic spectra herein, we succeed in searching for surface intersections as the minima on the seam of singlet-triplet surface crossings (SCs) at the CASSCF level of theory. By integration of the results available, the process of delayed fluorescence of triplet-triplet annihilation (TTA) and phosphorescence was displayed in detail with SCs playing the lead in monitoring the ISC. Copyright © 2014 Elsevier B.V. All rights reserved.

[The experiment research on solution refractive index sensor based on tilted fiber Bragg grating].

PubMed

Jiang, Qi; Lü, Dan-Dan; Yu, Ming-Hao; Kang, Li-Min; Ouyang, Jun

2013-12-01

The present paper analyzes the sensor's basic principle of the bare tilted fiber Bragg grating (TFBG) and surface plasmon resonance sensor (SPR) that deposited nanoscale gold-coating on the surface of the cladding. We simulated the transmission spectrums and some order cladding mode of TFBG in different concentration solutions by Integration and optical fiber grating software OptiGrating. So by the graphic observation and data analysis, a preliminary conclusion was got that in a certain sensing scope, the cladding modes of TFBG shift slightly to right with the increasing the solution refractive index(SRI),and the relation between resonance peak caused by the coupling of core mode and a certain cladding mode and the SRI was linear. Then the 45 nm thick gold coating was deposited on the surface of the TFBG cladding in a small-scale sputtering chamber KYKY SBC-12, and thermal field scanning electron microscopy presents that the effect of gold-coating was satisfactory to a certain extent in terms of microscopic level. The refractive index(RI) sensing experiments of different concentration solutions of NaCI, MgCI2, CaCI2 were carried out using bare and gold deposited TFBG. The RI sensing characteristics of both bare and gold deposited TFBGs respectively were studied by experiments. Meanwhile, it proved the conclusion that the cladding modes of TFBG drifted to right gradually when the SRI was increasing and the relations between resonance peak caused by the coupling of core mode and a certain cladding mode and the SRI were linear. And by quantitative analysis, we know that SPR sensor with the deposited namoscale gold layer on the surface of cladding enhanced the RI sensitivity dramatically by 2 to 500 nm RIU-1 which is 200 to 300 times larger than that of the bare tilted fiber Bragg grating approximately. The degrees of linear fittings of resonance peak caused by the coupling of core mode and a certain cladding mode and SRI of bare and gold-coating deposited SPR sensor are very good and both of them reach up to more than 0. 99.

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.

Enhanced adhesion by high energy bombardment

NASA Technical Reports Server (NTRS)

Griffith, Joseph E. (Inventor); Qiu, Yuanxun (Inventor); Tombrello, Thomas A. (Inventor)

1984-01-01

Films (12) of gold, copper, silicon nitride, or other materials are firmly bonded to insulator substrates (12) such as silica, a ferrite, or Teflon (polytetrafluorethylene) by irradiating the interface with high energy ions. Apparently, track forming processes in the electronic stopping region cause intermixing in a thin surface layer resulting in improved adhesion without excessive doping. Thick layers can be bonded by depositing or doping the interfacial surfaces with fissionable elements or alpha emitters.

Electron heating and thermal relaxation of gold nanorods revealed by two-dimensional electronic spectroscopy.

PubMed

Lietard, Aude; Hsieh, Cho-Shuen; Rhee, Hanju; Cho, Minhaeng

2018-03-01

To elucidate the complex interplay between the size and shape of gold nanorods and their electronic, photothermal, and optical properties for molecular imaging, photothermal therapy, and optoelectronic devices, it is a prerequisite to characterize ultrafast electron dynamics in gold nanorods. Time-resolved transient absorption (TA) studies of plasmonic electrons in various nanostructures have revealed the time scales for electron heating, lattice vibrational excitation, and phonon relaxation processes in condensed phases. However, because linear spectroscopic and time-resolved TA signals are vulnerable to inhomogeneous line-broadening, pure dephasing and direct electron heating effects are difficult to observe. Here we show that femtosecond two-dimensional electronic spectroscopy, with its unprecedented time resolution and phase sensitivity, can be used to collect direct experimental evidence for ultrafast electron heating, anomalously strong coherent and transient electronic plasmonic responses, and homogenous dephasing processes resulting from electron-vibration couplings even for polydisperse gold nanorods.

Sub-Optical Lithography With Nanometer Definition Masks

NASA Technical Reports Server (NTRS)

Hartley, Frank T.; Malek, Chantal Khan; Neogi, Jayant

2000-01-01

Nanometer feature size lithography represents a major paradigm shift for the electronics and micro-electro-mechanical industries. In this paper, we discuss the capacity of dynamic focused reactive ion beam (FIB) etching systems to undertake direct and highly anisotropic erosion of thick evaporated gold coatings on boron-doped silicon X-ray mask membranes. FIB offers a new level of flexibility in micro fabrication, allowing for fast fabrication of X-ray masks, where pattern definition and surface alteration are combined in the same step which eliminates the whole lithographic process, in particular resist, resist development, electro-deposition and resist removal. Focused ion beam diameters as small as 7 nm can be obtained enabling fabrication well into the sub-20 nm regime. In preliminary demonstrations of this X-ray mask fabrication technique 22 nm width lines were milled directly through 0.9 microns of gold and a miniature mass spectrometer pattern was milled through over 0.5 microns of gold. Also presented are the results of the shadow printing, using the large depth of field of synchrotron high energy parallel X-ray beam, of these and other sub-optical defined patterns in photoresist conformally coated over surfaces of extreme topographical variation. Assuming that electronic circuits and/or micro devices scale proportionally, the surface area of devices processed with X-ray lithography and 20 nm critical dimension X-ray masks would be 0.5% that of contemporary devices (350 nm CD). The 20 CD mask fabrication represents an initial effort - a further factor of three reduction is anticipated which represents a further order-of-magnitude reduction in die area.

Effect of surface plasmon resonance on the photocatalytic activity of Au/TiO2 under UV/visible illumination.

PubMed

Tseng, Yao-Hsuan; Chang, I-Guo; Tai, Yian; Wu, Kung-Wei

2012-01-01

In this study, gold-loaded titanium dioxide was prepared by an impregnation method to investigate the effect of surface plasmon resonance (SPR) on photoactivity. The deposited gold nanoparticles (NPs) absorb visible light because of SPR. The effects of both the gold content and the TiO2 size of Au/TiO2 on SPR and the photocatalytic efficiency were investigated. The morphology, crystal structure, light absorption, emission from the recombination of a photoexcited electron and hole, and the degree of aggregation were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-visible-diffuse reflectance spectra (UV-VIS-DRS), photoluminescence (PL) spectroscopy, and turbidimetry, respectively. Photocatalytic activity was evaluated by the decolorization of methyl orange solution over modified titania under UV and UV/GLED (green light emitting diode) illumination. Au/TiO2 NPs exhibited an absorption peak (530-570 nm) because of SPR. The results of our photocatalytic experiments indicated that the UV-inducedly photocatalytic reaction rate was improved by simultaneously using UV and green light illumination; this corresponds to the adsorption region of SPR. Au/TiO2 could use the enhanced electric field amplitude on the surface of the Au particle in the spectral vicinity of its plasmon resonance and thus improve the photoactivity. Experimental results show that the synergistic effect between UV and green light for the improvement of photoactivity increases with increasing the SPR absorption, which in turn is affected by the Au content and TiO2 size.

Monolayer-protected clusters of gold nanoparticles: impacts of stabilizing ligands on the heterogeneous electron transfer dynamics and voltammetric detection.

PubMed

Pillay, Jeseelan; Ozoemena, Kenneth I; Tshikhudo, Robert T; Moutloali, Richard M

2010-06-01

Surface electrochemistry of novel monolayer-protected gold nanoparticles (MPCAuNPs) is described. Protecting ligands, (1-sulfanylundec-11-yl)tetraethylene glycol (PEG-OH) and (1-sulfanylundec-11-yl)poly(ethylene glycol)ic acid (PEG-COOH), of three different percent ratios (PEG-COOH:PEG-OH), 1:99 (MPCAuNP-COOH(1%)), 50:50 (MPCAuNP-COOH(50%)), and 99:1 (MPCAuNP-COOH(99%)), were studied. The electron transfer rate constants (k(et)/s(-1)) in organic medium decreased as the concentration of the surface-exposed -COOH group in the protecting monolayer ligand is increased: MPCAuNP-COOH(1%) (approximately 5 s(-1)) > MPCAuNP-COOH(50%) (approximately 4 s(-1)) > MPCAuNP-COOH(99%) (approximately 0.5 s(-1)). In aqueous medium, the trend is reversed. The surface pK(a) was estimated as approximately 8.2 for the MPCAuNP-COOH(1%), while both MPCAuNP-COOH(50%) and MPCAuNP-COOH(99%) showed two pK(a) values of about 5.0 and approximately 8.0. These results have been interpreted in terms of the quasi-solidity and quasi-liquidity of the terminal -OH and -COOH head groups, respectively. MPCAuNP-COOH(99%) excellently suppressed the voltammetric response of the ascorbic acid but enhanced the electrocatalytic detection of epinephrine compared to the other MPCAuNPs studied. This study reveals important factors that should be considered when designing electrode devices that employ monolayer-protected gold nanoparticles and possibly for some other redox-active metal nanoparticles.

Aquatic Fern (Azolla Sp.) Assisted Synthesis of Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Jha, Anal K.; Prasad, K.

2016-02-01

Aquatic pteridophyte (Azolla sp.) was taken to assess its potential to synthesize the metal (Au) nanoparticles. The synthesized particles were characterized using X-ray, UV-visible, scanning and transmission electron microscopy analyses. Nanoparticles almost spherical in shape having the sizes of 5-17nm are found. UV-visible study revealed the surface plasmon resonance at 538nm. Responsible phytochemicals for the transformation were principally phenolics, tannins, anthraquinone glycosides and sugars present abundantly in the plant thereby bestowing it adaptive prodigality. Also, the use of Azolla sp. for the synthesis of gold nanoparticles offers the benefit of eco-friendliness.

Evaluation of the surface roughness of three heat-cured acrylic denture base resins with different conventional lathe polishing techniques: A comparative study.

PubMed

Rao, Duggineni Chalapathi; Kalavathy, N; Mohammad, H S; Hariprasad, A; Kumar, C Ravi

2015-01-01

Surface roughness promotes adhesion and colonization of denture plaque. Therefore, it is important to know the effects of polishing and finishing on the surface roughness of various acrylic resin materials. To evaluate and compare the effects of different conventional lathe polishing techniques on heat cured acrylic resins in producing surface roughness. Three different commercially available heat-cured acrylic resin materials namely DPI, Meliodent and Trevalon Hi were selected. 30 Specimens of each acrylic material (30 x 3 = 90, 10 x 60 x 2mm) were prepared and divided into 5 groups, each group consisted of 6 Nos. of specimens per material(6x3=18) and were grouped as Group A(unfinished), Group B (finished), Group C (Polishing Paste), Group D (Polishing Cake) and Group E (Pumice and Gold rouge). The resulted surface roughness (μm) was measured using Perthometer and observed under Scanning Electron Microscope. The values obtained were subjected statistical analyses. Among the materials tested, better results were obtained with Trevalon Hi followed by Meliodent and DPI. Among the polishing methods used, superior results were obtained with universal polishing paste followed by polishing cake; Pumice and Gold rouge. Although Pumice and Gold rouge values produced greater roughness value, they were well within the threshold value of 0.2 mm.

Lithographically fabricated gold nanowire waveguides for plasmonic routers and logic gates.

PubMed

Gao, Long; Chen, Li; Wei, Hong; Xu, Hongxing

2018-06-14

Fabricating plasmonic nanowire waveguides and circuits by lithographic fabrication methods is highly desired for nanophotonic circuitry applications. Here we report an approach for fabricating metal nanowire networks by using electron beam lithography and metal film deposition techniques. The gold nanowire structures are fabricated on quartz substrates without using any adhesion layer but coated with a thin layer of Al2O3 film for immobilization. The thermal annealing during the Al2O3 deposition process decreases the surface plasmon loss. In a Y-shaped gold nanowire network, the surface plasmons can be routed to different branches by controlling the polarization of the excitation light, and the routing behavior is dependent on the length of the main nanowire. Simulated electric field distributions show that the zigzag distribution of the electric field in the nanowire network determines the surface plasmon routing. By using two laser beams to excite surface plasmons in a Y-shaped nanowire network, the output intensity can be modulated by the interference of surface plasmons, which can be used to design Boolean logic gates. We experimentally demonstrate that AND, OR, XOR and NOT gates can be realized in three-terminal nanowire networks, and NAND, NOR and XNOR gates can be realized in four-terminal nanowire networks. This work takes a step toward the fabrication of on-chip integrated plasmonic circuits.

Laser-induced periodic surface structures formation: investigation of the effect of nonlinear absorption of laser energy in different materials

NASA Astrophysics Data System (ADS)

Levy, Yoann; Bulgakova, Nadezhda M.; Mocek, Tomáš

2017-05-01

To get insight into laser-induced periodic surface structures (LIPSS) formation, the relaxation of a modulation in the temperature profile is investigated numerically on surfaces of two different kinds of materials (metals and dielectrics; gold and fused silica as examples) upon irradiation by ultrashort laser pulses. The temperature modulation is assumed to originate from the interference between the incoming laser pulse and the surface electromagnetic wave, which is considered as the main mechanism of LIPSS formation. For comparative studies of laser energy dissipation, a simplified 2D approach is used. It is based on the two-temperature model (TTM) and considers the mechanisms of nonlinear absorption of laser light (multiphoton ionization in fused silica; temperature-dependent thermophysical and optical properties in gold) and relaxation (electron trapping to excitonic states in fused silica). The TTM is coupled with the Drude model, considering the evolution of optical properties as a function of free-carrier density and/or temperature. The development and decay of the lattice temperature modulation, which can govern the LIPSS formation, is followed during electron-lattice thermalization time and beyond. It is shown that strong temperature gradients can form along the surfaces of both kinds of materials under study within the fluence range typical for LIPSS formation. Considerable changes in optical properties of these materials are found as a function of time, including metals, for which a constant reflectivity is usually assumed. Effects of nonlinear absorption on the surface temperature dynamics are reported.

Stabilized gold nanoparticles by laser ablation in ferric chloride solutions

NASA Astrophysics Data System (ADS)

Nouraddini, M. I.; Ranjbar, M.; Dobson, P. J.; Farrokhpour, H.; Johnston, C.; Jurkschat, K.

2017-12-01

In this study, laser ablation of gold was performed in different ferric chloride solutions and water as a reference. The ferric chloride solutions included hexachloro iron(III) and aquachloro iron(III) having low and high hydrolysis degree. Transmission electron microscope (TEM) images showed spherical gold nanoparticles (GNPs) in water, particles which are strongly agglomerated with intimate contact at their interfaces in hexachloro iron(III) and individual separated particles with a halo of an iron component in aquachloro iron(III). In addition, no combination of Au and Fe was found in HAADF analysis or X-ray diffraction (XRD) patterns. In optical investigations, it was observed that gold nanoparticles made in hexachloro iron(III) solutions have localized surface plasmon resonance (LSPR) peaks broader than in the case of water that are quenched after a few hours, while ablation in the aquachloro iron(III) solution provides narrow LSPR absorption with a long-term stability. According to X-ray photoelectron spectroscopy (XPS) there are metallic Au and Fe2+ states in the drop-casted samples. By comparison of cyclic voltammetry of solutions before and after laser ablation, strong agglomeration in hexachloro iron(III) was attributed to the reducing role of iron(III) creating an unstable gold surface in the chloride solution. In aquachloro iron(III), however, the observed stability was attributed to the formation of the halo of an iron compound around the particles.

Surface area and pore size characteristics of nanoporous gold subjected to thermal, mechanical, or surface modification studied using gas adsorption isotherms, cyclic voltammetry, thermogravimetric analysis, and scanning electron microscopy

PubMed Central

Tan, Yih Horng; Davis, Jason A.; Fujikawa, Kohki; Ganesh, N. Vijaya; Demchenko, Alexei V.

2012-01-01

Nitrogen adsorption/desorption isotherms are used to investigate the Brunauer, Emmett, and Teller (BET) surface area and Barrett-Joyner-Halenda (BJH) pore size distribution of physically modified, thermally annealed, and octadecanethiol functionalized np-Au monoliths. We present the full adsorption-desorption isotherms for N2 gas on np-Au, and observe type IV isotherms and type H1 hysteresis loops. The evolution of the np-Au under various thermal annealing treatments was examined using scanning electron microscopy (SEM). The images of both the exterior and interior of the thermally annealed np-Au show that the porosity of all free standing np-Au structures decreases as the heat treatment temperature increases. The modification of the np-Au surface with a self-assembled monolayer (SAM) of C18-SH (coverage of 2.94 × 1014 molecules cm−2 based from the decomposition of the C18-SH using thermogravimetric analysis (TGA)), was found to reduce the strength of the interaction of nitrogen gas with the np-Au surface, as reflected by a decrease in the ‘C’ parameter of the BET equation. From cyclic voltammetry studies, we found that the surface area of the np-Au monoliths annealed at elevated temperatures followed the same trend with annealing temperature as found in the BET surface area study and SEM morphology characterization. The study highlights the ability to control free-standing nanoporous gold monoliths with high surface area, and well-defined, tunable pore morphology. PMID:22822294

Electrochemical behavior of gold nanoparticles modified nitrogen incorporated tetrahedral amorphous carbon and its application in glucose sensing.

PubMed

Liu, Aiping; Wu, Huaping; Qiu, Xu; Tang, Weihua

2011-12-01

Gold nanoparticles (NPs) with 10-50 nm in diameter were synthesized on nitrogen incorporated tetrahedral amorphous carbon (ta-C:N) thin film electrode by electrodeposition. The deposition and nucleation processes of Au on ta-C:N surface were investigated by cyclic voltammetry and chronoamperometry. The morphology of Au NPs was characterized by scanned electron microscopy. The electrochemical properties of Au NPs modified ta-C:N (ta-C:N/Au) electrode and its ability to sense glucose were investigated by voltammetric and amperometric measurements. The potentiostatic current-time transients showed a progressive nucleation process and diffusion growth of Au on the surface of ta-C:N film according to the Scharifker-Hills model. The Au NPs acted as microelectrodes improved the electron transfer and electrocatalytic oxidation of glucose on ta-C:N electrode. The ta-C:N/Au electrode exhibited fast current response, a linear detection range of glucose from 0.5 to 25 mM and a detection limit of 120 microM, which hinted its potential application as a glucose biosensor.

Application of three-dimensional reduced graphene oxide-gold composite modified electrode for direct electrochemistry and electrocatalysis of myoglobin.

PubMed

Shi, Fan; Xi, Jingwen; Hou, Fei; Han, Lin; Li, Guangjiu; Gong, Shixing; Chen, Chanxing; Sun, Wei

2016-01-01

In this paper a three-dimensional (3D) reduced graphene oxide (RGO) and gold (Au) composite was synthesized by electrodeposition and used for the electrode modification with carbon ionic liquid electrode (CILE) as the substrate electrode. Myoglobin (Mb) was further immobilized on the surface of 3D RGO-Au/CILE to obtain an electrochemical sensing platform. Direct electrochemistry of Mb on the modified electrode was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electron transfer of Mb with the modified electrode. The results can be ascribed to the presence of highly conductive 3D RGO-Au composite on the electrode surface that accelerate the electron transfer rate between the electroactive center of Mb and the electrode. The Mb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.2 to 36.0 mmol/L with the detection limit of 0.06 mmol/L (3σ). Copyright © 2015 Elsevier B.V. All rights reserved.

Efficient and scalable ionization of neutral atoms by an orderly array of gold-doped silicon nanowires

NASA Astrophysics Data System (ADS)

Bucay, Igal; Helal, Ahmed; Dunsky, David; Leviyev, Alex; Mallavarapu, Akhila; Sreenivasan, S. V.; Raizen, Mark

2017-04-01

Ionization of atoms and molecules is an important process in many applications and processes such as mass spectrometry. Ionization is typically accomplished by electron bombardment, and while it is scalable to large volumes, is also very inefficient due to the small cross section of electron-atom collisions. Photoionization methods can be highly efficient, but are not scalable due to the small ionization volume. Electric field ionization is accomplished using ultra-sharp conducting tips biased to a few kilovolts, but suffers from a low ionization volume and tip fabrication limitations. We report on our progress towards an efficient, robust, and scalable method of atomic and molecular ionization using orderly arrays of sharp, gold-doped silicon nanowires. As demonstrated in earlier work, the presence of the gold greatly enhances the ionization probability, which was attributed to an increase in available acceptor surface states. We present here a novel process used to fabricate the nanowire array, results of simulations aimed at optimizing the configuration of the array, and our progress towards demonstrating efficient and scalable ionization.

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

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.

Using gold nanostars modified pencil graphite electrode as a novel substrate for design a sensitive and selective Dopamine aptasensor.

PubMed

Talemi, Rasoul Pourtaghavi; Mousavi, Seyed Mehdi; Afruzi, Hossein

2017-04-01

For the first time, gold nanostars (GNS) were applied for electrostatic and covalent immobilizing a thiol modified Dopamine aptamer on the pencil graphite electrode and signal amplification. Dopamine aptamer was immobilized on the gold nanostars through electrostatic interaction between negatively charged phosphate groups of aptamer and positively charged gold nanostars and AuS well known covalent interaction. In the presence of Dopamine in the test solution, the charge transfer resistance (R CT ) on the electrode surface increased with the increase of the Dopamine concentration due to specific interaction between Dopamine aptamer and Dopamine molecules, which made a barrier for electrons and inhibited the electron-transfer. So, the proposed approach showed a high sensitivity and a wide linearity to Dopamine in the range from 1.0 (±0.1) to 100.0 (±0.3) ngL -1 (ppt) with detection and quantification limits of 0.29 (±0.10) and 0.90 (±0.08) ngL -1 (ppt), respectively. Finally, the sensor was successfully used for determination of Dopamine in biological (human blood plasma and urine) samples. The results open up the path for manufacturing cost effective aptasensors for other biomedical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Differentiating gold nanorod samples using particle size and shape distributions from transmission electron microscope images

NASA Astrophysics Data System (ADS)

Grulke, Eric A.; Wu, Xiaochun; Ji, Yinglu; Buhr, Egbert; Yamamoto, Kazuhiro; Song, Nam Woong; Stefaniak, Aleksandr B.; Schwegler-Berry, Diane; Burchett, Woodrow W.; Lambert, Joshua; Stromberg, Arnold J.

2018-04-01

Size and shape distributions of gold nanorod samples are critical to their physico-chemical properties, especially their longitudinal surface plasmon resonance. This interlaboratory comparison study developed methods for measuring and evaluating size and shape distributions for gold nanorod samples using transmission electron microscopy (TEM) images. The objective was to determine whether two different samples, which had different performance attributes in their application, were different with respect to their size and/or shape descriptor distributions. Touching particles in the captured images were identified using a ruggedness shape descriptor. Nanorods could be distinguished from nanocubes using an elongational shape descriptor. A non-parametric statistical test showed that cumulative distributions of an elongational shape descriptor, that is, the aspect ratio, were statistically different between the two samples for all laboratories. While the scale parameters of size and shape distributions were similar for both samples, the width parameters of size and shape distributions were statistically different. This protocol fulfills an important need for a standardized approach to measure gold nanorod size and shape distributions for applications in which quantitative measurements and comparisons are important. Furthermore, the validated protocol workflow can be automated, thus providing consistent and rapid measurements of nanorod size and shape distributions for researchers, regulatory agencies, and industry.

Atomic force microscopy imaging of fragments from the Martian meteorite ALH84001

NASA Technical Reports Server (NTRS)

Steele, A.; Goddard, D.; Beech, I. B.; Tapper, R. C.; Stapleton, D.; Smith, J. R.

1998-01-01

A combination of scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM) techniques, as well as atomic force microscopy (AFM) methods has been used to study fragments of the Martian meteorite ALH84001. Images of the same areas on the meteorite were obtained prior to and following gold/palladium coating by mapping the surface of the fragment using ESEM coupled with energy-dispersive X-ray analysis. Viewing of the fragments demonstrated the presence of structures, previously described as nanofossils by McKay et al. (Search for past life on Mars--possible relic biogenic activity in martian meteorite ALH84001. Science, 1996, pp. 924-930) of NASA who used SEM imaging of gold-coated meteorite samples. Careful imaging of the fragments revealed that the observed structures were not an artefact introduced by the coating procedure.

An investigation of the effect of scaling-induced surface roughness on bacterial adhesion in common fixed dental restorative materials.

PubMed

Checketts, Matthew R; Turkyilmaz, Ilser; Asar, Neset Volkan

2014-11-01

Bacterial plaque must be routinely removed from teeth, adjacent structures, and prostheses. However, the removal of this plaque can inadvertently increase the risk of future bacterial adhesion. The purpose of this investigation was to assess the change in the surface roughness of 3 different surfaces after dental prophylactic instrumentation and how this influenced bacterial adhesion. Forty specimens each of Type III gold alloy, lithium disilicate, and zirconia were fabricated in the same dimensions. The specimens were divided into 4 groups: ultrasonic scaler, stainless steel curette, prophylaxis cup, and control. Pretreatment surface roughness measurements were made with a profilometer. Surface treatments in each group were performed with a custom mechanical scaler. Posttreatment surface roughness values were measured. In turn, the specimens were inoculated with Streptococcus mutans, Lactobacillus acidophilus, and Actinomyces viscosus. Bacterial adhesion was assessed by rinsing the specimens with sterile saline to remove unattached cells. The specimens were then placed in sterile tubes with 1 mL of sterile saline. The solution was plated and quantified. Scanning electron microscopy was performed. The statistical analysis of surface roughness was completed by using repeated-measures single-factor ANOVA with a Bonferroni correction. The surface roughness values for gold alloy specimens increased as a result of prophylaxis cup treatment (0.221 to 0.346 Ra) (P<.01) and stainless steel curette treatment (0.264 to 1.835 Ra) (P<.01). The results for bacterial adhesion to gold alloy proved inconclusive. A quantitative comparison indicated no statistically significant differences in pretreatment and posttreatment surface roughness values for lithium disilicate and zirconia specimens. In spite of these similarities, the overall bacterial adherence values for lithium disilicate were significantly greater than those recorded for gold alloy or zirconia (P<.05). Instrumentation of the lithium disilicate and zirconia with the stainless steel curette significantly increased bacterial adhesion compared with the control (P<.05). The results of this investigation indicate that Type III gold alloy exhibited increased surface roughness values after stainless steel curette and prophylaxis cup treatments. Zirconia was less susceptible to bacterial adhesion than lithium disilicate, and greater bacterial adhesion was found for the stainless steel curette than the other instrumentation methods. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods

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

Lien, Miao-Bin; Kim, Ji-Young; Han, Myung-Geun

A systematic study is presented of the intensity-dependent nonlinear light scattering spectra of gold nanorods under resonant excitation of the longitudinal surface plasmon resonance (SPR). The spectra exhibit features due to coherent second and third harmonic generation as well as a broadband feature that has been previously attributed to multiphoton photoluminescence arising primarily from interband optical transitions in the gold. A detailed study of the spectral dependence of the scaling of the scattered light with excitation intensity shows unexpected scaling behavior of the coherent signals, which is quantitatively accounted for by optically induced damping of the SPR mode through amore » Fermi liquid model of the electronic scattering. The broadband feature is shown to arise not from luminescence, but from scattering of the secondorder longitudinal SPR mode with the electron gas, where efficient excitation of the 2nd order mode arises from an optical asymmetry of the nanorod. The electronic-temperature-dependent plasmon damping and the Fermi-Dirac distribution together determine the intensity dependence of the broadband emission, and the structure-dependent absorption spectrum determines the spectral shape through the fluctuation-dissipation theorem. Hence a complete self-consistent picture of both coherent and incoherent light scattering is obtained with a single set of physical parameters.« less

Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods

DOE PAGES

Lien, Miao-Bin; Kim, Ji-Young; Han, Myung-Geun; ...

2017-05-16

A systematic study is presented of the intensity-dependent nonlinear light scattering spectra of gold nanorods under resonant excitation of the longitudinal surface plasmon resonance (SPR). The spectra exhibit features due to coherent second and third harmonic generation as well as a broadband feature that has been previously attributed to multiphoton photoluminescence arising primarily from interband optical transitions in the gold. A detailed study of the spectral dependence of the scaling of the scattered light with excitation intensity shows unexpected scaling behavior of the coherent signals, which is quantitatively accounted for by optically induced damping of the SPR mode through amore » Fermi liquid model of the electronic scattering. The broadband feature is shown to arise not from luminescence, but from scattering of the secondorder longitudinal SPR mode with the electron gas, where efficient excitation of the 2nd order mode arises from an optical asymmetry of the nanorod. The electronic-temperature-dependent plasmon damping and the Fermi-Dirac distribution together determine the intensity dependence of the broadband emission, and the structure-dependent absorption spectrum determines the spectral shape through the fluctuation-dissipation theorem. Hence a complete self-consistent picture of both coherent and incoherent light scattering is obtained with a single set of physical parameters.« less

Z-scan studies of the nonlinear optical properties of gold nanoparticles prepared by electron beam deposition.

PubMed

Mezher, M H; Nady, A; Penny, R; Chong, W Y; Zakaria, R

2015-11-20

This paper details the fabrication process for placing single-layer gold (Au) nanoparticles on a planar substrate, and investigation of the resulting optical properties that can be exploited for nonlinear optics applications. Preparation of Au nanoparticles on the substrate involved electron beam deposition and subsequent thermal dewetting. The obtained thin films of Au had a variation in thicknesses related to the controllable deposition time during the electron beam deposition process. These samples were then subjected to thermal annealing at 600°C to produce a randomly distributed layer of Au nanoparticles. Observation from field-effect scanning electron microscope (FESEM) images indicated the size of Au nanoparticles ranges from ∼13 to ∼48  nm. Details of the optical properties related to peak absorption of localized surface plasmon resonance (LSPR) of the nanoparticle were revealed by use of UV-Vis spectroscopy. The Z-scan technique was used to measure the nonlinear effects on the fabricated Au nanoparticle layers where it strongly relates LSPR and nonlinear optical properties.

Efficient fluorescence quenching in electrochemically exfoliated graphene decorated with gold nanoparticles

NASA Astrophysics Data System (ADS)

Hurtado-Morales, M.; Ortiz, M.; Acuña, C.; Nerl, H. C.; Nicolosi, V.; Hernández, Y.

2016-07-01

High surface area graphene sheets were obtained by electrochemical exfoliation of graphite in an acid medium under constant potential conditions. Filtration and centrifugation processes played an important role in order to obtain stable dispersions in water. Scanning electron microscopy and transmission electron microscopy imaging revealed highly exfoliated crystalline samples of ∼5 μm. Raman, Fourier transform infrared and x-ray photoelectron spectroscopy further confirmed the high quality of the exfoliated material. The electrochemically exfoliated graphene (EEG) was decorated with gold nanoparticles (AuNPs) using sodium cholate as a buffer layer. This approach allowed for a non-covalent functionalization without altering the desirable electronic properties of the EEG. The AuNP-EEG samples were characterized with various techniques including absorbance and fluorescence spectroscopy. These samples displayed a fluorescence signal using an excitation wavelength of 290 nm. The calculated quantum yield (Φ) for these samples was 40.04%, a high efficiency compared to previous studies using solution processable graphene.

Structural and plasmonic properties of gold nanocrystals

NASA Astrophysics Data System (ADS)

Sivapalan, Sean T.

The design of gold nanoparticles for surface-enhanced Raman scattering (SERS) and plasmonic enhanced fluorescence are more involved than simply maximizing the local field enhancement. The enhancement is a function of the excitation wavelength relative to the plasmon resonance as well as the distance of the reporter molecules from the nanoparticles' surface. For suspension based measurements, additional considerations must also be made regarding absorption and scattering effects as light propagates through the sample. These effects are in addition to the other more commonly observed effects such as nanocrystal shape. With such a wide number of variables in play, a series of studies breaking down each of these components and their contribution to the observed enhancement is warranted. In this thesis, a series of experiments were undertaken using a platform based on polyelectrolyte coating of gold nanoparticles by layer-by-layer deposition. The reporter molecules are bound onto the surface of polyelectrolyte coated nanoparticles before trap coating them with an additional oppositely charged polyelectrolyte layer. By etching away the gold nanoparticle using potassium cyanide, we are then able to quantify the number of reporter molecule per nanoparticle using mass spectrometry. With this quantitative approach, we can the directly compare the effects of the aforementioned enhancement mechanisms on the observed signal intensity. This method overcomes some of the disparities in literature between reported values of enhancement due to assumption in the number of reporter molecules contribution to the signal intensity. Using our group's expertise, we synthesized gold nanoparticle libraries of nanorods, cubes, trisoctahedra and spheres of different sizes. Each geometric configuration was characterized using a recently developed TEM technique---nano-beam coherent area diffraction. The as-synthesized were exposed to a coherent electron beam with probe size similar to that of the nanoparticles. The nanoparticles were then tilted such that were oriented so that the electron beam was parallel to a major zone axis and the diffraction pattern recorded. We observed streaks at each Bragg reflection that changed depending on the shape of the nanoparticle. This is in contrast to the spots for the Bragg reflections observed for normal small area diffraction patterns of gold nanoparticles. The angles between the streaks were compared using vector analysis to theoretical simulated three dimensional models and showed good correlation. These studies indicate such a platform can be used to elucidate the structure of high-index gold nanoparticle shapes such as trisoctahedra. The as-synthesized gold nanoparticles had surface plasmon resonances that incrementally spanned the spectral region of 500-900 nm. The reporter molecules used all have an absorption maximum far from the excitation wavelength. This ensures that chemical resonant based effects are minimized and plasmonic electromagnetic effects dominate the observed signal enhancement. For gold nanorods, the highest SERS signal from six different aspect ratios was observed with absorption maxima blue-shifted from the laser excitation wavelength. This finding is in contrast to substrate measurements where the maximum observed signal is red-shifted from the laser excitation wavelength. A similar platform was used to compare the effects of changing the nanoparticle shape on the observed SERS enhancement. We synthesized trisoctahedral, cubic and spherical geometries with electronic absorption maxima that overlapped within 3 nm. The relative SERS enhancement with 785 nm excitation was compared to theoretical simulations using finite element analysis. The observed signal intensities correlated well to the theory, suggesting the electromagnetic fields focused towards sharp edges and corners dominated the spectral response. The final chapters of this thesis are tailored towards understanding the distance dependence of plasmonic effects on the two photon absorption (TPA) cross section of an organic chromophore. First, we optimized the protocol to coat as-synthesized gold nanorod with multiple polyelectrolyte layers. By varying the purification and complexation parameters we were able to obtain up to ten layers of wrapping without great losses in nanoparticle concentration. The TPA molecules were then electrostatically attached at different incremental distances to compare the relative enhancement as a function of distance. We compared the TPA enhancement for on-resonant excitation and find a 40 fold enhancement for the molecules closest to the surface of the nanoparticles. For the off-resonant excitation, we observed an interesting trend where the TPA enhancement recovers for higher number of polyelectrolyte layers.

The effect of 3 torque delivery systems on gold screw preload at the gold cylinder-abutment screw joint.

PubMed

Tan, Keson B; Nicholls, Jack I

2002-01-01

This study measured the gold screw preload at the gold cylinder-abutment screw joint interface obtained by 3 torque delivery systems. Using a precalibrated, strain-gauged standard abutment as the load cell, 3 torque delivery systems tested were shown to have significant differences in gold screw preload when a gold cylinder was attached. Mean preloads measured were 291.2 N for hand torque drivers set at 10 Ncm, 340.3 N for electronic torque controllers at low setting/10 Ncm, 384.4 N for electronic torque controllers at high setting/10 Ncm; and 140.8 N for hand-tightening with a prosthetic slot screwdriver. Significant differences in screw preload were also found between operators using a hand torque driver. Hand-tightening delivered insufficient preload and cannot be recommended for final gold screw tightening. Different electronic torque controller units set at 10 Ncm induced mean gold screw preloads that ranged from 264.1 N to as high as 501.2 N. Electronic torque controllers should be regularly recalibrated to ensure optimal output.

Gold Ultrathin Nanorods with Controlled Aspect Ratios and Surface Modifications: Formation Mechanism and Localized Surface Plasmon Resonance.

PubMed

Takahata, Ryo; Yamazoe, Seiji; Koyasu, Kiichirou; Imura, Kohei; Tsukuda, Tatsuya

2018-05-30

We synthesized gold ultrathin nanorods (AuUNRs) by slow reductions of gold(I) in the presence of oleylamine (OA) as a surfactant. Transmission electron microscopy revealed that the lengths of AuUNRs were tuned in the range of 5-20 nm while keeping the diameter constant (∼2 nm) by changing the relative concentration of OA and Au(I). It is proposed on the basis of time-resolved optical spectroscopy that AuUNRs are formed via the formation of small (<2 nm) Au spherical clusters followed by their one-dimensional attachment in OA micelles. The surfactant OA on AuUNRs was successfully replaced with glutathionate or dodecanethiolate by the ligand exchange approach. Optical extinction spectroscopy on a series of AuUNRs with different aspect ratios (ARs) revealed a single intense extinction band in the near-IR (NIR) region due to the longitudinal localized surface plasmon resonance (LSPR), the peak position of which is red-shifted with the AR. The NIR bands of AuUNRs with AR < 5 were blue-shifted upon the ligand exchange from OA to thiolates, in sharp contrast to the red shift observed in the conventional Au nanorods and nanospheres (diameter >10 nm). This behavior suggests that the NIR bands of thiolate-protected AuUNRs with AR < 5 are not plasmonic in nature, but are associated with a single-electron excitation between quantized states. The LSPR band was attenuated by thiolate passivation that can be explained by the direct decay of plasmons into an interfacial charge transfer state (chemical interface damping). The LSPR wavelengths of AuUNRs are remarkably longer than those of the conventional AuNRs with the same AR, demonstrating that the miniaturization of the diameter to below ∼2 nm significantly affects the optical response. The red shift of the LSPR band can be ascribed to the increase in the effective mass of electrons in AuUNRs.

A Golden Drachma From Bruttia: Counterfeit Money Revealed By Scanning Electron Microscopy and Cathodoluminescence.

NASA Astrophysics Data System (ADS)

Pingitore, Valentino; Barberio, Marianna; Oliva, Antonino; Noce, Nicoletta; Gattuso, Caterina; Davoli, Mariano

Diagnostic studies performed on an ancient coin are presented in order to find if the coin is authentic or is a coinage proof. Our investigation includes Scanning Electron Microscopy - Energy Dispersive X-ray (SEM-EDX) and Cathodoluminescence (CL). The coin is a Drachma representing on the obverse the portrait of Poseidon and, on the reverse the figure of Anfitrite riding a seahorse while Eros is shooting an arrow. The coin is well known in the numismatic studies and originals can also be found in Catanzaro, Naples or Milan museums. The EDX analysis, executed on narrow points of the surface, revealed Pb and Cu as main components of the coin on both sides: 51% of Pb and 35% of Cu their weight and surprisingly on both sides traces of gold was found. The maximum dimensions and the percentage in weight of the small revealed gold spots were respectively on the order of 20 μm and 95%. At the same time luminescence emission induced by electron bombardment (CL) on these spots was executed. This analysis confirmed SEM results, though the presence of Au was more evident than in SEM analysis. In fact CL analysis showed a little presence of Au throughout the sample surface.

Ultrathin Au film on polymer surface for surface plasmon polariton waveguide application

NASA Astrophysics Data System (ADS)

Liu, Tong; Ji, Lanting; He, Guobing; Sun, Xiaoqiang; Wang, Fei; Zhang, Daming

2017-11-01

Formation of laterally continuous ultrathin gold films on polymer substrates is a technological challenge. In this work, the vacuum thermal evaporation method is adopted to form continuous Au films in the thickness range of 7-17 nm on polymers of Poly(methyl-methacrylate-glycidly-methacrylate) and SU-8 film surface without using the adhesion or metallic seeding layers. Absorption spectrum, scanning electron microscope and atomic force microscope images are used to characterize the Au film thickness, roughness and optical loss. The result shows that molecular-scale structure, surface energy and electronegativity have impacts on the Au film morphology on polymers. Wet chemical etching is used to fabricate 7-nm thick Au stripes embedded in polymer claddings. These long-range surface plasmon polariton waveguides demonstrate the favorable morphological configurations and cross-sectional states. Through the end-fire excitation method, propagation losses of 6-μm wide Au stripes are compared to theoretical values and analyzed from practical film status. The smooth, patternable gold films on polymer provide potential applications to plasmonic waveguides, biosensing, metamaterials and optical antennas.

Green synthesis of gold nanoparticles using aqueous ethanol extract of Curcuma mangga rhizomes as reducing agent

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

Yee, Foo Yiing; Malek, Sri Nurestri Abd; Periasamy, Vengadesh

Green synthesis of gold nanoparticles (AuNPs) had been developed as an alternative to chemical and physical methods due to its simplicity, cost effectiveness and eco-friendliness. The high biocompatibility and biostability features of AuNPs have found importance in biomedical applications in recent years. In this study, aqueous ethanol extract of Curcuma mangga rhizomes which acts as reducing and stabilizing agent was used to synthesize stable AuNPs by bioreduction of chloroauric acid. The formation of AuNPs was highlighted by the color change of the suspension from light yellow to reddish purple. Time-evolution was monitored by UV-visible spectroscopy, while surface plasmon (SP) absorptionmore » band of the AuNPs suspension was observed at a maximum absorption of 540 nm. Hydrodynamic radii and size distribution of the AuNPs in the suspension were evaluated using dynamic light scattering (DLS) and zeta potential measurement demonstrated negative surface charge. The particle size was calculated in the range of 2-30 nm using High Resolution Transmission Electron Microscopy (HRTEM). The morphology and elemental composition were further determined by Field Effect Scanning Electron Microscopy (FESEM) and Energy Dispersive X-ray (EDX) spectroscopy. Fourier transform infrared (FTIR) spectroscopy meanwhile was used to confirm the presence of AuNPs and functional groups involved in the gold bio-reduction process. Influence of the volume of extract and concentration of gold (III) chloride trihydrate (HAuCl{sub 4}.3H{sub 2}O) on the synthesis of AuNPs were also investigated. The results obtained indicate potential optimization and functionalization of AuNPs for future applications in bionanotechnology especially in the field of medicine.« less

Green synthesis of gold nanoparticles using aqueous ethanol extract of Curcuma mangga rhizomes as reducing agent

NASA Astrophysics Data System (ADS)

Yee, Foo Yiing; Periasamy, Vengadesh; Malek, Sri Nurestri Abd

2015-04-01

Green synthesis of gold nanoparticles (AuNPs) had been developed as an alternative to chemical and physical methods due to its simplicity, cost effectiveness and eco-friendliness. The high biocompatibility and biostability features of AuNPs have found importance in biomedical applications in recent years. In this study, aqueous ethanol extract of Curcuma mangga rhizomes which acts as reducing and stabilizing agent was used to synthesize stable AuNPs by bioreduction of chloroauric acid. The formation of AuNPs was highlighted by the color change of the suspension from light yellow to reddish purple. Time-evolution was monitored by UV-visible spectroscopy, while surface plasmon (SP) absorption band of the AuNPs suspension was observed at a maximum absorption of 540 nm. Hydrodynamic radii and size distribution of the AuNPs in the suspension were evaluated using dynamic light scattering (DLS) and zeta potential measurement demonstrated negative surface charge. The particle size was calculated in the range of 2-30 nm using High Resolution Transmission Electron Microscopy (HRTEM). The morphology and elemental composition were further determined by Field Effect Scanning Electron Microscopy (FESEM) and Energy Dispersive X-ray (EDX) spectroscopy. Fourier transform infrared (FTIR) spectroscopy meanwhile was used to confirm the presence of AuNPs and functional groups involved in the gold bio-reduction process. Influence of the volume of extract and concentration of gold (III) chloride trihydrate (HAuCl4.3H2O) on the synthesis of AuNPs were also investigated. The results obtained indicate potential optimization and functionalization of AuNPs for future applications in bionanotechnology especially in the field of medicine.

Unraveling the complexity of the interactions of DNA nucleotides with gold by single molecule force spectroscopy

NASA Astrophysics Data System (ADS)

Bano, Fouzia; Sluysmans, Damien; Wislez, Arnaud; Duwez, Anne-Sophie

2015-11-01

Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine.Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine. Electronic supplementary information (ESI) available: Details of the data analysis; Fig. S1-S5 histograms of rupture lengths; histograms for Au-adenine and Au-amine interactions; Force-extension curve for MCH-Au interactions; normalized force-extension curves; theoretical length of the DNA oligomers. See DOI: 10.1039/c5nr05695k

[Effect of sintering gold paste coating on the bonding strength of pure titanium and three low-fusing porcelains].

PubMed

Zhang, Ya-li; Luo, Xiao-ping; Zhou, Li

2012-05-01

To study the effect of sintering gold paste coating of pure titanium on the adhesion of three porcelains following the protocol ISO 9693, and to investigate the titanium-porcelains interfaces. Sixty machined pure titanium samples were prepared in a rectangular shape according to ISO 9693 and divided equally into six groups. Half of the strips were coated with gold paste (Deckgold) and sintered. Three ultra-low-fusing dental porcelains (I: Initial Ti, S: Super porcelain Ti-22, T: TitanKeramik) were fused onto the titanium surfaces. A thin layer of bonding agent was only applied on the surfaces of uncoated gold specimens. The interface of the porcelain and titanium was observed with a field emission scanning electron microscope (FE-SEM) after metallographic preparation and sputtered with a very thin carbon layer of the embedded titanium-porcelain interface. After three-point bending test was performed, optical stereomicroscope was used to characterize the titanium-porcelains adhesion and determine the mode of failure. FE-SEM illustrated intermetallic compounds of Au-Ti formed with some visible microcracks in the gold layer and the interface of gold layer and ceramic. All the uncoated gold titanium-porcelain system showed predominately adhesive fracture at the titanium oxidation, whereas the failure modes in all gold coated systems were cohesive and adhesive, mainly cohesive. The three-point-bending test showed that the bonding strength of GS and GI groups [(37.08 ± 4.32) and (36.20 ± 2.40) MPa] were higher than those in uncoated groups [(31.56 ± 3.74) and (30.88 ± 2.60) MPa, P < 0.05], while no significant difference was found between T group and GT group (P > 0.05). The gold paste intermediate coatings can improve bond strengths of Super porcelain Ti-22 system and Initial Ti system, which have potential applications in clinical fields.

Elemental, microstructural, and mechanical characterization of high gold orthodontic brackets after intraoral aging.

PubMed

Hersche, Sepp; Sifakakis, Iosif; Zinelis, Spiros; Eliades, Theodore

2017-02-01

The purpose of the present study was to investigate the elemental composition, the microstructure, and the selected mechanical properties of high gold orthodontic brackets after intraoral aging. Thirty Incognito™ (3M Unitek, Bad Essen, Germany) lingual brackets were studied, 15 brackets as received (control group) and 15 brackets retrieved from different patients after orthodontic treatment. The surface of the wing area was examined by scanning electron microscopy (SEM). Backscattered electron imaging (BEI) was performed, and the elemental composition was determined by X-ray EDS analysis (EDX). After appropriate metallographic preparation, the mechanical properties tested were Martens hardness (HM), indentation modulus (EIT), elastic index (ηIT), and Vickers hardness (HV). These properties were determined employing instrumented indentation testing (IIT) with a Vickers indenter. The results were statistically analyzed by unpaired t-test (α=0.05). There were no statistically significant differences evidenced in surface morphology and elemental content between the control and the experimental group. These two groups of brackets showed no statistically significant difference in surface morphology. Moreover, the mean values of HM, EIT, ηIT, and HV did not reach statistical significance between the groups (p>0.05). Under the limitations of this study, it may be concluded that the surface elemental content and microstructure as well as the evaluated mechanical properties of the Incognito™ lingual brackets remain unaffected by intraoral aging.

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: structure-activity relationship

NASA Astrophysics Data System (ADS)

Guo, Yu; Gu, Dong; Jin, Zhao; Du, Pei-Pei; Si, Rui; Tao, Jing; Xu, Wen-Qian; Huang, Yu-Ying; Senanayake, Sanjaya; Song, Qi-Sheng; Jia, Chun-Jiang; Schüth, Ferdi

2015-03-01

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

Selective binding, uptake, and retrograde transport of tetanus toxin by nerve terminals in the rat iris. An electron microscope study using colloidal gold as a tracer

PubMed Central

1978-01-01

A series of specific macromolecules (tetanus toxin, cholera toxin, nerve growth factor [NGF], and several lectins) have been shown to be transported retrogradely with high selectivity from terminals to cell bodies in various types of neurons. Under identical experimental conditions (low protein concentrations injected), most other macromolecules, e.g. horseradish peroxidase (HRP), albumin, ferritin, are not transported in detectable amounts. In the present EM study, we demonstrate selective binding of tetanus toxin to the surface membrane of nerve terminals, followed by uptake and subsequent retorgrade axonal transport. Tetanus toxin or albumin was adsorbed to colloidal gold particles (diam 200 A). The complex was shown to be stable and well suited as an EM tracer. 1-4 h after injection into the anterior eye chamber of adult rats, tetanus toxin-gold particles were found to be selectively associated with membranes of nerve terminals and preterminal axons. Inside terminals and axons, the tracer was localized mainly in smooth endoplasmic reticulum (SER)-like membrane compartments. In contrast, association of albumin-gold complexes with nervous structures was never observed, in spite of extensive uptake into fibroblasts. Electron microscope and biochemical experiments showed selective retrograde transport of tetanus toxin-gold complexes to the superior cervical ganglion. Specific binding to membrane components at nerve terminals and subsequent internalization and retrograde transport may represent an important pathway for macromolecules carrying information from target organs to the perikarya of their innervating neurons. PMID:659508

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

DOE PAGES

Guo, Yu; Senanayake, Sanjaya; Gu, Dong; ...

2015-01-12

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO x catalysts with very similar structural characteristics in CO oxidation.« less

The stability of self-organized 1-nonanethiol-capped gold nanoparticle monolayer

NASA Astrophysics Data System (ADS)

Jiang, Peng; Xie, Si-shen; Yao, Jian-nian; Pang, Shi-jin; Gao, Hong-jun

2001-08-01

1-Nonanethiol-protected gold nanoparticles with the size of about 2 nm have been prepared by a wet chemical method through choosing a suitable ratio of Au:S (2.5:1). Size selective precipitation of nanoparticles has been used to narrow their size distribution, which facilitates the formation of an ordered nanoparticle close-packed structure. A Fourier transform infrared investigation provides the evidence of the encapsulation of Au nanoparticles by 1-nonanethiol while an ultraviolet-visible spectrum shows a broad absorption around 520 nm, corresponding to surface plasmon band of Au nanoparticles. X-ray photoelectron spectroscopy of the samples demonstrates the metallic state of the gold (Au0) and the existence of sulfur (S). The data from x-ray powder diffraction measurements confirm that the gold nanoparticles have the same face-centred cubic crystalline structure as the bulk gold phase. Finally, transmission electron microscopy (TEM) characterization indicates that the size of the monodisperse colloidal gold nanoparticles is about 2 nm and they can self-organize to form a two-dimensional hexagonal close-packed structure after evaporating a concentrated drop of nanoparticles-toluene solution on a carbon-coated TEM copper grid.

Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

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

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 wasmore » 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.« less

Anomalous Kondo resonance mediated by semiconducting graphene nanoribbons in a molecular heterostructure

DOE PAGES

Li, Yang; Ngo, Anh T.; DiLullo, Andrew; ...

2017-10-16

An unusually large spin-coupling of almost 100% is found in vertically stacked molecular hetrostructures composed of cobalt-porphyrin based magnetic molecules adsorbed on semiconducting armchair graphene nanoribbon on a Au(111) surface. Although the graphene nanoribbons are electronically decoupled from the gold substrate due to their band gaps and weak adsorption, they enable spin coupling between the magnetic moment of the molecule and the electrons from the substrate exhibiting a Kondo resonance. Surprisingly, the Kondo temperatures corresponding to three adsorption sites of the molecules on Au(111) surface are reproduced on the molecules adsorb on the graphene nanoribbons although the molecules are locatedmore » 7.5 Å away from the surface. This finding suggests that the molecules on graphene nanoribbons experience almost the same environment for spin-electron interactions as the ones directly adsorb on Au(111). This puzzling effect is further confirmed by density functional theory calculations that reveal no spin electron interactions if the molecule is left at the same height from the Au(111) surface without the graphene nanoribbon in between.« less

Anomalous Kondo resonance mediated by semiconducting graphene nanoribbons in a molecular heterostructure

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

Li, Yang; Ngo, Anh T.; DiLullo, Andrew

An unusually large spin-coupling of almost 100% is found in vertically stacked molecular hetrostructures composed of cobalt-porphyrin based magnetic molecules adsorbed on semiconducting armchair graphene nanoribbon on a Au(111) surface. Although the graphene nanoribbons are electronically decoupled from the gold substrate due to their band gaps and weak adsorption, they enable spin coupling between the magnetic moment of the molecule and the electrons from the substrate exhibiting a Kondo resonance. Surprisingly, the Kondo temperatures corresponding to three adsorption sites of the molecules on Au(111) surface are reproduced on the molecules adsorb on the graphene nanoribbons although the molecules are locatedmore » 7.5 Å away from the surface. This finding suggests that the molecules on graphene nanoribbons experience almost the same environment for spin-electron interactions as the ones directly adsorb on Au(111). This puzzling effect is further confirmed by density functional theory calculations that reveal no spin electron interactions if the molecule is left at the same height from the Au(111) surface without the graphene nanoribbon in between.« less

Atomistic simulation of laser-pulse surface modification: Predictions of models with various length and time scales

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

Starikov, Sergey V., E-mail: starikov@ihed.ras.ru; Pisarev, Vasily V.; Joint Institute for High Temperatures, Russian Academy of Sciences, Moscow 125412

2015-04-07

In this work, the femtosecond laser pulse modification of surface is studied for aluminium (Al) and gold (Au) by use of two-temperature atomistic simulation. The results are obtained for various atomistic models with different scales: from pseudo-one-dimensional to full-scale three-dimensional simulation. The surface modification after laser irradiation can be caused by ablation and melting. For low energy laser pulses, the nanoscale ripples may be induced on a surface by melting without laser ablation. In this case, nanoscale changes of the surface are due to a splash of molten metal under temperature gradient. Laser ablation occurs at a higher pulse energymore » when a crater is formed on the surface. There are essential differences between Al ablation and Au ablation. In the first step of shock-wave induced ablation, swelling and void formation occur for both metals. However, the simulation of ablation in gold shows an additional athermal type of ablation that is associated with electron pressure relaxation. This type of ablation takes place at the surface layer, at a depth of several nanometers, and does not induce swelling.« less

Mineralogy of chondritic interplanetary dust particle impact residues from LDEF

NASA Technical Reports Server (NTRS)

Barrett, R. A.; Zolensky, M. E.; Bernhard, R.

1993-01-01

A detailed structural and compositional analysis of several impactor residues was performed utilizing transmission electron microscopy, energy dispersive spectroscopy, and electron diffraction. Residues from the interior of several craters in gold surfaces were removed with a tungsten needle, mounted in EMBED-812 epoxy, and ultramicrotomed. The presence in these residues of equilibrated ferromagnesian minerals, recrystallization textures, glass, and melted metal and sulfide bodies decorating grain boundaries is indicative of varying degrees of shock metamorphism in all impact residues we have characterized.

Enhancing gold recovery from electronic waste via lixiviant metabolic engineering in Chromobacterium violaceum.

PubMed

Tay, Song Buck; Natarajan, Gayathri; Rahim, Muhammad Nadjad bin Abdul; Tan, Hwee Tong; Chung, Maxey Ching Ming; Ting, Yen Peng; Yew, Wen Shan

2013-01-01

Conventional leaching (extraction) methods for gold recovery from electronic waste involve the use of strong acids and pose considerable threat to the environment. The alternative use of bioleaching microbes for gold recovery is non-pollutive and relies on the secretion of a lixiviant or (bio)chemical such as cyanide for extraction of gold from electronic waste. However, widespread industrial use of bioleaching microbes has been constrained by the limited cyanogenic capabilities of lixiviant-producing microorganisms such as Chromobacterium violaceum. Here we show the construction of a metabolically-engineered strain of Chromobacterium violaceum that produces more (70%) cyanide lixiviant and recovers more than twice as much gold from electronic waste compared to wild-type bacteria. Comparative proteome analyses suggested the possibility of further enhancement in cyanogenesis through subsequent metabolic engineering. Our results demonstrated the utility of lixiviant metabolic engineering in the construction of enhanced bioleaching microbes for the bioleaching of precious metals from electronic waste.

Chemo-spectroscopic sensor for carboxyl terminus overexpressed in carcinoma cell membrane.

PubMed

Stanca, Sarmiza E; Matthäus, Christian; Neugebauer, Ute; Nietzsche, Sandor; Fritzsche, Wolfgang; Dellith, Jan; Heintzmann, Rainer; Weber, Karina; Deckert, Volker; Krafft, Christoph; Popp, Jürgen

2015-10-01

Certain carboxyl groups of the plasma membrane are involved in tumorgenesis processes. A gold core-hydroxyapatite shell (AuHA) nanocomposite is introduced as chemo-spectroscopic sensor to monitor these carboxyl groups of the cell membrane. Hydroxyapatite (HA) plays the role both of a chemical detector and of a biocompatible Raman marker. The principle of detection is based on chemical interaction between the hydroxyl groups of the HA and the carboxyl terminus of the proteins. The AuHA exhibits a surface enhanced Raman scattering (SERS) signal at 954 cm(-1) which can be used for its localization. The bio-sensing capacity of AuHA towards human skin epidermoid carcinoma (A431) and Chinese hamster ovary (CHO) cell lines is investigated using Raman microspectroscopic imaging. The localization of AuHA on cells is correlated with scanning electron microscopy, transmission electron microscopy and structured illumination fluorescence microscopy. This qualitative approach is a step towards a quantitative study of the proteins terminus. This method would enable further studies on the molecular profiling of the plasma membrane, in an attempt to provide accurate cell identification. Using a gold core-hydroxyapatite shell (AuHA) nanocomposite, the authors in this paper showed the feasibility of detecting and differentiating cell surface molecules by surface enhanced Raman scattering. Copyright © 2015 Elsevier Inc. All rights reserved.

An autonomous photosynthetic device in which all charge carriers derive from surface plasmons.

PubMed

Mubeen, Syed; Lee, Joun; Singh, Nirala; Krämer, Stephan; Stucky, Galen D; Moskovits, Martin

2013-04-01

Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.

Binding of a cyclic organoselenium compound with gold nanoparticles (GNP) and its effect on electron transfer properties.

PubMed

Kumar, Pavitra V; Singh, Beena G; Maiti, Nandita; Iwaoka, Michio; Priyadarsini, K Indira

2014-12-15

Binding of a cyclic organoselenium compound, DL-trans-3,4-dihydroxy-1-selenolane (DHSred) with gold nanoparticles (GNP) of different sizes was studied by absorption spectroscopy, dynamic light scattering (DLS), transmission electron microscope (TEM), surface enhanced Raman spectroscopy (SERS) and zeta-potential (ζ) measurements. GNP of different size were synthesized by varying the reaction conditions and their size was determined by DLS and TEM techniques. The absorption spectral data showed red shift in the surface plasmon resonance (SPR) band indicating increase in the size of GNP on binding to DHSred. SERS studies confirmed that the binding of DHSred with GNP is through selenium center with planar orientation of DHSred on the GNP surface. The product of the number of binding sites (n) in GNP and the binding constant (K) was estimated for GNP of different particle size. The zeta potential (ζ) value of GNP decreased marginally in the presence of DHSred. Further, the binding of DHSred with GNP was found to enhance its reactivity with 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals (ABTS(·-)) and the reactivity increased with decrease in the GNP size. Such enhancement in the reducing ability may have a greater impact on the antioxidant activity of DHSred. Copyright © 2014 Elsevier Inc. All rights reserved.

Seamless growth of a supramolecular carpet

PubMed Central

Kim, Ju-Hyung; Ribierre, Jean-Charles; Yang, Yu Seok; Adachi, Chihaya; Kawai, Maki; Jung, Jaehoon; Fukushima, Takanori; Kim, Yousoo

2016-01-01

Organic/metal interfaces play crucial roles in the formation of intermolecular networks on metal surfaces and the performance of organic devices. Although their purity and uniformity have profound effects on the operation of organic devices, the formation of organic thin films with high interfacial uniformity on metal surfaces has suffered from the intrinsic limitation of molecular ordering imposed by irregular surface structures. Here we demonstrate a supramolecular carpet with widely uniform interfacial structure and high adaptability on a metal surface via a one-step process. The high uniformity is achieved with well-balanced interfacial interactions and site-specific molecular rearrangements, even on a pre-annealed amorphous gold surface. Co-existing electronic structures show selective availability corresponding to the energy region and the local position of the system. These findings provide not only a deeper insight into organic thin films with high structural integrity, but also a new way to tailor interfacial geometric and electronic structures. PMID:26839053

Preparation of narrow dispersity gold nanorods by asymmetrical flow field-flow fractionation and investigation of surface plasmon resonance.

PubMed

Runyon, J Ray; Goering, Adam; Yong, Ken-Tye; Williams, S Kim Ratanathanawongs

2013-01-15

The development of an asymmetrical field-flow fractionation (AsFlFFF) method for separating gold nanorods (GNR) is reported. Collected fractions containing GNR subpopulations with aspect ratios, sizes, and shapes which are more narrowly dispersed than the original population were further characterized by UV-vis spectroscopy and transmission electron microscopy. This ability to obtain different sizes and shapes of nanoparticles enabled the evaluation of a new approach to estimating the retention time and hydrodynamic size of nanorods and the investigation of GNR optical properties at a previously unattainable level of detail. Experimental results demonstrate that the longitudinal surface plasmon absorption maximum of GNRs is correlated with the effective particle radius in addition to the aspect ratio. This may account for some of the variabilities reported in published empirical data from different research groups and supports reports of simulated absorption spectra of GNRs of different physical dimensions. The use of AsFlFFF with dual UV-vis detection to rapidly assess relative changes in GNR subpopulations was demonstrated for irregularly shaped gold nanoparticles formed at different synthesis temperatures.

Nano-imprint gold grating as refractive index sensor

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

Kumari, Sudha; Mohapatra, Saswat; Moirangthem, Rakesh S.

Large scale of fabrication of plasmonic nanostructures has been a challenging task due to time consuming process and requirement of expensive nanofabrication tools such as electron beam lithography system, focused ion beam system, and extreme UV photolithography system. Here, we present a cost-effective fabrication technique so called soft nanoimprinting to fabricate nanostructures on the larger sample area. In our fabrication process, a commercially available optical DVD disc was used as a template which was imprinted on a polymer glass substrate to prepare 1D polymer nano-grating. A homemade nanoimprinting setup was used in this fabrication process. Further, a label-free refractive indexmore » sensor was developed by utilizing the properties of surface plasmon resonance (SPR) of a gold coated 1D polymer nano-grating. Refractive index sensing was tested by exposing different solutions of glycerol-water mixture on the surface of gold nano-grating. The calculated bulk refractive index sensitivity was found to be 751nm/RIU. We believed that our proposed SPR sensor could be a promising candidate for developing low-cost refractive index sensor with high sensitivity on a large scale.« less

Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.

PubMed

Luo, Jingjie; Ersen, Ovidiu; Chu, Wei; Dintzer, Thierry; Petit, Pierre; Petit, Corinne

2016-11-15

The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles. Copyright © 2016. Published by Elsevier Inc.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

NASA Astrophysics Data System (ADS)

Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

The Morphology of Silver Layers on SU8 polymers prepared by Electroless Deposition

NASA Astrophysics Data System (ADS)

Dutta, Aniruddha; Yuan, Biao; Heinrich, Helge; Grabill, Chris; Williams, Henry; Kuebler, Stephen; Bhattacharya, Aniket

2010-03-01

Silver was deposited onto the functionalized surface of polymeric SU-8 where gold nanoparticles (Au-NPs) act as nucleation sites using electroless metallization chemistry. Here we report on the evolution of the nanoscale morphology of deposited Ag studied by Transmission Electron Microscopy (TEM). In TEM of sample cross sections correlations between the original gold and the silver nanoparticles were obtained while plan-view TEM results showed the distribution of nanoparticles on the surface. Scanning TEM with a high-angle annular dark field detector was used to obtain atomic number contrast. The morphology of the deposited Ag was controlled through the presence and absence of gum Arabic. The thickness and height fluctuations of the Ag layer were determined as a function of time and a statistical analysis of the growth process was conducted for the initial deposition periods.

Gold nanoparticles enlighten the future of cancer theranostics

PubMed Central

Guo, Jianfeng; Rahme, Kamil; He, Yan; Li, Lin-Lin; Holmes, Justin D; O’Driscoll, Caitriona M

2017-01-01

Development of multifunctional nanomaterials, one of the most interesting and advanced research areas in the field of nanotechnology, is anticipated to revolutionize cancer diagnosis and treatment. Gold nanoparticles (AuNPs) are now being widely utilized in bio-imaging and phototherapy due to their tunable and highly sensitive optical and electronic properties (the surface plasmon resonance). As a new concept, termed “theranostics,” multifunctional AuNPs may contain diagnostic and therapeutic functions that can be integrated into one system, thereby simultaneously facilitating diagnosis and therapy and monitoring therapeutic responses. In this review, the important properties of AuNPs relevant to diagnostic and phototherapeutic applications such as structure, shape, optics, and surface chemistry are described. Barriers for translational development of theranostic AuNPs and recent advances in the application of AuNPs for cancer diagnosis, photothermal, and photodynamic therapy are discussed. PMID:28883725

Interaction of β-sheet folds with a gold surface.

PubMed

Hoefling, Martin; Monti, Susanna; Corni, Stefano; Gottschalk, Kay Eberhard

2011-01-01

The adsorption of proteins on inorganic surfaces is of fundamental biological importance. Further, biomedical and nanotechnological applications increasingly use interfaces between inorganic material and polypeptides. Yet, the underlying adsorption mechanism of polypeptides on surfaces is not well understood and experimentally difficult to analyze. Therefore, we investigate here the interactions of polypeptides with a gold(111) surface using computational molecular dynamics (MD) simulations with a polarizable gold model in explicit water. Our focus in this paper is the investigation of the interaction of polypeptides with β-sheet folds. First, we concentrate on a β-sheet forming model peptide. Second, we investigate the interactions of two domains with high β-sheet content of the biologically important extracellular matrix protein fibronectin (FN). We find that adsorption occurs in a stepwise mechanism both for the model peptide and the protein. The positively charged amino acid Arg facilitates the initial contact formation between protein and gold surface. Our results suggest that an effective gold-binding surface patch is overall uncharged, but contains Arg for contact initiation. The polypeptides do not unfold on the gold surface within the simulation time. However, for the two FN domains, the relative domain-domain orientation changes. The observation of a very fast and strong adsorption indicates that in a biological matrix, no bare gold surfaces will be present. Hence, the bioactivity of gold surfaces (like bare gold nanoparticles) will critically depend on the history of particle administration and the proteins present during initial contact between gold and biological material. Further, gold particles may act as seeds for protein aggregation. Structural re-organization and protein aggregation are potentially of immunological importance.

Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces

NASA Astrophysics Data System (ADS)

Singh, Jagdeep

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups. UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure. Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shortened by UMI.)

SU-E-T-645: Dose Enhancement to Cell Nucleus Due to Hard Collisions of Protons with Electrons in Gold Nanospheres

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

Eley, J; Krishnan, S

2014-06-15

Purpose: The purpose of this study was to investigate the theoretical dose enhancement to a cell nucleus due to increased fluence of secondary electrons when gold nanospheres are present in the cytoplasm during proton therapy. Methods: We modeled the irradiation of prostate cancer cells using protons of variable energies when 10,000 gold nanoparticles, each with radius of 10 nm, were randomly distributed in the cytoplasm. Using simple analytical equations, we calculated the increased mean dose to the cell nucleus due to secondary electrons produced by hard collisions of 0.1, 1, 10, and 100 MeV protons with orbital electrons in gold.more » We only counted electrons with kinetic energy higher than 1 keV. In addition to calculating the increase in the mean dose to the cell nucleus, we also calculated the increase in local dose in the “shadow,” i.e., the umbra, of individual gold nanospheres due to forward scattered electrons. Results: For proton energies of 0.1, 1, 10, and 100 MeV, we calculated increases to the mean nuclear dose of 0.15, 0.09, 0.05, and 0.04%, respectively. When we considered local dose increases in the shadows of individual gold spheres, we calculated local dose increases of 5.5, 3.2, 1.9, and 1.3%, respectively. Conclusion: We found negligible, less than 0.2%, increases in the mean dose to the cell nucleus due to electrons produced by hard collisions of protons with electrons in gold nanospheres. However, we observed increases up to 5.5% in the local dose in the shadow of gold nanospheres. Considering the shadow radius of 10 nm, these local dose enhancements may have implications for slightly increased probability of clustered DNA damage when gold nanoparticles are close to the nuclear membrane.« less

Electron tunnelling through single azurin molecules can be on/off switched by voltage pulses

NASA Astrophysics Data System (ADS)

Baldacchini, Chiara; Kumar, Vivek; Bizzarri, Anna Rita; Cannistraro, Salvatore

2015-05-01

Redox metalloproteins are emerging as promising candidates for future bio-optoelectronic and nano-biomemory devices, and the control of their electron transfer properties through external signals is still a crucial task. Here, we show that a reversible on/off switching of the electron current tunnelling through a single protein can be achieved in azurin protein molecules adsorbed on gold surfaces, by applying appropriate voltage pulses through a scanning tunnelling microscope tip. The observed changes in the hybrid system tunnelling properties are discussed in terms of long-sustained charging of the protein milieu.

Green synthesis of Nerium oleander-conjugated gold nanoparticles and study of its in vitro anticancer activity on MCF-7 cell lines and catalytic activity

NASA Astrophysics Data System (ADS)

Barai, Abir Chandan; Paul, Koushik; Dey, Aditi; Manna, Subhankar; Roy, Somenath; Bag, Braja Gopal; Mukhopadhyay, Chiradeep

2018-04-01

The phytochemicals present in the stem bark extract of Nerium oleander (commonly known as Karabi) have been utilized for the green synthesis of stable gold-conjugated nanoparticles at room temperature under very mild conditions. The green synthesized gold-conjugated nanoparticles were characterized by surface plasmon resonance spectroscopy, High resolution transmission electron microscopy, X-ray diffraction studies and dynamic light scattering. A mechanism for the synthesis and stabilization of gold-conjugated nanoparticles (AuNPs) has been proposed. Anticancer activity of the stabilized AuNPs studied against MCF-7 breast cancer cell line revealed that the stabilized AuNPs were highly effective for the apoptosis of cancer cells selectively. The antioxidant activity of the stem bark extract of Nerium oleander has also been studied against a long lived 2,2-diphenylpicrylhydrazyl radical at room temperature. Moreover, the utilization of the stabilized AuNPs as a catalyst has also been demonstrated. [Figure not available: see fulltext.

Plasmonic Optical Fiber Sensor Based on Double Step Growth of Gold Nano-Islands

PubMed Central

Vasconcelos, Helena

2018-01-01

It is presented the fabrication and characterization of optical fiber sensors for refractive index measurement based on localized surface plasmon resonance (LSPR) with gold nano-islands obtained by single and by repeated thermal dewetting of gold thin films. Thin films of gold deposited on silica (SiO2) substrates and produced by different experimental conditions were analyzed by Scanning Electron Microscope/Dispersive X-ray Spectroscopy (SEM/EDS) and optical means, allowing identifying and characterizing the formation of nano-islands. The wavelength shift sensitivity to the surrounding refractive index of sensors produced by single and by repeated dewetting is compared. While for the single step dewetting, a wavelength shift sensitivity of ~60 nm/RIU was calculated, for the repeated dewetting, a value of ~186 nm/RIU was obtained, an increase of more than three times. It is expected that through changing the fabrication parameters and using other fiber sensor geometries, higher sensitivities may be achieved, allowing, in addition, for the possibility of tuning the plasmonic frequency. PMID:29677108

Green synthesis of Nerium oleander-conjugated gold nanoparticles and study of its in vitro anticancer activity on MCF-7 cell lines and catalytic activity.

PubMed

Barai, Abir Chandan; Paul, Koushik; Dey, Aditi; Manna, Subhankar; Roy, Somenath; Bag, Braja Gopal; Mukhopadhyay, Chiradeep

2018-01-01

The phytochemicals present in the stem bark extract of Nerium oleander (commonly known as Karabi) have been utilized for the green synthesis of stable gold-conjugated nanoparticles at room temperature under very mild conditions. The green synthesized gold-conjugated nanoparticles were characterized by surface plasmon resonance spectroscopy, High resolution transmission electron microscopy, X-ray diffraction studies and dynamic light scattering. A mechanism for the synthesis and stabilization of gold-conjugated nanoparticles (AuNPs) has been proposed. Anticancer activity of the stabilized AuNPs studied against MCF-7 breast cancer cell line revealed that the stabilized AuNPs were highly effective for the apoptosis of cancer cells selectively. The antioxidant activity of the stem bark extract of Nerium oleander has also been studied against a long lived 2,2-diphenylpicrylhydrazyl radical at room temperature. Moreover, the utilization of the stabilized AuNPs as a catalyst has also been demonstrated.

Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

NASA Astrophysics Data System (ADS)

Abdellatif, M. H.; Ghosh, S.; Liakos, I.; Scarpellini, A.; Marras, S.; Diaspro, A.; Salerno, M.

2016-02-01

The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.

Photothermal Nanotherapeutics and Nanodiagnostics for Selective Killing of Bacteria Targeted with Gold Nanoparticles

PubMed Central

Zharov, Vladimir P.; Mercer, Kelly E.; Galitovskaya, Elena N.; Smeltzer, Mark S.

2006-01-01

We describe a new method for selective laser killing of bacteria targeted with light-absorbing gold nanoparticles conjugated with specific antibodies. The multifunctional photothermal (PT) microscope/spectrometer provides a real-time assessment of this new therapeutic intervention. In this integrated system, strong laser-induced overheating effects accompanied by the bubble-formation phenomena around clustered gold nanoparticles are the main cause of bacterial damage. PT imaging and time-resolved monitoring of the integrated PT responses assessed these effects. Specifically, we used this technology for selective killing of the Gram-positive bacterium Staphylococcus aureus by targeting the bacterial surface using 10-, 20-, and 40-nm gold particles conjugated with anti-protein A antibodies. Labeled bacteria were irradiated with focused laser pulses (420–570 nm, 12 ns, 0.1–5 J/cm2, 100 pulses), and laser-induced bacterial damage observed at different laser fluences and nanoparticle sizes was verified by optical transmission, electron microscopy, and conventional viability testing. PMID:16239330

Plasmonic Optical Fiber Sensor Based on Double Step Growth of Gold Nano-Islands.

PubMed

de Almeida, José M M M; Vasconcelos, Helena; Jorge, Pedro A S; Coelho, Luis

2018-04-20

It is presented the fabrication and characterization of optical fiber sensors for refractive index measurement based on localized surface plasmon resonance (LSPR) with gold nano-islands obtained by single and by repeated thermal dewetting of gold thin films. Thin films of gold deposited on silica (SiO₂) substrates and produced by different experimental conditions were analyzed by Scanning Electron Microscope/Dispersive X-ray Spectroscopy (SEM/EDS) and optical means, allowing identifying and characterizing the formation of nano-islands. The wavelength shift sensitivity to the surrounding refractive index of sensors produced by single and by repeated dewetting is compared. While for the single step dewetting, a wavelength shift sensitivity of ~60 nm/RIU was calculated, for the repeated dewetting, a value of ~186 nm/RIU was obtained, an increase of more than three times. It is expected that through changing the fabrication parameters and using other fiber sensor geometries, higher sensitivities may be achieved, allowing, in addition, for the possibility of tuning the plasmonic frequency.

Plasmonic properties and enhanced fluorescence of gold and dye-doped silica nanoparticle aggregates

NASA Astrophysics Data System (ADS)

Green, Nathaniel Scott

The development of metal-enhanced fluorescence has prompted a great interest in augmenting the photophysical properties of fluorescent molecules with noble metal nanostructures. Our research efforts, outlined in this dissertation, focus on augmenting properties of fluorophores by conjugation with gold nanostructures. The project goals are split into two separate efforts; the enhancement in brightness of fluorophores and long distance non-radiative energy transfer between fluorophores. We believe that interacting dye-doped silica nanoparticles with gold nanoparticles can facilitate both of these phenomena. Our primary research interest is focused on optimizing brightness, as this goal should open a path to studying the second goal of non-radiative energy transfer. The two major challenges to this are constructing suitable nanomaterials and functionalizing them to promote plasmonically active complexes. The synthesis of dye-doped layered silica nanoparticles allows for control over the discrete location of the dye and a substrate that can be surface functionalized. Controlling the exact location of the dye is important to create a silica spacer, which promotes productive interactions with metal nanostructures. Furthermore, the synthesis of silica nanoparticles allows for various fluorophores to be studied in similar environments (removing solvent and other chemo-sensitive issues). Functionalizing the surface of silica nanoparticles allows control over the degree of silica and gold nanoparticle aggregation in solution. Heteroaggregation in solution is useful for producing well-aggregated clusters of many gold around a single silica nanoparticle. The dye-doped surface functionalized silica nanoparticles can than be mixed efficiently with gold nanomaterials. Aggregating multiple gold nanospheres around a single dye-doped silica nanoparticle can dramatically increase the fluorescent brightness of the sample via metal-enhanced fluorescence due to increase plasmonic scattering. Our aim is to promote heteroaggregation with functionalized silica nanoparticles while minimizing homoaggregation of silica-silica or gold-gold species. Reproducible production of multiple gold nanospheres about a dye-doped silica nanoparticle should lead to dramatic fluorescence brightness enhancements in solution. Gold nanorods can potentially be used to establish radiationless energy transfer between hetero dye-doped silica nanoparticles via gold nanorod plasmon mediated FRET by aggregating two different dye-doped silica nanoparticles preferentially at opposite ends of the nanorod. End-cap binding is accomplished by tuning the strength of gold binding ligands that functionalize the surface of the silica nanoparticles. The gold nanorod can then theoretically serve as a waveguide by employing the longitudinal plasmon as a non-radiative energy transfer agent between the two different fluorophores, giving rise to a new ultrafast signaling paradigm. Heteroaggregation of dye-doped silica nanoparticles and gold nanorods can be potentially employed to as nano waveguides. Construction and aggregation of functionalized silica and gold nano-materials provides an opportunity to advance the field of fluorescence. The synthesis of gold nano-particles allows control over their size and shape, which give rise to useful optical and electronic properties. Silica nanoparticles provide a framework allowing control over a requisite distance for increasing beneficial and deceasing non-radiative dye-metal interactions as well fluorophore protection. Our aim is to take advantage of fine-tuned synthetic control of functionalized nanomaterials to realize the great potential of solution based metal-enhanced fluorescence for future applications.

Effect of surface roughness on substrate-tuned gold nanoparticle gap plasmon resonances.

PubMed

Lumdee, Chatdanai; Yun, Binfeng; Kik, Pieter G

2015-03-07

The effect of nanoscale surface roughness on the gap plasmon resonance of gold nanoparticles on thermally evaporated gold films is investigated experimentally and numerically. Single-particle scattering spectra obtained from 80 nm diameter gold particles on a gold film show significant particle-to-particle variation of the peak scattering wavelength of ±28 nm. The experimental results are compared with numerical simulations of gold nanoparticles positioned on representative rough gold surfaces, modeled based on atomic force microscopy measurements. The predicted spectral variation and average resonance wavelength show good agreement with the measured data. The study shows that nanometer scale surface roughness can significantly affect the performance of gap plasmon-based devices.

Abroma augusta Linn bark extract-mediated green synthesis of gold nanoparticles and its application in catalytic reduction

NASA Astrophysics Data System (ADS)

Das, Subhajit; Bag, Braja Gopal; Basu, Ranadhir

2015-10-01

The bark extract of Abroma augusta Linn is rich in medicinally important phytochemicals including antioxidants and polyphenols. First one step green synthesis of gold nanoparticles (AuNPs) has been described utilizing the bark extract of Abroma augusta L. and chloroauric acid under very mild reaction conditions. The phytochemicals present in the bark extract acted both as a reducing as well as a stabilizing agent, and no additional stabilizing and capping agents were needed. Detailed characterizations of the stabilized AuNPs were carried out by surface plasmon resonance spectroscopy, high resolution transmission electron microscopy, and X-ray diffraction studies. The catalytic activity of the freshly synthesized gold nanoparticles has been demonstrated for the sodium borohydride reduction of 4-nitrophenol to 4-aminophenol, and the kinetics of the reduction reaction have been studied spectrophotometrically.

Gold nanorod vaccine for respiratory syncytial virus

NASA Astrophysics Data System (ADS)

Stone, John W.; Thornburg, Natalie J.; Blum, David L.; Kuhn, Sam J.; Wright, David W.; Crowe, James E., Jr.

2013-07-01

Respiratory syncytial virus (RSV) is a major cause of pneumonia and wheezing in infants and the elderly, but to date there is no licensed vaccine. We developed a gold nanorod construct that displayed the major protective antigen of the virus, the fusion protein (F). Nanorods conjugated to RSV F were formulated as a candidate vaccine preparation by covalent attachment of viral protein using a layer-by-layer approach. In vitro studies using ELISA, electron microscopy and circular dichroism revealed that conformation-dependent epitopes were maintained during conjugation, and transmission electron microscopy studies showed that a dispersed population of particles could be achieved. Human dendritic cells treated with the vaccine induced immune responses in primary human T cells. These results suggest that this vaccine approach may be a potent method for immunizing against viruses such as RSV with surface glycoproteins that are targets for the human immune response.

Retrieving plasmonic near-field information: A quantum-mechanical model for streaking photoelectron spectroscopy of gold nanospheres

NASA Astrophysics Data System (ADS)

Li, Jianxiong; Saydanzad, Erfan; Thumm, Uwe

2016-11-01

Streaked photoemission from nanostructures is characterized by size- and material-dependent nanometer-scale variations of the induced nanoplasmonic response to the electronic field of the streaking pulse and thus holds promise of allowing photoelectron imaging with both subfemtosecond temporal and nanometer spatial resolution. In order to scrutinize the driven collective electronic dynamics in 10-200-nm-diameter gold nanospheres, we calculated the plasmonic field induced by streaking pulses in the infrared and visible spectral range and developed a quantum-mechanical model for streaked photoemission by extreme ultraviolet pulses. Our simulated photoelectron spectra reveal a significant amplitude enhancement and phase shift of the photoelectron streaking trace relative to calculations that exclude the induced plasmonic field. Both are most pronounced for streaking pulses tuned to the plasmon frequency and retrace the plasmonic electromagnetic field enhancement and phase shift near the nanosphere surface.

Metal-assisted exfoliation (MAE): green process for transferring graphene to flexible substrates and templating of sub-nanometer plasmonic gaps (Presentation Recording)

NASA Astrophysics Data System (ADS)

Zaretski, Aliaksandr V.; Marin, Brandon C.; Moetazedi, Herad; Dill, Tyler J.; Jibril, Liban; Kong, Casey; Tao, Andrea R.; Lipomi, Darren J.

2015-09-01

This paper describes a new technique, termed "metal-assisted exfoliation," for the scalable transfer of graphene from catalytic copper foils to flexible polymeric supports. The process is amenable to roll-to-roll manufacturing, and the copper substrate can be recycled. We then demonstrate the use of single-layer graphene as a template for the formation of sub-nanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a sub-nanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming sub-nanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

Spectroscopic studies of conformational changes of β-lactoglobulin adsorbed on gold nanoparticle surfaces.

PubMed

Winuprasith, Thunnalin; Suphantharika, Manop; McClements, David Julian; He, Lili

2014-02-15

In this work, we investigated the conformational changes of a globular protein (β-lactoglobulin, β-lg) coated on the surface of 200 nm gold nanoparticles (GNPs) using a number of analytical techniques: dynamic light scattering (DLS); particle electrophoresis (ζ-potential); localized surface plasmon resonance (LSPR) spectroscopy; transmission electron microscopy (TEM); and surface-enhanced Raman scattering (SERS). The β-lg (pH 3) concentration had a pronounced effect on the aggregation and surface charge of β-lg-coated GNPs. The surface charge of GNPs changed from negative to positive as increasing amounts of β-lg molecule were added, indicating that the globular protein molecules adsorbed to the surfaces of the particles. Extensive particle aggregation occurred when β-lg did not saturate the GNP surfaces, which was attributed to electrostatic bridging flocculation. Modifications in LSPR and SERS spectra after addition of β-lg to the GNP suspensions supported the adsorption of β-lg to the particle surfaces. Moreover, SERS highlighted the importance of a number of specific molecular groups in the binding interaction, and suggested conformational changes of the globular protein after adsorption. This research provides useful information for characterizing and understanding the interactions between globular proteins and colloidal particles. Copyright © 2013 Elsevier Inc. All rights reserved.

Fabrication and surface-modification of implantable microprobes for neuroscience studies

NASA Astrophysics Data System (ADS)

Cao, H.; Nguyen, C. M.; Chiao, J. C.

2012-06-01

In this work implantable micro-probes for central nervous system (CNS) studies were developed on silicon and polyimide substrates. The probes which contained micro-electrode arrays with different surface modifications were designed for implantation in the CNS. The electrode surfaces were modified with nano-scale structures that could greatly increase the active surface area in order to enhance the electrochemical current outputs while maintaining micro-scale dimensions of the electrodes and probes. The electrodes were made of gold or platinum, and designed with different sizes. The silicon probes were modified by silicon nanowires fabricated with the vapor-liquid-solid mechanism at high temperatures. With polyimide substrates, the nanostructure modification was carried out by applying concentrated gold or silver colloid solutions onto the micro-electrodes at room temperature. The surfaces of electrodes before and after modification were observed by scanning electron microscopy. The silicon nanowire-modified surface was characterized by cyclic voltammetry. Experiments were carried out to investigate the improvement in sensing performance. The modified electrodes were tested with H2O2, electrochemical L-glutamate and dopamine. Comparisons between electrodes with and without nanostructure modification were conducted showing that the modifications have enhanced the signal outputs of the electrochemical neurotransmitter sensors.

Fabrication of Periodic Gold Nanocup Arrays Using Colloidal Lithography

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

DeVetter, Brent M.; Bernacki, Bruce E.; Bennett, Wendy D.

Within recent years, the field of plasmonics has exploded as researchers have demonstrated exciting applications related to chemical and optical sensing in combination with new nanofabrication techniques. A plasmon is a quantum of charge density oscillation that lends nanoscale metals such as gold and silver unique optical properties. In particular, gold and silver nanoparticles exhibit localized surface plasmon resonances—collective charge density oscillations on the surface of the nanoparticle—in the visible spectrum. Here, we focus on the fabrication of periodic arrays of anisotropic plasmonic nanostructures. These half-shell (or nanocup) structures can exhibit additional unique light-bending and polarization dependent optical properties thatmore » simple isotropic nanostructures cannot. Researchers are interested in the fabrication of periodic arrays of nanocups for a wide variety of applications such as low-cost optical devices, surface-enhanced Raman scattering, and tamper indication. We present a scalable technique based on colloidal lithography in which it is possible to easily fabricate large periodic arrays of nanocups using spin-coating and self-assembled commercially available polymeric nanospheres. Electron microscopy and optical spectroscopy from the visible to near-IR was performed to confirm successful nanocup fabrication. We conclude with a demonstration of the transfer of nanocups to a flexible, conformal adhesive film.« less

Radiation of the high-order plasmonic modes of large gold nanospheres excited by surface plasmon polaritons.

PubMed

Chen, Jing-Dong; Xiang, Jin; Jiang, Shuai; Dai, Qiao-Feng; Tie, Shao-Long; Lan, Sheng

2018-05-17

Large metallic nanoparticles with sizes comparable to the wavelength of light are expected to support high-order plasmon modes exhibiting resonances in the visible to near infrared spectral range. However, the radiation behavior of high-order plasmon modes, including scattering spectra and radiation patterns, remains unexplored. Here, we report on the first observation and characterization of the high-order plasmon modes excited in large gold nanospheres by using the surface plasmon polaritons generated on the surface of a thin gold film. The polarization-dependent scattering spectra were measured by inserting a polarization analyzer in the collection channel and the physical origins of the scattering peaks observed in the scattering spectra were clearly identified. More interestingly, the radiation of electric quadrupoles and octupoles was resolved in both frequency and spatial domains. In addition, the angular dependences of the radiation intensity for all plasmon modes were extracted by fitting the polarization-dependent scattering spectra with multiple Lorentz line shapes. A significant enhancement of the electric field was found in the gap plasmon modes and it was employed to generate hot-electron intraband luminescence. Our findings pave the way for exploiting the high-order plasmon modes of large metallic nanoparticles in the manipulation of light radiation and light-matter interaction.

Gold nanoparticles-based electrochemical method for the detection of protein kinase with a peptide-like inhibitor as the bioreceptor

PubMed Central

Sun, Kai; Chang, Yong; Zhou, Binbin; Wang, Xiaojin; Liu, Lin

2017-01-01

This article presents a general method for the detection of protein kinase with a peptide-like kinase inhibitor as the bioreceptor, and it was done by converting gold nanoparticles (AuNPs)-based colorimetric assay into sensitive electrochemical analysis. In the colorimetric assay, the kinase-specific aptameric peptide triggered the aggregation of AuNPs in solution. However, the specific binding of peptide to the target protein (kinase) inhibited its ability to trigger the assembly of AuNPs. In the electrochemical analysis, peptides immobilized on a gold electrode and presented as solution triggered together the in situ formation of AuNPs-based network architecture on the electrode surface. Nevertheless, the formation of peptide–kinase complex on the electrode surface made the peptide-triggered AuNPs assembly difficult. Electrochemical impedance spectroscopy was used to measure the change in surface property in the binding events. When a ferrocene-labeled peptide (Fc-peptide) was used in this design, the network of AuNPs/Fc-peptide produced a good voltammetric signal. The competitive assay allowed for the detection of protein kinase A with a detection limit of 20 mU/mL. This work should be valuable for designing novel optical or electronic biosensors and likely lead to many detection applications. PMID:28331314

Interaction of β-Sheet Folds with a Gold Surface

PubMed Central

Hoefling, Martin; Monti, Susanna; Corni, Stefano; Gottschalk, Kay Eberhard

2011-01-01

The adsorption of proteins on inorganic surfaces is of fundamental biological importance. Further, biomedical and nanotechnological applications increasingly use interfaces between inorganic material and polypeptides. Yet, the underlying adsorption mechanism of polypeptides on surfaces is not well understood and experimentally difficult to analyze. Therefore, we investigate here the interactions of polypeptides with a gold(111) surface using computational molecular dynamics (MD) simulations with a polarizable gold model in explicit water. Our focus in this paper is the investigation of the interaction of polypeptides with β-sheet folds. First, we concentrate on a β-sheet forming model peptide. Second, we investigate the interactions of two domains with high β-sheet content of the biologically important extracellular matrix protein fibronectin (FN). We find that adsorption occurs in a stepwise mechanism both for the model peptide and the protein. The positively charged amino acid Arg facilitates the initial contact formation between protein and gold surface. Our results suggest that an effective gold-binding surface patch is overall uncharged, but contains Arg for contact initiation. The polypeptides do not unfold on the gold surface within the simulation time. However, for the two FN domains, the relative domain-domain orientation changes. The observation of a very fast and strong adsorption indicates that in a biological matrix, no bare gold surfaces will be present. Hence, the bioactivity of gold surfaces (like bare gold nanoparticles) will critically depend on the history of particle administration and the proteins present during initial contact between gold and biological material. Further, gold particles may act as seeds for protein aggregation. Structural re-organization and protein aggregation are potentially of immunological importance. PMID:21687744

The SERS and TERS effects obtained by gold droplets on top of Si nanowires.

PubMed

Becker, M; Sivakov, V; Andrä, G; Geiger, R; Schreiber, J; Hoffmann, S; Michler, J; Milenin, A P; Werner, P; Christiansen, S H

2007-01-01

We show that hemispherical gold droplets on top of silicon nanowires when grown by the vapor-liquid-solid (VLS) mechanism, can produce a significant enhancement of Raman scattered signals. Signal enhancement for a few or even just single gold droplets is demonstrated by analyzing the enhanced Raman signature of malachite green molecules. For this experiment, trenches (approximately 800 nm wide) were etched in a silicon-on-insulator (SOI) wafer along <110> crystallographic directions that constitute sidewalls ({110} surfaces) suitable for the growth of silicon nanowires in <111> directions with the intention that the gold droplets on the silicon nanowires can meet somewhere in the trench when growth time is carefully selected. Another way to realize gold nanostructures in close vicinity is to attach a silicon nanowire with a gold droplet onto an atomic force microscopy (AFM) tip and to bring this tip toward another gold-coated AFM tip where malachite green molecules were deposited prior to the measurements. In both experiments, signal enhancement of characteristic Raman bands of malachite green molecules was observed. This indicates that silicon nanowires with gold droplets atop can act as efficient probes for tip-enhanced Raman spectroscopy (TERS). In our article, we show that a nanowire TERS probe can be fabricated by welding nanowires with gold droplets to AFM tips in a scanning electron microscope (SEM). TERS tips made from nanowires could improve the spatial resolution of Raman spectroscopy so that measurements on the nanometer scale are possible.

Gold as hydrogen: Structural and electronic properties and chemical bonding in Si3Au3+/0/- and comparisons to Si3H3+/0/-

NASA Astrophysics Data System (ADS)

Kiran, Boggavarapu; Li, Xi; Zhai, Hua-Jin; Wang, Lai-Sheng

2006-10-01

A single Au atom has been shown to behave like H in its bonding to Si in several mono- and disilicon gold clusters. In the current work, we investigate the Au /H analogy in trisilicon gold clusters, Si3Au3+/0/-. Photoelectron spectroscopy and density functional calculations are combined to examine the geometric and electronic structure of Si3Au3-. We find that there are three isomers competing for the ground state of Si3Au3- as is the case for Si3H3-. Extensive structural searches show that the potential energy surfaces of the trisilicon gold clusters (Si3Au3-, Si3Au3, and Si3Au3+) are similar to those of the corresponding silicon hydrides. The lowest energy isomers for Si3Au3- and Si3Au3 are structurally similar to a Si3Au four-membered ring serving as a common structural motif. For Si3Au3+, the 2π aromatic cyclotrisilenylium auride ion, analogous to the aromatic cyclotrisilenylium ion (Si3H3+), is the most stable species. Comparison of the structures and chemical bonding between Si3Au3+/0/- and the corresponding silicon hydrides further extends the isolobal analogy between Au and H.

Coumarin-gold nanoparticle bioconjugates: preparation, antioxidant, and cytotoxic effects against MCF-7 breast cancer cells

NASA Astrophysics Data System (ADS)

Mahendran, Gokila; Ponnuchamy, Kumar

2018-05-01

In recent, the conjugation of gold nanoparticles (AuNPs) with biomolecules has shown great potential especially in disease diagnostics and treatment. Taking this in account, we report the methodology involved in the conjugation of coumarin onto the surface of citrate-capped AuNPs by a simple in situ method. Herein, we systematically performed UV-Vis spectroscopy, transmission electron microscopy, dynamic light scattering, and zeta potential measurements to characterize citrate-capped AuNPs and bioconjugates. Our results demonstrate in-depth surface chemistry of bioconjugates with improved surface plasmon resonance (529 nm), morphology (near spherical shape), hydrodynamic diameter (25.3 nm) as well as surface charge (- 35 mV). Furthermore, the bioconjugates displayed dose-dependent response in scavenging free radicals and exhibited cytotoxicity against MCF-7 breast cancer cell lines. In addition, phase-contrast microscopic analysis revealed that bioconjugates promote apoptosis in cancer cells in a time-dependent manner. Overall, we ascertain the fact that this kind of bioconjugation of AuNPs with coumarin further enhances the efficacy of inorganic nanomaterials and thus make them a better bio-therapeutic candidate.

Formation of Surface and Quantum-Well States in Ultra Thin Pt Films on the Au(111) Surface

PubMed Central

Silkin, Igor V.; Koroteev, Yury M.; Echenique, Pedro M.; Chulkov, Evgueni V.

2017-01-01

The electronic structure of the Pt/Au(111) heterostructures with a number of Pt monolayers n ranging from one to three is studied in the density-functional-theory framework. The calculations demonstrate that the deposition of the Pt atomic thin films on gold substrate results in strong modifications of the electronic structure at the surface. In particular, the Au(111) s-p-type Shockley surface state becomes completely unoccupied at deposition of any number of Pt monolayers. The Pt adlayer generates numerous quantum-well states in various energy gaps of Au(111) with strong spatial confinement at the surface. As a result, strong enhancement in the local density of state at the surface Pt atomic layer in comparison with clean Pt surface is obtained. The excess in the density of states has maximal magnitude in the case of one monolayer Pt adlayer and gradually reduces with increasing number of Pt atomic layers. The spin–orbit coupling produces strong modification of the energy dispersion of the electronic states generated by the Pt adlayer and gives rise to certain quantum states with a characteristic Dirac-cone shape. PMID:29232833

Surface-enhanced Raman spectroscopy of double-shell hollow nanoparticles: electromagnetic and chemical enhancements.

PubMed

Mahmoud, Mahmoud A

2013-05-28

Enhancements of the Raman signal by the newly prepared gold-palladium and gold-platinum double-shell hollow nanoparticles were examined and compared with those using gold nanocages (AuNCs). The surface-enhanced Raman spectra (SERS) of thiophenol adsorbed on the surface of AuNCs assembled into a Langmuir-Blodgett monolayer were 10-fold stronger than AuNCs with an inner Pt or Pd shell. The chemical and electromagnetic enhancement mechanisms for these hollow nanoparticles were further proved by comparing the Raman enhancement of nitrothiophenol and nitrotoulene. Nitrothiophenol binds to the surface of the nanoparticles by covalent interaction, and Raman enhancement by both the two mechanisms is possible, while nitrotoulene does not form any chemical bond with the surface of the nanoparticles and hence no chemical enhancement is expected. Based on discrete dipole approximation (DDA) calculations and the experimental SERS results, AuNCs introduced a high electromagnetic enhancement, while the nanocages with inner Pt or Pd shell have a strong chemical enhancement. The optical measurements of the localized surface plasmon resonance (LSPR) of the nanocages with an outer Au shell and an inner Pt or Pd shell were found, experimentally and theoretically, to be broad compared with AuNCs. The possible reason could be due to the decrease of the coherence time of Au oscillated free electrons and fast damping of the plasmon energy. This agreed well with the fact that a Pt or Pd inner nanoshell decreases the electromagnetic field of the outer Au nanoshell while increasing the SERS chemical enhancement.

Enhancing gold recovery from electronic waste via lixiviant metabolic engineering in Chromobacterium violaceum

PubMed Central

Tay, Song Buck; Natarajan, Gayathri; Rahim, Muhammad Nadjad bin Abdul; Tan, Hwee Tong; Chung, Maxey Ching Ming; Ting, Yen Peng; Yew, Wen Shan

2013-01-01

Conventional leaching (extraction) methods for gold recovery from electronic waste involve the use of strong acids and pose considerable threat to the environment. The alternative use of bioleaching microbes for gold recovery is non-pollutive and relies on the secretion of a lixiviant or (bio)chemical such as cyanide for extraction of gold from electronic waste. However, widespread industrial use of bioleaching microbes has been constrained by the limited cyanogenic capabilities of lixiviant-producing microorganisms such as Chromobacterium violaceum. Here we show the construction of a metabolically-engineered strain of Chromobacterium violaceum that produces more (70%) cyanide lixiviant and recovers more than twice as much gold from electronic waste compared to wild-type bacteria. Comparative proteome analyses suggested the possibility of further enhancement in cyanogenesis through subsequent metabolic engineering. Our results demonstrated the utility of lixiviant metabolic engineering in the construction of enhanced bioleaching microbes for the bioleaching of precious metals from electronic waste. PMID:23868689

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

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

Chou Chau, Yuan-Fong, E-mail: chou.fong@ubd.edu.bn; Lim, Chee Ming; Kumara, N. T. R. N.

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 behaviorsmore » 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.« less

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.

Submolecular Structure and Orientation of Oligonucleotide Duplexes Tethered to Gold Electrodes Probed by Infrared Reflection Absorption Spectroscopy: Effect of the Electrode Potentials.

PubMed

Kékedy-Nagy, László; Ferapontova, Elena E; Brand, Izabella

2017-02-23

Unique electronic and ligand recognition properties of the DNA double helix provide basis for DNA applications in biomolecular electronic and biosensor devices. However, the relation between the structure of DNA at electrified interfaces and its electronic properties is still not well understood. Here, potential-driven changes in the submolecular structure of DNA double helices composed of either adenine-thymine (dAdT) 25 or cytosine-guanine (dGdC) 20 base pairs tethered to the gold electrodes are for the first time analyzed by in situ polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) performed under the electrochemical control. It is shown that the conformation of the DNA duplexes tethered to gold electrodes via the C 6 alkanethiol linker strongly depends on the nucleic acid sequence composition. The tilt of purine and pyrimidine rings of the complementary base pairs (dAdT and dGdC) depends on the potential applied to the electrode. By contrast, neither the conformation nor orientation of the ionic in character phosphate-sugar backbone is affected by the electrode potentials. At potentials more positive than the potential of zero charge (pzc), a gradual tilting of the double helix is observed. In this tilted orientation, the planes of the complementary purine and pyrimidine rings lie ideally parallel to each other. These potentials do not affect the integral stability of the DNA double helix at the charged interface. At potentials more negative than the pzc, DNA helices adopt a vertical to the gold surface orientation. Tilt of the purine and pyrimidine rings depends on the composition of the double helix. In monolayers composed of (dAdT) 25 molecules the rings of the complementary base pairs lie parallel to each other. By contrast, the tilt of purine and pyrimidine rings in (dGdC) 20 helices depends on the potential applied to the electrode. Such potential-induced mobility of the complementary base pairs can destabilize the helix structure at a submolecular level. These pioneer results on the potential-driven changes in the submolecular structure of double stranded DNA adsorbed on conductive supports contribute to further understanding of the potential-driven sequence-specific electronic properties of surface-tethered oligonucleotides.

Experimental studies of fundamental issues in electron transfer through nanometer scale devices

NASA Astrophysics Data System (ADS)

Yamamoto, Hiromichi

Electron transfer reactions constitute many of the primary events in materials science, chemistry, physics, and biochemistry, e.g. the electron transport properties and photoexcited processes in solids and molecules, chemical reactions, corrosion, photosynthesis, respiration, and so forth. A self-assembled monolayer (SAM) film provides us with a unique environment not only to understand and manipulate the surface electronic properties of a solid, but also to control electron transfer processes at the interface. The first topic in this thesis describes the structure and electron tunneling characterization of alkanethiol SAMs on InP(100). Angle-resolved X-ray photoelectron spectroscopy was used to characterize the bonding of alkanethiols to n-InP surfaces and to measure the monolayer thickness. The results showed that the sulfur binds to In atoms on the surface, and provided film thicknesses of 6.4 A for C8H17SH, 11.1 A for C12H25SH, and 14.9 A for C16H 33SH, resulting in an average tilt angle of 55°. The analysis indicated that super-exchange coupling between the alkane chains plays an important role in defining electron tunneling barriers, especially for highly tilted chains. The second topic describes studies of cytochrome c bound to pure and mixed SAMs of o-terminated alkanethiol (terminated with pyridine, imidazole or nitrile groups) and alkanethiol on gold. Electrochemical methods are used to determine electron transfer rate constants of cytochrome c, and scanning tunneling microscopy to observe the cytochrome c on the SAM. Detailed analysis revealed direct association of the heme of cytochrome c with the terminal groups of the SAMs and a 'turning-over' of the electron transfer of cytochrome c from adiabatic to non-adiabatic regime. The third topic describes studies of oxidation and reduction of cytochrome c in solution through eleven different self-assembled monolayers (SAMs) on gold electrodes by cyclic voltammetry. Electron transfer rate constants of cytochrome c through the eleven SAMs ranged from ≤10-4 to ˜10-1 cm/sec. A strong correlation between the electron transfer rate constants and the hydrogen bonding ability of the SAM is identified. This correlation is discussed in terms of the dependence of the rate constant on the outer-sphere reorganization energy and the electronic coupling between the cytochrome and the differently terminated monolayer films.

Fabrication, Characterization and Cytotoxicity of Spherical-Shaped Conjugated Gold-Cockle Shell Derived Calcium Carbonate Nanoparticles for Biomedical Applications

NASA Astrophysics Data System (ADS)

Kiranda, Hanan Karimah; Mahmud, Rozi; Abubakar, Danmaigoro; Zakaria, Zuki Abubakar

2018-01-01

The evolution of nanomaterial in science has brought about a growing increase in nanotechnology, biomedicine, and engineering fields. This study was aimed at fabrication and characterization of conjugated gold-cockle shell-derived calcium carbonate nanoparticles (Au-CSCaCO3NPs) for biomedical application. The synthetic technique employed used gold nanoparticle citrate reduction method and a simple precipitation method coupled with mechanical use of a Programmable roller-ball mill. The synthesized conjugated nanomaterial was characterized for its physicochemical properties using transmission electron microscope (TEM), field emission scanning electron microscope (FESEM) equipped with energy dispersive X-ray (EDX) and Fourier transform infrared spectroscopy (FTIR). However, the intricacy of cellular mechanisms can prove challenging for nanomaterial like Au-CSCaCO3NPs and thus, the need for cytotoxicity assessment. The obtained spherical-shaped nanoparticles (light-green purplish) have an average diameter size of 35 ± 16 nm, high carbon and oxygen composition. The conjugated nanomaterial, also possesses a unique spectra for aragonite polymorph and carboxylic bond significantly supporting interactions between conjugated nanoparticles. The negative surface charge and spectra absorbance highlighted their stability. The resultant spherical shaped conjugated Au-CSCaCO3NPs could be a great nanomaterial for biomedical applications.

On-chip remote charger model using plasmonic island circuit

NASA Astrophysics Data System (ADS)

Ali, J.; Youplao, P.; Pornsuwancharoen, N.; Aziz, M. S.; Chiangga, S.; Amiri, I. S.; Punthawanunt, S.; Singh, G.; Yupapin, P.

2018-06-01

We propose the remote charger model using the light fidelity (LiFi) transmission and integrate microring resonator circuit. It consists of the stacked layers of silicon-graphene-gold materials known as a plasmonic island placed at the center of the modified add-drop filter. The input light power from the remote LiFi can enter into the island via a silicon waveguide. The optimized input power is obtained by the coupled micro-lens on the silicon surface. The induced electron mobility generated in the gold layer by the interfacing layer between silicon-graphene. This is the reversed interaction of the whispering gallery mode light power of the microring system, in which the generated power is fed back into the microring circuit. The electron mobility is the required output and obtained at the device ports and characterized for the remote current source applications. The obtained calculation results have shown that the output current of ∼2.5 × 10-11 AW-1, with the gold height of 1.0 μm and the input power of 5.0 W is obtained at the output port, which is shown the potential application for a short range free pace remote charger.

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

Rodriguez, J.A.; Liu, P.; Takahashi, Y.

2011-05-30

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

J Rodriguez; P Liu; Y Takahashi

2011-12-31

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Roles of aromatic side chains and template effects of the hydrophobic cavity of a self-assembled peptide nanoarchitecture for anisotropic growth of gold nanocrystals.

PubMed

Tomizaki, Kin-ya; Kishioka, Kohei; Kobayashi, Hiroki; Kobayashi, Akitsugu; Yamada, Naoki; Kataoka, Shunsuke; Imai, Takahito; Kasuno, Megumi

2015-11-15

Gold nanocrystals are promising as catalysts and for use in sensing/imaging systems, photonic/plasmonic devices, electronics, drug delivery systems, and for photothermal therapy due to their unique physical, chemical, and biocompatible properties. The use of various organic templates allows control of the size, shape, structure, surface modification and topology of gold nanocrystals; in particular, currently the synthesis of gold nanorods requires a cytotoxic surfactant to control morphology. To control the shape of gold nanocrystals, we previously demonstrated the de novo design and synthesis of a β-sheet-forming nonapeptide (RU006: Ac-AIAKAXKIA-NH2, X=L-2-naphthylalanine, Nal) and the fabrication of gold nanocrystals by mixing RU006 and HAuCl4 in water. The reaction afforded ultrathin gold nanoribbons 50-100 nm wide, several nanometers high, and microns long. To understand the mechanism underlying gold nanoribbon formation by the RU006 system, we here report (i) the effects of replacement of the Nal aromatic side chain in the RU006 sequence with other aromatic moieties, (ii) the electrochemical properties of aromatic side chains in the de novo designed template peptides to estimate the redox potential and number of electrons participating in the gold crystallization process, and (iii) the stoichiometry of the RU006 system for gold nanoribbon synthesis. Interestingly, RU006 bearing a naphthalene moiety (oxidation peak potential of 1.50 V vs Ag/Ag(+)) and an analog [Ant(6)]-RU006 bearing a bulky anthracene moiety (oxidation peak potential of 1.05 V vs Ag/Ag(+)) allowed the growth of anisotropic (ribbon-like) and isotropic (round) gold nanocrystals, respectively. This trend in morphology of gold nanocrystals was attributed to spatially-arranged hydrophobic cavities sufficiently large to accommodate the gold precursor and to allow directed crystal growth driven by cross-linking reactions among the naphthalene rings. Support for this mechanism was obtained by decreasing the mole fraction of [Ant(6)]-RU006 against the total concentration of [Ant(6)]-RU006 and [Phe(6)]-RU006: absorption spectra similar to that for RU006 were obtained. Differences in the redox properties of the anthracene and naphthalene moieties scarcely affected morphology. We propose that construction of an appropriate hydrophobic cavity is important for templating gold nanocrystal architectures by peptide self-assembly. This mechanism would be applicable for developing simple, low toxicity, mild synthetic methods for constructing metallic nanomaterials for therapeutic use. Copyright © 2015 Elsevier Ltd. All rights reserved.

Concentration Dependence of Gold Nanoparticles for Fluorescence Enhancement

NASA Astrophysics Data System (ADS)

Solomon, Joel; Wittmershaus, Bruce

Noble metal nanoparticles possess a unique property known as surface plasmon resonance in which the conduction electrons oscillate due to incoming light, dramatically increasing their absorption and scattering of light. The oscillating electrons create a varying electric field that can affect nearby molecules. The fluorescence and photostability of fluorophores can be enhanced significantly when they are near plasmonic nanoparticles. This effect is called metal enhanced fluorescence (MEF). MEF from two fluorescence organic dyes, Lucifer Yellow CH and Riboflavin, was measured with different concentrations of 50-nm colloidal gold nanoparticles (Au-NP). The concentration range of Au-NP was varied from 2.5 to 250 pM. To maximize the interaction, the dyes were chosen so their emission spectra had considerable overlap with the absorption spectra of the Au-NP, which is common in MEF studies. If the dye molecules are too close to the surface of Au-NP, fluorescence quenching can occur instead of MEF. To try to observe this difference, silica-coated Au-NP were compared to citrate-based Au-NP; however, fluorescence quenching was observed with both Au-NP. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

Measuring Nanoscale Heat Transfer for Gold-(Gallium Oxide)-Gallium Nitride Interfaces as a Function

NASA Astrophysics Data System (ADS)

Szwejkowski, Chester; Sun, Kai; Constantin, Costel; Giri, Ashutosh; Saltonstall, Christopher; Hopkins, Patrick; NanoSynCh Team; Exsite Team

2014-03-01

Gallium nitride (GaN) is considered the most important semiconductor after the discovery of Silicon. Understanding the properties of GaN is imperative in determining the utility and applicability of this class of materials to devices. We present results of time domain thermoreflectance (TDTR) measurements as a function of surface root mean square (RMS) roughness. We used commercially available 5mm x 5mm, single-side polished GaN (3-7 μm)/Sapphire (430 μm) substrates that have a Wurtzite crystal structure and are slightly n-type doped. The GaN substrates were annealed in the open atmosphere for 10 minutes (900-1000 °C). This high-temperature treatment produced RMS values from 1-60 nm and growth of gallium oxide (GaO) as measured with an atomic force microscopy and transmission electron microscopy respectively. A gold film (80nm) was deposited on the GaN surface using electron beam physical vapor deposition which was verified using ellipsometry and profilometry. The TDTR measurements suggest that the thermal conductivity decays exponentially with RMS roughness and that there is a minimum value for thermal boundary conductance at a roughness of 15nm.

Synergistic Enhancement of Electrocatalytic CO 2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes

DOE PAGES

Rogers, Cameron; Perkins, Wade S.; Veber, Gregory; ...

2017-02-24

Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here in this paper, we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO 2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO 2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrodemore » (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO 2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.« less

Gold nanoparticle flow sensors designed for dynamic X-ray imaging in biofluids.

PubMed

Ahn, Sungsook; Jung, Sung Yong; Lee, Jin Pyung; Kim, Hae Koo; Lee, Sang Joon

2010-07-27

X-ray-based imaging is one of the most powerful and convenient methods in terms of versatility in applicable energy and high performance in use. Different from conventional nuclear medicine imaging, contrast agents are required in X-ray imaging especially for effectively targeted and molecularly specific functions. Here, in contrast to much reported static accumulation of the contrast agents in targeted organs, dynamic visualization in a living organism is successfully accomplished by the particle-traced X-ray imaging for the first time. Flow phenomena across perforated end walls of xylem vessels in rice are monitored by a gold nanoparticle (AuNP) (approximately 20 nm in diameter) as a flow tracing sensor working in nontransparent biofluids. AuNPs are surface-modified to control the hydrodynamic properties such as hydrodynamic size (DH), zeta-potential, and surface plasmonic properties in aqueous conditions. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray nanoscopy (XN), and X-ray microscopy (XM) are used to correlate the interparticle interactions with X-ray absorption ability. Cluster formation and X-ray contrast ability of the AuNPs are successfully modulated by controlling the interparticle interactions evaluated as flow-tracing sensors.

Green synthesis of gold nanoparticles using Stevia rebaudiana leaf extracts: Characterization and their stability.

PubMed

Sadeghi, Babak; Mohammadzadeh, M; Babakhani, B

2015-07-01

Various methods invented and developed for the synthesis of gold nanoparticles that increases daily consumed. According to this method, including potential environmental pollution problems and the complexity of the synthesis, in this study, the feasibility of using the leaves extract of Stevia rebaudiana (SR) for the reduction of gold ions to nanoparticles form have been studied. Stevia leaves were used to prepare the aqueous extract for this study. Gold nanoparticles were characterized with different techniques such as UV-vis spectroscopy, FT-IR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Transmission electron microscopy experiments showed that these nanoparticles are spherical and uniformly distributed and its size is from 5 to 20 nm. FT-IR spectroscopy revealed that gold nanoparticles were functionalized with biomolecules that have primary amine group (NH2), carbonyl group, OH groups and other stabilizing functional groups. X-ray diffraction pattern showed high purity and face centered cubic structure of gold nanoparticles with size of 17 nm. The scanning electron microscopy (SEM) implies the right of forming gold nanoparticles. The results, confirm that gold nanoparticles have synthesized by the leaves extract of S. rebaudiana (SR). Copyright © 2015 Elsevier B.V. All rights reserved.

Velocity-Map Imaging for Emittance Characterization of Multiphoton Electron Emission from a Gold Surface

NASA Astrophysics Data System (ADS)

Ye, Hong; Trippel, Sebastian; Di Fraia, Michele; Fallahi, Arya; Mücke, Oliver D.; Kärtner, Franz X.; Küpper, Jochen

2018-04-01

A velocity-map-imaging spectrometer is demonstrated to characterize the normalized emittance (root-mean-square, rms) of photoemitted electron bunches. Both the two-dimensional spatial distribution and the projected velocity distribution images of photoemitted electrons are recorded by the detection system and analyzed to obtain the normalized emittance (rms). With the presented distribution function of the electron photoemission angles, a mathematical method is implemented to reconstruct the three-dimensional velocity distribution. As a first example, multiphoton emission from a planar Au surface is studied via irradiation at a glancing angle by intense 45-fs laser pulses at a central wavelength of 800 nm. The reconstructed energy distribution agrees very well with the Berglund-Spicer theory of photoemission. The normalized emittance (rms) of the intrinsic electron bunch is characterized to be 128 and 14 nm rad in the X and Y directions, respectively. The demonstrated imaging spectrometer has the ability to characterize the normalized emittance (rms) in a few minutes with a fine energy resolution of 0.2 meV in the image center and will, thereby, foster the further development of x-ray free-electron-laser injectors and ultrafast electron diffraction, and it opens up opportunities for studying correlated electron emission from surfaces and vacuum nanoelectronic devices.

Enhanced light-harvesting by plasmonic hollow gold nanospheres for photovoltaic performance

PubMed Central

Lv, Jindian; Wu, Huaping; Chai, Guozhong; Liu, Aiping

2018-01-01

A ‘sandwich'-structured TiO2NR/HGN/CdS photoanode was successfully fabricated by the electrophoretic deposition of hollow gold nanospheres (HGNs) on the surface of TiO2 nanorods (NRs). The HGNs presented a wide surface plasmon resonance character in the visible region from 540 to 630 nm, and further acted as the scatter elements and light energy ‘antennas' to trap the local-field light near the TiO2NR/CdS layer, resulting in the increase of the light harvesting. An outstanding enhancement in the photochemical behaviour of TiO2NR/HGN/CdS photoanodes was attained by the contribution of HGNs in increasing the light absorption and the number of electron-hole pairs of photosensitive semiconductors. The optimized photochemical performance of TiO2NR/HGN/CdS photoanodes by using plasmonic HGNs demonstrated their potential application in energy conversion devices. PMID:29410838

Enhanced light-harvesting by plasmonic hollow gold nanospheres for photovoltaic performance.

PubMed

Ding, Hao; Lv, Jindian; Wu, Huaping; Chai, Guozhong; Liu, Aiping

2018-01-01

A 'sandwich'-structured TiO 2 NR/HGN/CdS photoanode was successfully fabricated by the electrophoretic deposition of hollow gold nanospheres (HGNs) on the surface of TiO 2 nanorods (NRs). The HGNs presented a wide surface plasmon resonance character in the visible region from 540 to 630 nm, and further acted as the scatter elements and light energy 'antennas' to trap the local-field light near the TiO 2 NR/CdS layer, resulting in the increase of the light harvesting. An outstanding enhancement in the photochemical behaviour of TiO 2 NR/HGN/CdS photoanodes was attained by the contribution of HGNs in increasing the light absorption and the number of electron-hole pairs of photosensitive semiconductors. The optimized photochemical performance of TiO 2 NR/HGN/CdS photoanodes by using plasmonic HGNs demonstrated their potential application in energy conversion devices.

Temperature dependent localized surface plasmon resonance properties of supported gold nanoparticles

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

Laha, Ranjit; Ranjan, Pranay

2016-05-23

The well known localized surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) supported on a dielectric substrate depends on the particle shape, size and type of dielectric material. The particle size and shape mainly vary with the method of preparation and the parameters involved there in. In this report, we show preparation of AuNPs supported on quartz substrate by direct current sputtering followed by thermal annealing at an optimized temperature of 400 °C. The samples were characterized using optical absorption spectra, scanning electron microscopy (SEM) and the energy dispersive x-ray spectrum. The LSPR position could be tuned by varying annealingmore » temperature. The LSPR was found to be blue shifted up to 10 nm with annealing temperature varying from 400 °C to 800 °C. The change in LSPR was ascribed to the morphology of AuNPs over quartz.« less

Stabilization of Au Monatomic-High Islands on the (2 ×2 )-Nad Reconstructed Surface of Wurtzite AlN(0001)

NASA Astrophysics Data System (ADS)

Eydoux, Benoit; Baris, Bulent; Khoussa, Hassan; Guillermet, Olivier; Gauthier, Sébastien; Bouju, Xavier; Martrou, David

2017-10-01

Noncontact atomic force microscopy images show that gold grows on the (2 ×2 )-Nad reconstructed polar (0001) surface of AlN insulating films, in the form of large monatomic islands. High-resolution images and in situ reflection high-energy electron diffraction spectra reveal two moiré patterns from which an atomic model can be built. Density functional theory calculations confirm this model and give insight into the mechanisms that lead to the stabilization of the monolayer. Gold adsorption is accompanied, first, by a global vertical charge transfer from the AlN substrate that fulfills the electrostatic stability criterion for a polar material, and second, by lateral charge transfers that are driven by the local chemical properties of the (2 ×2 )-Nad reconstruction. These results present alternative strategies to grow metal electrodes onto nitride compounds with a better controlled interface, a crucial issue for applications.

Application of a Nanostructured Enzymatic Biosensor Based on Fullerene and Gold Nanoparticles to Polyphenol Detection.

PubMed

Tortolini, Cristina; Sanzò, Gabriella; Antiochia, Riccarda; Mazzei, Franco; Favero, Gabriele

2017-01-01

Electrochemical biosensors provide an attractive means of analyzing the content of a biological sample due to the direct conversion of a biological event to an electronic signal. The signal transduction and the general performance of electrochemical biosensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. We show herein a novel electrochemical biosensing platform based on the coupling of two different nanostructured materials (gold nanoparticles and fullerenols) displaying interesting electrochemical features. The use of these nanomaterials improved the electrochemical performance of the proposed biosensor.An application of the nanostructured enzyme-based biosensor has been developed for evaluating the detection of polyphenols either in buffer solution or in real wine samples.

Temperature dependent localized surface plasmon resonance properties of supported gold nanoparticles

NASA Astrophysics Data System (ADS)

Laha, Ranjit; Ranjan, Pranay

2016-05-01

The well known localized surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) supported on a dielectric substrate depends on the particle shape, size and type of dielectric material. The particle size and shape mainly vary with the method of preparation and the parameters involved there in. In this report, we show preparation of AuNPs supported on quartz substrate by direct current sputtering followed by thermal annealing at an optimized temperature of 400 °C. The samples were characterized using optical absorption spectra, scanning electron microscopy (SEM) and the energy dispersive x-ray spectrum. The LSPR position could be tuned by varying annealing temperature. The LSPR was found to be blue shifted up to 10 nm with annealing temperature varying from 400 °C to 800 °C. The change in LSPR was ascribed to the morphology of AuNPs over quartz.

Paper-Based Analytical Devices Relying on Visible-Light-Enhanced Glucose/Air Biofuel Cells.

PubMed

Wu, Kaiqing; Zhang, Yan; Wang, Yanhu; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-11-04

A strategy that combines visible-light-enhanced biofuel cells (BFCs) and electrochemical immunosensor into paper-based analytical devices was proposed for sensitive detection of the carbohydrate antigen 15-3 (CA15-3). The gold nanoparticle modified paper electrode with large surface area and good conductibility was applied as an effective matrix for primary antibodies. The glucose dehydrogenase (GDH) modified gold-silver bimetallic nanoparticles were used as bioanodic biocatalyst and signal magnification label. Poly(terthiophene) (pTTh), a photoresponsive conducting polymer, served as catalyst in cathode for the reduction of oxygen upon illumination by visible light. In the bioanode, electrons were generated through the oxidation of glucose catalyzed by GDH. The amount of electrons is determined by the amount of GDH, which finally depended on the amount of CA15-3. In the cathode, electrons from the bioanode could combine with the generated holes in the HOMO energy level of cathode catalysts pTTh. Meanwhile, the high energy level photoexcited electrons were generated in the LUMO energy level and involved in the oxygen reduction reaction, finally resulting in an increasing current and a decreasing overpotential. According to the current signal, simple and efficient detection of CA15-3 was achieved.

Vitis vinifera peel and seed gold nanoparticles exhibit chemopreventive potential, antioxidant activity and induce apoptosis through mutant p53, Bcl-2 and pan cytokeratin down-regulation in experimental animals.

PubMed

Nirmala, J Grace; Narendhirakannan, R T

2017-05-01

Several studies suggest surface modifications of gold nanoparticles (AuNPs) by capping agents or surface coatings could play an important role in biological systems, and site directed delivery. The present study was carried out to assess the antioxidant and apoptotic activities of the Vitis vinifera peel and seed gold nanoparticles in experimentally induced cancer in Swiss albino mice. 12-dimethylbenz [a] anthracene (DMBA) (single application) and 12-O-tetradecanoylphorbol 13-acetate (TPA) (thrice a week) were applied on the dorsal area of the skin to induce skin papillomagenesis in Swiss albino mice for 16 weeks. Gold nanoparticles were synthesized using Vitis vinifera peel and seed aqueous extracts and characterized by Transmission electron microscopic (TEM) analyses. On topical application, peel and seed gold nanoparticles demonstrated chemopreventive potential by significantly (p<0.05) reducing the cumulative number of tumors while increasing the antioxidant enzyme activities in the gold nanoparticles treated mice. The down-regulated expression of mutant p53, Bcl-2 and the levels of pan-cytokeratins might have facilitated the process of apoptosis in the chemical carcinogenesis process. The results were supported by the histopathological evaluation which exhibited mild dysplasia and acanthosis in the skin tissues of Vitis vinifera peel and seed AuNPs treated mice. Based on the present study, the chemopreventive action of Vitis vinifera peel and seed AuNPs is probably due to its ability to stimulate the antioxidant enzymes within the cells and suppressed abnormal skin cell proliferation that occurred during DMBA-induced skin papillomagenesis. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

NASA Astrophysics Data System (ADS)

Park, Jisu; Cha, Song-Hyun; Cho, Seonho; Park, Youmie

2016-06-01

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of -41.98 mV for the gold nanoparticles and -53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV-visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7-99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.

A high figure of merit localized surface plasmon sensor based on a gold nanograting on the top of a gold planar film

NASA Astrophysics Data System (ADS)

Zhang, Zu-Yin; Wang, Li-Na; Hu, Hai-Feng; Li, Kang-Wen; Ma, Xun-Peng; Song, Guo-Feng

2013-10-01

We investigate the sensitivity and figure of merit (FOM) of a localized surface plasmon (LSP) sensor with gold nanograting on the top of planar metallic film. The sensitivity of the localized surface plasmon sensor is 317 nm/RIU, and the FOM is predicted to be above 8, which is very high for a localized surface plasmon sensor. By employing the rigorous coupled-wave analysis (RCWA) method, we analyze the distribution of the magnetic field and find that the sensing property of our proposed system is attributed to the interactions between the localized surface plasmon around the gold nanostrips and the surface plasmon polarition on the surface of the gold planar metallic film. These findings are important for developing high FOM localized surface plasmon sensors.

Synergistic effect of reductase and keratinase for facile synthesis of protein-coated gold nanoparticles.

PubMed

Gupta, Sonali; Singh, Surinder P; Singh, Rajni

2015-05-01

We have synthesized gold nanoparticles (GNPs) using chicken feathers (poultry waste) and Bacillus subtilis RSE163. Disulfide reductase and keratinase produced by Bacillus subtilis during the degradation of chicken feather has been used to reduce Au(3+) from HAuCl4 precursor to produce gold nanoparticles. The synthesized biogenic GNPs were characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), and zeta potential measurements. Fourier transform infrared (FTIR) spectroscopy indicated the presence of protein capping on synthesized GNPs, imparting multifunctionality to the GNP surface. Furthermore, the nontoxic nature of biogenic GNPs was insured by interaction with Escherichia coli (ATCC11103), where TEM images and enhancement of growth rate of E. coli in log phase signified their nontoxic nature. The results indicate that the synthesis of biocompatible GNPs using poultry waste may find potential applications in drug delivery and sensing.

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

Characterization and in vitro studies on anticancer, antioxidant activity against colon cancer cell line of gold nanoparticles capped with Cassia tora SM leaf extract

NASA Astrophysics Data System (ADS)

Abel, Ezra Elumalai; John Poonga, Preetam Raj; Panicker, Shirly George

2016-01-01

This study was aimed to determine the effectiveness of synthesized gold nanoparticles of an ethnobotanically and medicinally important plant species Cassia tora against colon cancer cells and to find its antibacterial and antioxidant activities. In order to improve the bioavailability of C. tora, we synthesized gold nanoparticles through green synthesis, by simple mixing and stirring of C. tora leaf powder and tetrachloroauric acid (HAuCl4) solution which gave a dispersion of gold nanoparticles conjugate with C. tora secondary metabolites (SMs) with characteristic surface plasmon resonance. It was characterized by Fourier transform infrared spectroscopy, zeta sizer, zeta potential and transmission electron microscopy. Antibacterial activity was carried out for gold nanoparticles conjugated with C. tora SMs, using well-diffusion method. The MTT assay for cell viability and markers such as catalase, nitric oxide and lipid peroxidation was predictable to confirm the cytotoxicity and antioxidant properties. The treatment of gold nanoparticles conjugated with C. tora SMs on Col320 cells showed reduction in the cell viability through MTT assay, and it also significantly suppressed the release of H2O2, LPO and NO production in a dose-dependent manner. C. tora SMs conjugate gold nanoparticles showed enhanced bioavailability, antioxidant and anticancer effect against colon cancer cell line (Col320).

TiO2 nanorods thin-films embedded with gold nanoparticles for enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Raval, Dhyey; Jani, Margi; Mukhopadhyay, Indrajit; Ray, Abhijit

2018-05-01

This article reports on the gold nanoparticle (Au-NP) induced absorption enhancement in the hydrothermally grown titanium dioxide nanorods (TiO2-NRs). The localized surface plasmon resonance (LSPR) and transfer of electron from Au-NPs attached to the TiO2-NR have been related to their photocatalytic response. The photocurrent enhancement observed in the studies of IPCE has been explained on the basis of electrons in the conduction band of TiO2-NR. The electrons from the Au-NP to the conduction band of TiO2-NR with respect to the wavelength of the incident spectrum shows an increase in efficiency over pristine TiO2-NRs sample. Further, to investigate the role of Au-NP, an absorption spectra with its incident wavelength shows an increase in the visible spectrum in the present study. This provides an explanation for the response to the absorption of the wide bandgap semiconductor oxide which gives an opportunity to develop a hybrid structure on the transparent substrates. The better response of Au-NPs/TiO2-NRs system can be used in photocatalytic processes.

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

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

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

DOE PAGES

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue; ...

2017-12-08

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

Multi-modality nanoparticles having optically responsive shape

DOEpatents

Chen, Fanqing; Bouchard, Louis-Serge

2015-05-19

In certain embodiments novel nanoparticles (nanowontons) are provided that are suitable for multimodal imaging and/or therapy. In one embodiment, the nanoparticles include a first biocompatible (e.g., gold) layer, an inner core layer (e.g., a non-biocompatible material), and a biocompatible (e.g., gold) layer. The first gold layer includes a concave surface that forms a first outer surface of the layered nanoparticle. The second gold layer includes a convex surface that forms a second outer surface of the layered nanoparticle. The first and second gold layers encapsulate the inner core material layer. Methods of fabricating such nanoparticles are also provided.

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.

Magnetic memory of a single-molecule quantum magnet wired to a gold surface.

PubMed

Mannini, Matteo; Pineider, Francesco; Sainctavit, Philippe; Danieli, Chiara; Otero, Edwige; Sciancalepore, Corrado; Talarico, Anna Maria; Arrio, Marie-Anne; Cornia, Andrea; Gatteschi, Dante; Sessoli, Roberta

2009-03-01

In the field of molecular spintronics, the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. Although simple paramagnetic molecules can show surface-induced magnetic ordering and hysteresis when deposited on ferromagnetic surfaces, information storage at the molecular level requires molecules exhibiting an intrinsic remnant magnetization, like the so-called single-molecule magnets (SMMs). These have been intensively investigated for their rich quantum behaviour but no magnetic hysteresis has been so far reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, we have now found that robust, tailor-made Fe(4) complexes retain magnetic hysteresis at gold surfaces. Our results demonstrate that isolated SMMs can be used for storing information. The road is now open to address individual molecules wired to a conducting surface in their blocked magnetization state, thereby enabling investigation of the elementary interactions between electron transport and magnetism degrees of freedom at the molecular scale.

Polymer-coated surface enhanced Raman scattering (SERS) gold nanoparticles for multiplexed labeling of chronic lymphocytic leukemia cells

NASA Astrophysics Data System (ADS)

MacLaughlin, Christina M.; Parker, Edward P. K.; Walker, Gilbert C.; Wang, Chen

2012-01-01

The ease and flexibility of functionalization and inherent light scattering properties of plasmonic nanoparticles make them suitable contrast agents for measurement of cell surface markers. Immunophenotyping of lymphoproliferative disorders is traditionally undertaken using fluorescence detection methods which have a number of limitations. Herein, surface-enhanced Raman scattering (SERS) gold nanoparticles conjugated to monoclonal antibodies are used for the selective targeting of CD molecules on the surface of chronic lymphocytic leukemia (CLL) cells. Raman-active reporters were physisorbed on to the surface of 60 nm spherical Au nanoparticles, the particles were coated with 5kDa polyethylene glycol (PEG) including functionalities for conjugation to monoclonal IgG1 antibodies. A novel method for quantifying the number of antibodies bound to SERS probes on an individual basis as opposed to obtaining averages from solution was demonstrated using metal dots in transmission electron microscopy (TEM). The specificity of the interaction between SERS probes and surface CD molecules of CLL cells was assessed using Raman spectroscopy and dark field microscopy. An in-depth study of SERS probe targeting to B lymphocyte marker CD20 was undertaken, and proof-of-concept targeting using different SERS nanoparticle dyes specific for cell surface CD19, CD45 and CD5 demonstrated using SERS spectroscopy.

Relationship between axenic growth of Dictyostelium discoideum strains and their track morphology on substrates coated with gold particles

PubMed Central

1983-01-01

Amoebae of Dictyostelium discoideum produce tracks with two distinct morphologies on gold-coated coverslips. The wild-type strain and other strains that feed only by phagocytosis produced indistinct, fuzzy tracks, whereas mutants capable of axenic growth produced clear, sharp tracks. The sharp track morphology was found to be a recessive phenotype that segregates with axenicity and probably requires a previously unidentified axenic mutation. Axenic and nonaxenic strains also differed in their ability to pinocytose. When the two types of cells were shifted from bacterial growth plates to nutrient media, within 24 h the axenic strain established a rapid rate of pinocytosis, approximately 100-fold higher than the low rate detectable for the nonaxenic strain. However, track formation did not appear to be directly related to endocytosis. Electron microscopic examination of cells during track formation showed that both axenic and nonaxenic strains accumulated gold particles on their surfaces, but neither strain internalized the gold to any significant degree. Observation of living cells revealed that axenic strains collected all particles that they contacted, whereas wild-type strains left many particles undisturbed. The size of the gold particle clusters discarded by the cells also contributed to track morphology. PMID:6619183

Biosynthesis of nanoparticles of metals and metalloids by basidiomycetes. Preparation of gold nanoparticles by using purified fungal phenol oxidases.

PubMed

Vetchinkina, Elena P; Loshchinina, Ekaterina A; Vodolazov, Ilya R; Kursky, Viktor F; Dykman, Lev A; Nikitina, Valentina E

2017-02-01

The work shows the ability of cultured Basidiomycetes of different taxonomic groups-Lentinus edodes, Pleurotus ostreatus, Ganoderma lucidum, and Grifola frondosa-to recover gold, silver, selenium, and silicon, to elemental state with nanoparticles formation. It examines the effect of these metal and metalloid compounds on the parameters of growth and accumulation of biomass; the optimal cultivation conditions and concentrations of the studied ion-containing compounds for recovery of nanoparticles have been identified. Using the techniques of transmission electron microscopy, dynamic light scattering, X-ray fluorescence and X-ray phase analysis, the degrees of oxidation of the bioreduced elements, the ζ-potential of colloidal solutions uniformity, size, shape, and location of the nanoparticles in the culture fluid, as well as on the surface and the inside of filamentous hyphae have been determined. The study has found the part played by homogeneous chromatographically pure fungal phenol-oxidizing enzymes (laccases, tyrosinases, and Mn-peroxidases) in the recovery mechanism with formation of electrostatically stabilized colloidal solutions. A hypothetical mechanism of gold(III) reduction from HAuCl 4 to gold(0) by phenol oxidases with gold nanoparticles formation of different shapes and sizes has been introduced.

The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

PubMed Central

Kamalakar, M Venkata; Prendergast, Úna; Kübel, Christian; Lemma, Tibebe; Dayen, Jean-François

2014-01-01

Summary We prepare and investigate two-dimensional (2D) single-layer arrays and multilayered networks of gold nanoparticles derivatized with conjugated hetero-aromatic molecules, i.e., S-(4-{[2,6-bipyrazol-1-yl)pyrid-4-yl]ethynyl}phenyl)thiolate (herein S-BPP), as capping ligands. These structures are fabricated by a combination of self-assembly and microcontact printing techniques, and are characterized by electron microscopy, UV–visible spectroscopy and Raman spectroscopy. Selective binding of the S-BPP molecules to the gold nanoparticles through Au–S bonds is found, with no evidence for the formation of N–Au bonds between the pyridine or pyrazole groups of BPP and the gold surface. Subtle, but significant shifts with temperature of specific Raman S-BPP modes are also observed. We attribute these to dynamic changes in the orientation and/or increased mobility of the molecules on the gold nanoparticle facets. As for their conductance, the temperature-dependence for S-BPP networks differs significantly from standard alkanethiol-capped networks, especially above 220 K. Relating the latter two observations, we propose that dynamic changes in the molecular layers effectively lower the molecular tunnel barrier for BPP-based arrays at higher temperatures. PMID:25383278

The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands.

PubMed

Devid, Edwin J; Martinho, Paulo N; Kamalakar, M Venkata; Prendergast, Úna; Kübel, Christian; Lemma, Tibebe; Dayen, Jean-François; Keyes, Tia E; Doudin, Bernard; Ruben, Mario; van der Molen, Sense Jan

2014-01-01

We prepare and investigate two-dimensional (2D) single-layer arrays and multilayered networks of gold nanoparticles derivatized with conjugated hetero-aromatic molecules, i.e., S-(4-{[2,6-bipyrazol-1-yl)pyrid-4-yl]ethynyl}phenyl)thiolate (herein S-BPP), as capping ligands. These structures are fabricated by a combination of self-assembly and microcontact printing techniques, and are characterized by electron microscopy, UV-visible spectroscopy and Raman spectroscopy. Selective binding of the S-BPP molecules to the gold nanoparticles through Au-S bonds is found, with no evidence for the formation of N-Au bonds between the pyridine or pyrazole groups of BPP and the gold surface. Subtle, but significant shifts with temperature of specific Raman S-BPP modes are also observed. We attribute these to dynamic changes in the orientation and/or increased mobility of the molecules on the gold nanoparticle facets. As for their conductance, the temperature-dependence for S-BPP networks differs significantly from standard alkanethiol-capped networks, especially above 220 K. Relating the latter two observations, we propose that dynamic changes in the molecular layers effectively lower the molecular tunnel barrier for BPP-based arrays at higher temperatures.

Direct electron transfer of glucose oxidase and biosensing for glucose based on PDDA-capped gold nanoparticle modified graphene/multi-walled carbon nanotubes electrode.

PubMed

Yu, Yanyan; Chen, Zuanguang; He, Sijing; Zhang, Beibei; Li, Xinchun; Yao, Meicun

2014-02-15

In this work, poly (diallyldimethylammonium chloride) (PDDA)-capped gold nanoparticles (AuNPs) functionalized graphene (G)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were fabricated. Based on the electrostatic attraction, the G/MWCNTs hybrid material can be decorated with AuNPs uniformly and densely. The new hierarchical nanostructure can provide a larger surface area and a more favorable microenvironment for electron transfer. The AuNPs/G/MWCNTs nanocomposite was used as a novel immobilization platform for glucose oxidase (GOD). Direct electron transfer (DET) was achieved between GOD and the electrode. Field emission scanning electron microscopy (FESEM), UV-vis spectroscopy and cyclic voltammetry (CV) were used to characterize the electrochemical biosensor. The glucose biosensor fabricated based on GOD electrode modified with AuNPs/G/MWCNTs demonstrated satisfactory analytical performance with high sensitivity (29.72mAM(-1)cm(-2)) and low limit of detection (4.8 µM). The heterogeneous electron transfer rate constant (ΚS) and the apparent Michaelis-Menten constant (Km) of GOD were calculated to be 11.18s(-1) and 2.09 mM, respectively. With satisfactory selectivity, reproducibility, and stability, the nanostructure we proposed offered an alternative for electrode fabricating and glucose biosensing. © 2013 Elsevier B.V. All rights reserved.

Enhancement of radiosensitivity of melanoma cells by pegylated gold nanoparticles under irradiation of megavoltage electrons.

PubMed

Mousavi, Mehdi; Nedaei, Hassan Ali; Khoei, Samideh; Eynali, Samira; Khoshgard, Karim; Robatjazi, Mostafa; Iraji Rad, Rasoul

2017-02-01

Gold nanoparticles (GNP) have significant potential as radiosensitizer agents due to their distinctive properties. Several studies have shown that the surface modification of nanoparticles with methyl polyethylene glycol (mPEG) can increase their biocompatibility. However, the present study investigated the radiosensitization effects of mPEG-coated GNP (mPEG-GNP) in B16F10 murine melanoma cells under irradiation of 6 MeV Electron beam. The synthesized GNP were characterized by UV-Visible spectroscopy, dynamic light scattering, transmission electron microscopy, and zeta potential. Enhancement of radiosensitization was evaluated by the clonogenic assay at different radiation doses of megavoltage electron beams. It was observed that mPEG-GNP with a hydrodynamic size of approximately 50 nm are almost spherical and cellular uptake occurred at all concentrations. Both proliferation efficiency and survival fraction decreased with increasing mPEG-GNP concentration. Furthermore, significant GNP sensitization occurred with a maximum dose enhancement factor of 1.22 at a concentration of 30 μM. Pegylated-GNP are taken up by B16F10 cancer cells and cause radiosensitization in the presence of 6 MeV electrons. The radiosensitization effects of GNP may probably be due to biological processes. Therefore, the underlying biological mechanisms beyond the physical dose enhancement need to be further clarified.

Proton Irradiation-Induced Metal Voids in Gallium Nitride High Electron Mobility Transistors

DTIC Science & Technology

2015-09-01

13. ABSTRACT (maximum 200 words) Gallium nitride/aluminum gallium nitride high electron mobility transistors with nickel/ gold (Ni/Au) and...platinum/ gold (Pt/Au) gating are irradiated with 2 MeV protons. Destructive physical analysis revealed material voids underneath the gate finger of the...nickel/ gold (Ni/Au) and platinum/ gold (Pt/Au) gating are irradiated with 2 MeV protons. Destructive physical analysis revealed material voids underneath

[Biosynthesis of gold nanoparticles by Azospirillum brasilense].

PubMed

Kupriashina, M A; Vetchinkina, E P; Burov, A M; Ponomareva, E G; Nikitina, V E

2014-01-01

Plant-associated nitrogen-fixing soil bacteria Azospirillum brasilense were shown to reduce the gold of chloroauric acid to elemental gold, resulting in formation of gold nanoparicles. Extracellular phenoloxidizing enzymes (laccases and Mn peroxidases) were shown to participate in reduction of Au+3 (HAuCl4) to Au(0). Transmission electron microscopy revealed accumulation of colloidal gold nanoparticles of diverse shape in the culture liquid of A. brasilense strains Sp245 and Sp7. The size of the electron-dense nanospheres was 5 to 50 nm, and the size of nanoprisms varied from 5 to 300 nm. The tentative mechanism responsible for formation of gold nanoparticles is discussed.

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.

Coordination-based gold nanoparticle layers.

PubMed

Wanunu, Meni; Popovitz-Biro, Ronit; Cohen, Hagai; Vaskevich, Alexander; Rubinstein, Israel

2005-06-29

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.

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

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

Rana, Aniket; Lochan, Abhiram; Chand, Suresh

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)more » 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.« less

Scanning EM of non-heavy metal stained biosamples: Large-field of view, high contrast and highly efficient immunolabeling

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

Kuipers, Jeroen; Boer, Pascal de; Giepmans, Ben N.G., E-mail: b.n.g.giepmans@umcg.nl

Scanning electron microscopy (SEM) is increasing its application in life sciences for electron density measurements of ultrathin sections. These are traditionally analyzed with transmission electron microscopy (TEM); by most labs, SEM analysis still is associated with surface imaging only. Here we report several advantages of SEM for thin sections over TEM, both for structural inspection, as well as analyzing immuno-targeted labels such as quantum dots (QDs) and gold, where we find that QD-labeling is ten times more efficient than gold-labeling. Furthermore, we find that omitting post-staining with uranyl and lead leads to QDs readily detectable over the ultrastructure, but undermore » these conditions ultrastructural contrast was even almost invisible in TEM examination. Importantly, imaging in SEM with STEM detection leads to both outstanding QDs and ultrastructural contrast. STEM imaging is superior over back-scattered electron imaging of these non-contrasted samples, whereas secondary electron detection cannot be used at all. We conclude that examination of ultrathin sections by SEM, which may be immunolabeled with QDs, will allow rapid and straightforward analysis of large fields with more efficient labeling than can be achieved with immunogold. The large fields of view routinely achieved with SEM, but not with TEM, allows straightforward raw data sharing using virtual microscopy, also known as nanotomy when this concerns EM data in the life sciences. - Highlights: • High resolution and large fields of view via nanotomy or virtual microscopy. • Highly relevant for EM‐datasets where information density is high. • Sample preparation with low contrast good for STEM, not TEM. • Quantum dots now stand out in STEM‐based detection. • 10 Times more efficient labeling with quantum dots compared to gold.« less

Why Gold and Copper Are Colored but Silver Is Not.

ERIC Educational Resources Information Center

Guerrero, Ariel H.; Fasoli, Hector J.; Costa, Jose Luis

1999-01-01

Explains why silver, which has the same external electronic configuration as copper and gold, does not appear yellow: white light reflects on most metals without color absorption or change to the naked eye; however, copper and gold appear yellow because they absorb "blue" and "red" photons during electron transitions between…

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.

Colloidal gold-modified optical fiber for chemical and biochemical sensing.

PubMed

Cheng, Shu-Fang; Chau, Lai-Kwan

2003-01-01

A novel class of fiber-optic evanescent-wave sensor was constructed on the basis of modification of the unclad portion of an optical fiber with self-assembled gold colloids. The optical properties and, hence, the attenuated total reflection spectrum of self-assembled gold colloids on the optical fiber changes with different refractive index of the environment near the colloidal gold surface. With sucrose solutions of increasing refractive index, the sensor response decreases linearly. The colloidal gold surface was also functionalized with glycine, succinic acid, or biotin to enhance the selectivity of the sensor. Results show that the sensor response decreases linearly with increasing concentration of each analyte. When the colloidal gold surface was functionalized with biotin, the detection limit of the sensor for streptavidin was 9.8 x 10(-11) M. Using this approach, we demonstrate proof-of-concept of a class of refractive index sensor that is sensitive to the refractive index of the environment near the colloidal gold surface and, hence, is suitable for label-free detection of molecular or biomolecular binding at the surface of gold colloids.

Plasmonic gold nanoparticles modified titania nanotubes for antibacterial application

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

Li, Jinhua; Zhou, Huaijuan; Qian, Shi

Close-packed TiO{sub 2} nanotube arrays are prepared on metallic Ti surface by electrochemical anodization. Subsequently, by magnetron sputtering, Au nanoparticles are coated onto the top sidewall and tube inwall. The Au@TiO{sub 2} systems can effectively kill Staphylococcus aureus and Escherichia coli in darkness due to the existence of Au nanoparticles. On the basis of classical optical theories, the antibacterial mechanism is proposed from the perspective of localized surface plasmon resonance. Respiratory electrons of bacterial membrane transfer to Au nanoparticles and then to TiO{sub 2}, which makes bacteria steadily lose electrons until death. This work provides insights for the better understandingmore » and designing of noble metal nanoparticles-based plasmonic heterostructures for antibacterial application.« less

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

Yang, Li; Zhu, Zihua; Yu, Xiao-Ying

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 membranemore » 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.« less

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.

Polarization-selective infrared bandpass filter based on a two-layer subwavelength metallic grating

NASA Astrophysics Data System (ADS)

Hohne, Andrew J.; Moon, Benjamin; Baumbauer, Carol L.; Gray, Tristan; Dilts, James; Shaw, Joseph A.; Dickensheets, David L.; Nakagawa, Wataru

2017-08-01

We present the design, fabrication, and characterization of a polarization-selective infrared bandpass filter based on a two-layer subwavelength metallic grating for use in polarimetric imaging. Gold nanowires were deposited via physical vapor deposition (PVD) onto a silicon surface relief grating that was patterned using electron beam lithography (EBL) and fabricated using standard silicon processing techniques. Optical characterization with a broad-spectrum tungsten halogen light source and a grating spectrometer showed normalized peak TM transmission of 53% with a full-width at half-maximum (FWHM) of 122 nm, which was consistent with rigorous coupled-wave analysis (RCWA) simulations. Simulation results suggested that device operation relied on suppression of the TM transmission caused by surface plasmon polariton (SPP) excitation at the gold-silicon interface and an increase in TM transmission caused by a Fabry-Perot (FP) resonance in the cavity between the gratings. TE rejection occurred at the initial air/gold interface. We also present simulation results of an improved design based on a two-dielectric grating where two different SPP resonances allowed us to improve the shape of the passband by suppressing the side lobes. This newer design resulted in improved side-band performance and increased peak TM transmission.